THE QUANTUM

IN CHEMISTRY:
An Experimentalists View
Roger rinter
School of Chemical Sciences and Pharmacy
University of East Anglia
THE QUANTUM
IN CHEMISTRY:
An Experimentalists View
THE QUANTUM
IN CHEMISTRY:
An Experimentalists View
Roger rinter
School of Chemical Sciences and Pharmacy
University of East Anglia
Copyright 2005 John Wiley & Sons Ltd, The Atrium, Southern Gate, Chichester,
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Library of Congress Cataloging-in-Publication Data:
Grinter, :oger7
The 0uantum in chemistry 1 an eperimentalistGs /ie6 H :oger Grinter7
p7 cm7
Ancludes 3i3liographical re.erences and inde7
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#7 &uantum chemistry7 27 Spectrum analysis7 ,7 &uantum measure theory7
A7 Title7
&<*?27 G-5 2005
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A catalogue record .or this 3oo4 is a/aila3le .rom the British Li3rary
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Contents
!re"a#e . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . iii
C$apter % The :ole o. Theory in the !hysical Sciences . . . . . . . . . . . . . . . #
#70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #
#7# What is the role o. theory in scienceJ . . . . . . . . . . . . . . . . . . . . . . . . . . #
#72 The gas la6s o. Boyle and Gay2Lussac . . . . . . . . . . . . . . . . . . . . . . . . . ,
#7, An a3solute Kero o. temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *
#7* The gas e0uation o. 8an der Waals . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
#75 !hysical la6s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
#7? La6s, postulates, hypotheses, etc7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?
#7- Theory at the end o. the #$th century . . . . . . . . . . . . . . . . . . . . . . . . . . -
#7% Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %
C$apter & Drom Classical to &uantum Cechanics . . . . . . . . . . . . . . . . . . . . $
270 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $
27# The motion o. the planets1 Tycho Brahe and >epler . . . . . . . . . . . . . . . #0
272 ;e6ton, Lagrange and 9amilton . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##
27, The po6er o. classical mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2
27* The .ailure o. classical physics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2
275 The 3lac423ody radiator and !lanc4Gs 0uantum hypothesis . . . . . . . . . . . #,
2757# !lanc4Gs solution to the 3lac423ody radiation pro3lem . . . . . . . . #5
27572 A 0ualitati/e interpretation o. the .orm o. the 3lac423ody
emission cur/e in the light o. !lanc4Gs hypothesis . . . . . . . . . . #?
2757, &uantisation in classical mechanics . . . . . . . . . . . . . . . . . . . . . #%
27? The photoelectric e..ect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
27?7# 'insteinGs theory o. the photoelectric e..ect conLrmed
eperimentally . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
27- The emission spectra o. atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2,
27-7# BohrGs theory o. the structure o. the hydrogen atom . . . . . . . . . 2*
27-72 Comparison o. BohrGs model 6ith eperiment . . . . . . . . . . . . . 2?
27-7, Durther de/elopment o. BohrGs theory . . . . . . . . . . . . . . . . . . . 2?
27% de BroglieGs proposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?
27$ The SchroM dinger e0uation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2%
27$7# 'igen.unctions and eigen/alues . . . . . . . . . . . . . . . . . . . . . . . . 2$
/i Contents
27#0 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0
!ro3lems .or Chapter 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*
C$apter ' The Application o. &uantum Cechanics . . . . . . . . . . . . . . . . . . . ,-
,70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,%
,7# "3ser/a3les, operators, eigen.unctions and eigen/alues . . . . . . . . . . . . . ,%
,72 The SchroM dinger method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,$
,7, An electron on a ring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *0
,7,7# The 9amiltonian operator .or the electron on a ring . . . . . . . . . *0
,7,72 Solution o. the SchroM dinger e0uation . . . . . . . . . . . . . . . . . . . . *#
,7,7, The accepta3le eigen.unctions . . . . . . . . . . . . . . . . . . . . . . . . . *#
,7* 9uM c4elGs (*N
+
2+ rule1 aromaticity . . . . . . . . . . . . . . . . . . . . . . . . . . . **
,75 ;ormalisation and orthogonality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *?
,7? An electron in a linear 3o . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *?
,7?7# The 9amiltonian operator .or an electron in a linear 3o . . . . . *?
,7?72 The accepta3le eigen.unctions . . . . . . . . . . . . . . . . . . . . . . . . . *-
,7?7, Boundary conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *%
,7- The linear and angular momenta o. electrons conLned 6ithin a
one2dimensional 3o or on a ring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *%
,7-7# The linear momentum o. an electron in a 3o . . . . . . . . . . . . . . *$
,7-72 The angular momentum o. an electron on a ring . . . . . . . . . . . . 50
,7% The eigen.unctions o. di..erent operators . . . . . . . . . . . . . . . . . . . . . . . . 52
,7$ 'igen.unctions, eigen/alues and eperimental measurements . . . . . . . . . 5,
,7#0 Core a3out measurement1 the 9eisen3erg uncertainty principle . . . . . . . 55
,7## The commutation o. operators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-
,7#2 Com3inations o. eigen.unctions and the superposition o. states . . . . . . . 5%
,7#, "perators and their .ormulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5$
,7#,7# !osition or co2ordinate, x . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5$
,7#,72 !otential energy, V

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5$
,7#,7, Linear momentum, p

x
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#,7* >inetic energy, W

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#,75 Angular momentum, L

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#* Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#5 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?#
!ro3lems .or Chapter , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -#
C$apter ( Angular Comentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -,
*70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -,
*7# Angular momentum in classical mechanics . . . . . . . . . . . . . . . . . . . . . . -,
*72 The conser/ation o. angular momentum . . . . . . . . . . . . . . . . . . . . . . . . -5
Contents /ii
*7, Angular momentum as a /ector 0uantity . . . . . . . . . . . . . . . . . . . . . . . . -5
*7* "r3ital angular momentum in 0uantum mechanics . . . . . . . . . . . . . . . . . -?
*7*7# The /ector model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . --
*75 Spin angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -%
*7? Total angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -%
*7?7# The addition and conser/ation o. angular momentum in
0uantum mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -$
*7?72 The la6s o. 0uantum2mechanical angular momentum . . . . . . . . %#
*7- Angular momentum operators and eigen.unctions . . . . . . . . . . . . . . . . . %2
*7-7# The raising and lo6ering, shi.t or ladder operators . . . . . . . . . . %2
*7% ;otation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %,
*7$ Some eamples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %*
*7#0 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %?
!ro3lems .or Chapter * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $,
C$apter ) The Structure and Spectroscopy o. the Atom . . . . . . . . . . . . . . . $5
570 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $?
57# The eigen/alues o. the hydrogen atom . . . . . . . . . . . . . . . . . . . . . . . . . $?
572 The 6a/e .unctions o. the hydrogen atom . . . . . . . . . . . . . . . . . . . . . . . $-
5727# The radial .unction, R
nl
!r " . . . . . . . . . . . . . . . . . . . . . . . . . . . $%
57272 The angular .unctions,
lm
!# " and
m
!$" . . . . . . . . . . . . . . . . $$
57, !olar diagrams o. the angular .unctions . . . . . . . . . . . . . . . . . . . . . . . . #00
57,7# The s2.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0#
57,72 The %2.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0#
57,7, The d 2.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0,
57* The complete or3ital 6a/e .unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . #0*
575 "ther one2electron atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0*
57? 'lectron spin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #05
57- Atoms and ions 6ith more than one electron . . . . . . . . . . . . . . . . . . . . . #05
57-7# The sel.2consistent Leld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0?
57-72 'lectron correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0?
57-7, The periodic ta3le o. the elements . . . . . . . . . . . . . . . . . . . . . . #0-
57% The electronic states o. the atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0-
57%7# The L/e 0uantum num3ers o. a single electron . . . . . . . . . . . . . #0%
57%72 &uantum num3ers .or the many2electron atom . . . . . . . . . . . . . #0%
57%7, The assignment o. term sym3ols . . . . . . . . . . . . . . . . . . . . . . . #0%
57%7* Term energies and 9undGs rules . . . . . . . . . . . . . . . . . . . . . . . . ##0
57$ Spin2or3it coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ###
57$7# :ussell I Saunders or LS coupling . . . . . . . . . . . . . . . . . . . . . . ###
57$72 && coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##2
57$7, Antermediate coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##,
57$7* Anter2electronic spin2or3it coupling . . . . . . . . . . . . . . . . . . . . . . ##5
57#0 Selection rules in atomic spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . ##5
57#07# Angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##5
57#072 !arity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##?
/iii Contents
57## The Neeman e..ect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##-
57##7# The normal Neeman e..ect . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##%
57##72 The anomalous Neeman e..ect . . . . . . . . . . . . . . . . . . . . . . . . . #20
57#2 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2#
!ro3lems .or Chapter 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2$
C$apter * The Co/alent Chemical Bond . . . . . . . . . . . . . . . . . . . . . . . . . . . #,#
?70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #,2
?7# The 3inding energy o. the hydrogen molecule . . . . . . . . . . . . . . . . . . . . #,,
?72 The 9amiltonian operator .or the hydrogen molecule . . . . . . . . . . . . . . . #,*
?7, The Born I "ppenheimer approimation . . . . . . . . . . . . . . . . . . . . . . . . . #,?
?7* 9eitler and London1 The /alence 3ond (8B+ model . . . . . . . . . . . . . . . . #,-
?75 9und and Culli4en1 the molecular or3ital (C"+ model . . . . . . . . . . . . . #,$
?7? Ampro/ing the 6a/e .unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*0
?7?7# The /alue o. N . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*0
?7?72 !olarisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*0
?7- =niLcation1 Aonic structures and conLguration interaction . . . . . . . . . . . #*#
?7% 'lectron correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*,
?7$ Bonding and anti3onding C"s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*5
?7#0 Why is there no 9e I 9e BondJ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*?
?7## Atomic or3ital o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*?
?7##7# ' (sigma+ o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*-
?7##72 ( (pi+ o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*-
?7##7, ) (delta+ o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*%
?7##7* ;on23onding o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*%
?7#2 The 9omonuclear diatomic molecules .rom lithium to Ouorine . . . . . . . #*$
?7#, 9eteronuclear diatomic molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #5#
?7#* Charge distri3ution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #5,
?7#5 9y3ridisation and resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #5,
?7#57# 9y3ridisation1 !auling #$,# . . . . . . . . . . . . . . . . . . . . . . . . . . . #5,
?7#572 9y3ridisation and the /alence 3ond theory . . . . . . . . . . . . . . . . #5?
?7#57, 9y3ridisation o. car3on A"s . . . . . . . . . . . . . . . . . . . . . . . . . . #5?
?7#57* The choice o. hy3rid or3itals . . . . . . . . . . . . . . . . . . . . . . . . . . #?#
?7#575 The properties o. hy3rid2or3ital 3onds . . . . . . . . . . . . . . . . . . . #?2
?7#? :esonance and the /alence 3ond theory . . . . . . . . . . . . . . . . . . . . . . . . #?,
?7#- Colecular geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #?,
?7#-7# The /alence2shell electron2pair repulsion (8S'!:+ model . . . . . #?*
?7#-72 The 8S'!: model and multiple 3onds . . . . . . . . . . . . . . . . . . . #?5
?7#% Computational de/elopments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #?-
?7#$ Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #?%
!ro3lems .or Chapter ? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #-?
C$apter + Bonding, Spectroscopy and Cagnetism in Transition2Cetal
Complees . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%#
-70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%#
Contents i
-7# 9istorical de/elopment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%2
-72 The crystal Leld theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%2
-7, The electronic energy le/els o. transition2metal complees . . . . . . . . . .
-7,7# The 6ea42Leld scheme .or d
2
(eample o.
,
D in an octahedral
#%-
Leld+ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%$
-7,72 The 6ea42Leld scheme .or d
2
(inclusion o.
,
!+ . . . . . . . . . . . . .
-7,7, The d
2
energy le/els .or 6ea4, strong and intermediate
#$0
octahedral Lelds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #$#
-7,7* The strong2Leld scheme .or d
2
in an octahedral Leld . . . . . . . . #$,
-7,75 Spin2or3it coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #$5
-7* The electronic spectroscopy o. transition2metal complees . . . . . . . . . . . #$?
-75 !airing energiesP lo62spin and high2spin complees . . . . . . . . . . . . . . . . #$-
-7? The magnetism o. transition2metal complees . . . . . . . . . . . . . . . . . . . . #$-
-7- Co/alency and the ligand Leld theory . . . . . . . . . . . . . . . . . . . . . . . . . . #$$
-7% Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20,
!ro3lems .or Chapter - . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#2
C$apter , Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#5
%70 The interaction o. radiation 6ith matter . . . . . . . . . . . . . . . . . . . . . . . . 2#?
%7# 'lectromagnetic radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#?
%7#7# The electric Leld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#-
%7#72 The magnetic Leld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#$
%72 !olarised light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#$
%727# Linearly polarised light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
%7272 Circularly polarised light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22#
%7, The electromagnetic spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
%7,7# Three .orms o. electromagnetic radiation . . . . . . . . . . . . . . . . . 222
%7* !hotons and their properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22,
%7*7# 8elocity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22,
%7*72 'nergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22*
%7*7, Cass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22*
%7*7* Linear momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22*
%7*75 Angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
%7*7? !arity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
%75 Selection rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
%757# The Bohr I 'instein condition . . . . . . . . . . . . . . . . . . . . . . . . . . 22?
%7? The 0uantum mechanics o. transition pro3a3ility . . . . . . . . . . . . . . . . . . 22-
%7- The nature o. the time2independent interaction $
.
|V

! y K"|$
i
. . . . . . 2,,
%7-7# The transition dipole moment . . . . . . . . . . . . . . . . . . . . . . . . . . 2,*
%7-72 The relati/e intensities o. =8 I 8AS, A: and ;C: transitions . . 2,%
%7-7, The particle and 6a/e /ie6s o. spectroscopic transitions . . . . . 2*2
%7% Spectroscopic time scales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2*5
%7$ &uantum electrodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2*-
%7#0 Spectroscopic units and notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2*-
%7#07# The energyH.re0uencyH6a/elength ais . . . . . . . . . . . . . . . . . . . 2*%
%7#072 The intensityHa3sor3ance ais . . . . . . . . . . . . . . . . . . . . . . . . . . 2*$
Contents
%7## The 'instein coe.Lcients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
%7#2 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
!ro3lems .or Chapter % . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25$
C$apter - ;uclear Cagnetic :esonance Spectroscopy . . . . . . . . . . . . . . . . . 2?#
$70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?#
$7# The magnetic properties o. atomic nuclei . . . . . . . . . . . . . . . . . . . . . . . 2?2
$72 The .re0uency region o. ;C: spectroscopy . . . . . . . . . . . . . . . . . . . . . 2?*
$7, The ;C: selection rule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?*
$7* The chemical shi.t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?-
$7*7# The delta ()+ scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?%
$7*72 The shielding constant, ' (sigma+ . . . . . . . . . . . . . . . . . . . . . . 2-0
$75 ;uclear spin I spin coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-0
$7? The energy le/els o. a nuclear spin system . . . . . . . . . . . . . . . . . . . . . . 2-,
$7?7# Dirst order spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-*
$7?72 Second order spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-5
$7- The intensities o. ;C: spectral lines . . . . . . . . . . . . . . . . . . . . . . . . . . 2-?
$7% &uantum mechanics and ;C: spectroscopy . . . . . . . . . . . . . . . . . . . . . 2--
$7$ Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-%
!ro3lems .or Chapter $ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2%-
C$apter %. An.rared Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2%$
#070 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2%$
#07# The origin o. the in.rared spectra o. molecules . . . . . . . . . . . . . . . . . . . 2$0
#072 Simple harmonic motion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2$0
#07, The 0uantum2mechanical harmonic oscillator . . . . . . . . . . . . . . . . . . . . 2$,
#07,7# &uantisation o. the energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2$,
#07,72 Nero2point energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2$*
#07,7, 8i3rational eigen.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2$*
#07* :otation o. a diatomic molecule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2$*
#07*7# 'igen.unctions o. the rigid rotator . . . . . . . . . . . . . . . . . . . . . . 2$-
#075 Selection rules .or /i3rational and rotational transitions . . . . . . . . . . . . . 2$-
#0757# A semi2classical /ie6 o. the selection rules . . . . . . . . . . . . . . . ,0#
#07572 An.rared intensities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0#
#07? :eal diatomic molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,02
#07- !olyatomic molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
#07-7# ;ormal co2ordinates, normal /i3rations, /i3rational
,0,
eigen.unctions and eigen/alues . . . . . . . . . . . . . . . . . . . . . . . . ,0,
#07-72 8i3rations o. real polyatomic molecules . . . . . . . . . . . . . . . . . . ,05
#07-7, Characteristic group .re0uencies . . . . . . . . . . . . . . . . . . . . . . . . ,0%
#07-7* Large molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0%
#07% Anharmonicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0$
#07%7# Dermi resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0$
#07%72 8i3rational angular momentum and the Coriolis interaction . . . . ,##
#07$ The a*+initio calculation o. A: spectra . . . . . . . . . . . . . . . . . . . . . . . . . ,#?
##757, The t6o2electron, i7e7 electron2repulsion, energyP operator #,r
#2
,,?
##757* The total energies o. singlet and triplet state . . . . . . . . . . . . . . . ,,%
##7575 'lectron repulsion in the triplet and singlet states o. the ecited
helium atom1 a diagrammatic illustration . . . . . . . . . . . . . . . . . ,,$
##757? Summary o. Section ##75 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*#
##7? The ( 2electron spectrum o. 3enKene . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*#
##7- Selection rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,**
##7-7# 'lectron spin (multiplicity+ and transition pro3a3ility . . . . . . . . ,**
##7-72 Spatial aspects o. transition pro3a3ility .or an allo6ed electronic
transition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*?
##7-7, The /i3rational .actor in the transition pro3a3ility . . . . . . . . . . . ,*-
##7% Slater determinants (Appendi ?+ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*%
##7$ Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*%
!ro3lems .or Chapter ## . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*%
Contents i
#07#0 The special case o. near in.rared spectroscopy . . . . . . . . . . . . . . . . . . . ,#-
#07## Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,#-
!ro3lems .or Chapter #0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2*
C$apter %% 'lectronic Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2-
##70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2-
##7# Atomic and molecular or3itals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2%
##72 The spectra o. co/alent molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2$
##727# (

(

transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2$
##7272 n

(

transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,,0
##727, Transition2metal complees . . . . . . . . . . . . . . . . . . . . . . . . . . . ,,0
##7, Charge trans.er (CT+ spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,,0
##7* Cany2electron 6a/e .unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,,2
##75 The #s
#
2s
#
conLguration o. the helium atomP singlet and triplet states . . ,,,
##757# The energies o. the #s 2s ecited states o. the helium atom . ,,5
##7572 The one2electron energiesP operator
# 2

2

#
# 2

2

2
2,r
#
2,r
2
. . . . . . . . . . . . . . . . . . . . . . . . . ,,5
C$apter %& Some Special Topics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,5#
#270 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,52
#27# The 9uM c4el molecular or3ital (9C"+ theory . . . . . . . . . . . . . . . . . . . . . ,52
#27#7# The 3asis o. 9uM c4elGs approach . . . . . . . . . . . . . . . . . . . . . . . . ,52
#27#72 The method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,5,
#27#7, 9uM c4elGs assumptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,5*
#27#7* <etermination o. 9C" energies and A" coe.Lcients . . . . . . . . ,5*
#27#75 Applications o. 9C" energies . . . . . . . . . . . . . . . . . . . . . . . . . ,5-
#27#7? Applications o. 9C" coe.Lcients . . . . . . . . . . . . . . . . . . . . . . ,?#
#27#7- Some Lnal comments on the 9uM c4el theory . . . . . . . . . . . . . . . ,?2
#272 Cagnetism in chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,?,
#2727# Cagnetic suscepti3ility1 diamagnetism and paramagnetism . . . . ,?*
ii Contents
#27272 Cagnetic suscepti3ility1 .erromagnetism and anti.erromagnetism ,?5
#2727, Cagnetic Lelds and dipoles1 some deLnitions . . . . . . . . . . . . . . ,?5
#2727* The magnetic e..ect o. electronic or3ital motion . . . . . . . . . . . . ,??
#27275 The conse0uences o. chemical 3onding . . . . . . . . . . . . . . . . . . ,?%
#2727? The magnetic e..ect o. electron spin . . . . . . . . . . . . . . . . . . . . . ,?$
#2727- Cagnetism in practice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,-0
#2727% Systems o. interacting molecular magnets . . . . . . . . . . . . . . . . . ,-*
#2727$ A note o. 6arning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,-?
#2727#0 An application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,--
#27, The 3and theory o. solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,-%
#27,7# The tight 3inding approimation . . . . . . . . . . . . . . . . . . . . . . . ,-%
#27,72 The electron I gas (.ree2electron+ approimation . . . . . . . . . . . . ,%#
#27,7, Colecular and ionic solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,%?
#27,7* Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,%-
#27,75 Cetals, insulators and semiconductors . . . . . . . . . . . . . . . . . . . ,%-
#27,7? "ptical properties o. solids . . . . . . . . . . . . . . . . . . . . . . . . . . . ,$0
#27,7- Cechanical properties o. solids . . . . . . . . . . . . . . . . . . . . . . . . ,$0
#27* Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,$0
!ro3lems .or Chapter #2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,$-
Appen/i#es . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
% Dundamental Constants and Atomic =nits . . . . . . . . . . . . . . . . . . . . . . . . . *0#
& The 8ariation Cethod and the Secular '0uations . . . . . . . . . . . . . . . . . . . . *0,
' 'nergies and Wa/e Dunctions 3y Catri <iagonalisation . . . . . . . . . . . . . . *##
( !ertur3ation Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *#-
) The Spherical 9armonics and 9ydrogen Atom Wa/e Dunctions . . . . . . . . . *25
* Slater <eterminants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *2$
+ Spherical !olar Co2ordinates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *,#
, ;um3ers1 :eal, Amaginary and Comple . . . . . . . . . . . . . . . . . . . . . . . . . . *,,
- <ipole and Transition <ipole Coments . . . . . . . . . . . . . . . . . . . . . . . . . . . *,5
%. Wa/e Dunctions .or the
,
D States o. d
2
using Shi.t "perators . . . . . . . . . . . *,$
In/ex . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . **,
!re"a#e
An his prologue to Q-he .o+/et0eenG L7!7 9artley 6rote1 Q-he %ast is a foreign co1ntry2
they do things differently there7G 9e might ha/e 3een descri3ing 0uantum mechanics,
6hich goes some 6ay to eplaining 6hy it is normally only the deniKens o. that strange
land, the theoreticians, 6ho dare to enter into print a3out it7 So 6hat is a sel.2con.essed
eperimentalist doing thereJ
". the many .actors that ha/e inOuenced the de/elopment o. chemistry in the second
hal. o. the 20th century, none has 3een more important than the ineora3le di..usion across
the traditional su3@ect 3oundaries o. concepts, 6hich ha/e their origins in theoretical
physics7 Students o. chemistry and research scientists ali4e, not only in chemistry, are
under continual pressure to assimilate and apply these ideasP 0uantum mechanics .orms
a central part o. many o. them7 But the learning is hard, and although there are many
ecellent 3oo4s they tend to 3e 6ritten 3y authors 6ho are 3y nature theoreticians and
6hose approach to the su3@ect di..ers .rom that o. the eperimentalist in many 6ays7 A
4no6, 3ecause A ha/e 3een in this position all my 6or4ing li.e7
Cy original moti/ation, 6hich has not changed 6ith the years, 6as to interpret mysel.,
in as eact a 6ay as A 6as a3le, the eperimental o3ser/ations that A as a spectroscopist
6as ma4ing7 An the course o. my studies A spent a lot o. time 6ith most o. the classic tets
on the su3@ect 6hich are directed at chemists and some intended .or physicists7 Those in
the 'nglish language that is7 9o6e/er, as ecellent as they mostly are, t6o aspects o. them
o.ten .ailed to satis.y me7 Dirstly, their authors are /ery good mathematicians and do not
al6ays ma4e allo6ances .or the lesser eperience and a3ility in those realms o. people li4e
me7 This also has the un.ortunate side e..ect o. encouraging students at all le/els to 3elie/e
that their di.Lculties are attri3uta3le to a lac4 o. mathematical epertise 6hen they are, in
.act, more commonly due to a .ailure to grasp some essential 0uantum2mechanical concept7
An my eperience, once the concept has 3een grasped, the mathematical epression o. it
is much easier to understand7 Secondly, epositions o. 0uantum mechanics .re0uently
lac4 eamples o. chemical applications7 A am o. the /ie6 that a real eample, e/en 6hen
it is much simpliLed and gi/es a result 6hich does not agree 6ell 6ith eperiment, is
al6ays 3etter than no eample at all7 The tets 6hich do contain eamples are usually
those directed at a particular 3ranch o. eperimental measurement, a particular 3ranch o.
spectroscopy .or eample, and they, naturally, cannot concern themsel/es 6ith a 3roader
/ie6 o. the 0uantum mechanics 6hich they apply7 An this 3oo4 A ha/e tried to 3ring
the 3asic 0uantum2mechanical theory closer to real chemical eamples and to ma4e the
ine/ita3le mathematics in/ol/ed su3ordinate to the understanding o. the principles7
A o6e a great deal to many .riends 6ith 6hom A ha/e 6or4ed7 Cy interest in the
interpretation o. physical I chemical measurements 6as Lrst aroused 3y Stephen Cason
and continued 3y 'dgar 9eil3ronner7 When A arri/ed at the =ni/ersity o. 'ast Anglia
i/ !re.ace
(='A+ A had the great good .ortune o. entering into a period o. colla3orati/e research
6ith Andre6 Thomson 6ho 6as as determined as A to learn some 0uantum mechanics7
Together 6ith some ecellent post2doctoral .ello6s and graduate students, 6e spent many
a lunch hour che6ing literally on our pac4ed lunches and Lgurati/ely on the theory
o. groups, ligand Lelds, angular momentum, irreduci3le tensors etc7 This 6as .or me a
learning eperience li4e no other and A am in de3t to all 6ho too4 part in the struggleP
especially to Andre67
Then, as this 3oo4 3egan to gro6, A 6as most grate.ul to ;orman Sheppard 6hen
he epressed an interest in reading se/eral o. the early chapters and commenting on
them 6ith his usual, meticulous care7 A ha/e also 3eneLted .rom discussions o. particular
pro3lems 6ith many other colleagues here at ='A7 !ositi/e and encouraging suggestions
made 3y re/ie6ers o. sample chapters 6ere also much appreciated and A ha/e tried to
ta4e account o. them7
An spite o. the help A ha/e recei/ed, it is too much to hope that no errors andHor
misconceptions remain and A 6ould li4e to epand a little on that su3@ect7 ;o error in a
3oo4 .rom 6hich a reader is trying to learn something can 3e tri/ialP e/en typographical
errors can seriously mislead a student 6ho is insecure in hisHher 4no6ledge o. the su3@ect7
:eaders 6ill surely detect such errors and A 6ould 3e most grate.ul i. they 6ould in.orm
me o. them7 But misconceptions are an altogether more serious pro3lem and in this
connection A ma4e a special appeal7 An attempting to ma4e 0uantum mechanics more
approacha3le A ha/e not hesitated to simpli.y and to dra6 on classical analogies 6here/er
possi3le7 An so doing A .ear that A may ha/e /entured out on a num3er o. lim3s too 6ea4
to support the 6eight 6hich A ha/e placed upon them7 A hope that readers 6ho detect this
type o. pro3lem or 6ho .eel uneasy a3out statements 6hich A ha/e made 6ill 3e good
enough to point their concerns out to me7
A Lnal 6ord o. than4s must go to .our people7 To my parents 6ho, though they
themsel/es had only elementary educations, did e/erything they could to .urther mine7
And to my 6i.e, Charlotte, and daughter, :e3ecca, 6ho ha/e gi/en me so much support
and encouragement in my scientiLc endea/ours7 A trust that they 6ill .eel that this 3oo4
6as a 6orth6hile enterprise7
A also 6ish to than4 A/an :od6ell .or pro/ision o. the three cartoons in this 3oo47
Roger .rinter
http1HH6667grinter7o rgH0uantum7htmlH
Chapter #
T$e Role o" T$eor0
in t$e !$0si#al S#ien#es
#70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #
#7# What is the role o. theory in scienceJ . . . . . . . . . . . . . . . . . . . . . . . . . . #
#72 The gas la6s o. Boyle and Gay2Lussac . . . . . . . . . . . . . . . . . . . . . . . . . ,
#7, An a3solute Kero o. temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *
#7* The gas e0uation o. 8an der Waals . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
#75 !hysical la6s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
#7? La6s, postulates, hypotheses, etc7 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?
#7- Theory at the end o. the #$th century . . . . . . . . . . . . . . . . . . . . . . . . . . -
#7% Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %
%1. INTR23UCTI2N
An this chapter 6e shall consider the role o. theory in science and en0uire 6hat is meant
6hen 6e spea4 o. a Qla6G in the physical sciences7 We shall as41 6hat are these la6s, ho6
do they arise and 6hat is their /alue or purpose 6ithin scienceJ There are t6o reasons
.or approaching the su3@ect o. the 0uantum in chemistry in this 6ay7 Dirstly, these are
0uestions o. interest in their o6n right to 6hich, in my /ie6, insu.Lcient attention is
paid in the teaching o. science7 This can result in a degree o. con.usion, especially in a
su3@ect as inherently comple as 0uantum theory, 6here ne6comers to the su3@ect are apt
to thin4 that i. only they 4ne6 more mathematics they could deri/e results 6hich, in .act,
cannot 3e and ne/er 6ere deri/ed7 This leads to an undesira3le .ocus o. attention upon
the mathematical rather than the conceptual aspects o. the pro3lem7 Thus, the second
reason .or discussing scientiLc la6s is an attempt to place the la6s o. 0uantum theory
in a perspecti/e in 6hich their origin, /alue and meaning can 3e 3etter appreciated 3y
3eginners in the Leld7
%1% 4HAT IS THE R25E 26 THE2RY IN SCIENCE7
At is a matter o. historical .act that man has 3een o3ser/ing the natural 6orld, and recording
his o3ser/ations, since ancient times7 We may sa.ely conclude that the /er3al communi2
cation o. o3ser/ation is e/en older, as the times and routes o. migrating animals, 3irds
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
2 The :ole o. Theory in the !hysical Sciences
and Lsh are o. crucial importance to people 6ho li/e 3y hunting, 6hile a 4no6ledge o.
the seasons, o. rain.all etc7 is essential to .ood gatherers7
#
The importance o. these and
other natural phenomena made those 6hose 4no6ledge o. them 6as most etensi/e the
leaders o. their communities and eceptional status 6as accorded to those 6ho had, or
6ere 3elie/ed to ha/e, the a3ility to predict such e/ents7
9istorically, prediction has 3een attempted either through an appeal to the supernatural
or 3y means o. a reasoned etrapolation o. .acts already 4no6n7 These t6o approaches to
the same pro3lem are not as di..erent as they might appear7 A. an o3ser/ed .act, the annual
Oooding o. a ri/er .or eample, is 3elie/ed to 3e under the direct and immediate control
o. the gods, then it is 0uite rational to consult those gods a3out such e/ents7 ;or does
the in/ol/ement o. the supernatural necessarily conOict 6ith the ma4ing and recording o.
o3ser/ations7 At has 3een suggested that a preoccupation 6ith astrology may 6ell account
.or the .act that the Cesopotamians o. the Lrst millennium BC ecelled in astronomy7
2
Thus, the ancient .ascination 6ith the prediction o. the .uture led not only to the use o.
rite and ritual 3ut also to the recording and ordering o. o3ser/ations, a tendency 6hich
also recei/ed support .rom the 6idespread 3elie. that there must 3e a system or order
in the uni/erse7 The challenge o. Lnding this system, and o. demonstrating that one has
.ound it 3y predicting the results o. o3ser/ations yet to 3e made, is the dri/ing .orce o.
science and necessitates not only the collection o. data 3ut also the arrangement o. that
data 6ithin some conceptual .rame6or4 that ma4es it easier to remem3er, understand
and use7
We can distinguish t6o 3road categories o. such conceptual .rame6or4s, or models7
The Lrst comprises models o. an essentially descripti/e nature in 6hich the phenomenon
in 0uestion is li4ened to o3@ects o. our e/eryday eperience7 An eample o. this type
o. model 6ould 3e the description o. the .undamental constituents o. matter gi/en 3y
Lucretius, a :oman o. the Lrst century BC7 An his /ie6, all su3stances 6ere composed o.
indestructi3le atoms and . . . QThings that seem to us to 3e hard and sti.. must 3e composed
o. deeply indented and hoo4ed atoms held Lrmly 3y their intertangling 3ranches7 . . .
Li0uids, on the other hand, must o6e their Ouid consistency to component atoms that are
hard and round, .or poppy seed can 3e poured as easily as i. it 6ere 6ater . . . 7G
,
The
molecular models used 3y modern chemists .all into this categoryP atoms are represented
3y coloured spheres and 3onds 3y metal rods7
The second category o. model is the mathematical model in 6hich natural phenomena
are represented 3y a set o. sym3ols, the meanings o. 6hich ha/e 3een deLned, and 6hich
o3ey some particular rules o. mathematical manipulation7 A di..erential e0uation, .or
eample, may 3e used to model a chemical reaction 3y pro/iding a description o. the
rates o. change 6ith time o. the concentrations o. the reagents in/ol/ed in the reaction7 At
is this 4ind o. model to 6hich 6e re.er 6hen 6e spea4 o. the theoretical structure o. the
natural sciences7 At is the type o. model 6hich is most use.ul to us 6hen 6e are comparing
numerical eperimental data 6ith theoretical predictions, i7e7 in 0uantitati/e 6or47
A theoretical structure is essential to all the natural sciences7 At pro/ides the .rame6or4
into 6hich the pieces o. the @igsa6 o. eperimental data are Ltted, thus re/ealing their
inter2relationships and eposing gaps in our 4no6ledge 6hich need to 3e Llled 6ith the
results o. ne6 eperiments7 An Llling these gaps theory plays a leading roleP it not only
sho6s 6here ne6 measurements are re0uired 3ut also tells the eperimentalist 6hat to
epect 6hen the eperiments in 0uestion are per.ormed7 This is /ery important since,
The Gas La6s o. Boyle and Gay2Lussac ,
clearly, the apparatus must 3e designed so that it is capa3le o. measuring the phenomena
to 3e studied and the 0uantities used must 3e appropriate to the e0uipment7
Dor eample, suppose 6e 6ish to determine the amount o. sil/er in the 6aste solution
.rom a photographic processing la3oratory 3y precipitating insolu3le sil/er chloride 6ith
hydrochloric acid and 6eighing it7 "ur theory is em3odied in the chemical e0uation1
AgF !in solution" + 9Cl AgCl !precipitated" +
9F
The .ormula AgCl in this e0uation pro/ides the in.ormation 6here3y the amount o.
sil/er in the precipitated sil/er chloride can 3e determinedP pro/ided, o. course, that 6e
4no6 the relati/e atomic masses o. sil/er and chlorine7 The 6hole e0uation allo6s us to
calculate ho6 much sil/er chloride 6ill 3e .ormed .or a gi/en amount o. sil/er in the
a0ueous miture7 This in.ormation is re0uired not only to determine the amount o. sil/er,
3ut also to plan the eperiment in such a 6ay that the precipitate to 3e 6eighed is o. a
mass appropriate .or the chemical 3alance 6ith 6hich 6e propose to 6eigh it7 To do this
6e may need to ma4e a preliminary estimate o. the amount o. sil/er in the 6aste7
When, using a more ela3orate eample, 6e say that the length o. the "I9 3ond
in the 6ater molecule is $5.- #0
#2
m and the 9"9 3ond angle #0*75

, then
these
Lgures ha/e 3een o3tained using a theory, 0uantum mechanics in .act, 6hich relates
the measured a3sorption 3y 6ater /apour o. electromagnetic radiation in the micro6a/e
region (6a/elengths o. the order o. # I 2 cm+ to the masses o. the nuclei and the
molecular geometry7 Theory is not simply a su3stitute .or eperiment, it is a /ital
ad@unct to it7
But theory is al6ays a suggestion or hy%othesis, the correctness, or other6ise, o. 6hich
can only 3e tested against eperimental .act7 There.ore, theory must al6ays 3e su3ordinate
to eperiment7 A., a.ter thorough chec4ing .or errors, the results o. an eperiment are
.ound to di..er .rom those predicted 3y theoretical calculations, then the theory must 3e
amended, or perhaps e/en discarded7 Thus, although the theoretical .rame6or4 o. science
is an essential aspect 6hich guides our progress to6ards a deeper understanding, 6e must
al6ays recognise that a current theory may one day pro/e to 3e inade0uate and re0uire
replacement7 These points can 3e illustrated 3y means o. the gas la6s7
%1& THE AS 5A4S 26 82Y5E AN3 AY95USSAC
An #??2 :o3ert Boyle (#?2- I #?$#+ pu3lished the results o. a series o. eperiments on
the compression o. air in the closed, short arm o. a J2shaped tu3e7 Boyle o3ser/ed that as
the pressure, P , measured 3y the di..erence o. height o. the columns o. mercury in the
t6o arms o. the tu3e, increased, the /olume, V , o. air in the closed end o. the tu3e
decreased7 Durther, he noted that at constant tem%erat1re the vol1me is inversely
%ro%ortional to the %ress1re, a 0uantitati/e result 6hich could 3e epressed in the simple
e0uation1
P #,V or PV = constant !#.2.#"
The 6ords in italics and '0uation (#727#+ are 3oth epressions o. 6hat 6e no6 4no6
as BoyleGs la6, and in ans6er to t6o o. the 0uestions posed a3o/e 6e may say that
BoyleGs la6 arose .rom o. a series o. eperiments and that it epresses the results o.
those eperiments in a con/enient and precise mathematical .orm7
The dependence o. the /olume o. a gas upon temperature, t , at constant pressure 6as
studied 3y .our Drench scientists, Guillaume Amontons (#??, I #-05+, Jac0ues
Charles
* The :ole o. Theory in the !hysical Sciences
V = V
0
ep(tH2-,+
V = V
0
(# + tH2-,+
!
r
e
s
s
u
r
e

(
V
H
V
0
+
(#-*? I #%2,+, Joseph Gay2Lussac (#--% I #%50+ and 9enri :egnault (#%#0 I #%-%+7
The result o. their la3ours is 4no6n as the la6 o. Gay2Lussac, 6hich 6as pu3lished in #%*-
3y :egnault7 9e reLned the earlier eperimental methods and epressed the la6 in the
.orm1
V = V
0
!# + t ,2-,"
!#.2.2"
Where V
0
is the /olume o. the gas at 0

C7 9ere again 6e ha/e a la6 6hich has

3een disco/ered 3y eperimental measurements and, i. 6e consider it care.ully, 6e Lnd
that it says that, at constant pressure, the /olume o. a gas increases 3y #H2-, o. its /olume
at 0

C
.or e/ery degree rise in temperature7 Clearly, '0uations (#727#+ and (#7272+ are o. great
practical /alue7 They can, .or eample, 3e used to calculate the /olumes and pressures o.
gases at high temperatures7 Such calculations are essential in the design o. industrial plant
.or chemical processes, many o. 6hich ta4e place at /ery high temperatures and pressures7
%1' AN A8S25UTE :ER2 26 TEM!ERATURE
But '0uation (#7272+ carries a .ar more .undamental message, as Amontons had realised7
As 6e decrease the temperature o. the gas 3elo6 0

C, i7e7 6hen t 3ecomes negati/e,

the
/olume o. the gas decreases7 But this process must ha/e a limit, since there is no such
thing as a negati/e /olume, and it is clear .rom '0uation (#7272+ that the limit o. Kero
/olume is reached at t = 2-,

C7 There.ore, 2-,

C must 3e the lo6est

temperature
6hich can 3e achie/ed7 We are .orced to a remar4a3le conclusionP although 6e can go
up in temperature indeLnitely, there is a clear lo6er limit7 This surprising result has 3een
su3stantiated eperimentally and a more eact Lgure .or the a3solute Kero o. temperature
is 2-,7#5

C, 6hich is the origin o. the scale o. a3solute temperature 6here

temperature,
- , is measured in degrees >el/in or >1
- !>" = t !

C" + 2-,.#5
!#.,.#"
At is interesting to note here the importance o. the accuracy o. eperimental data in
.ormulating scientiLc la6s7 The mere o3ser/ation that the /olume o. a Led 0uantity o.
270
#75
#70
075
070
?00 *00 200 0 200
5 The :ole o. Theory in the !hysical Sciences
Temperature, t (C+
6ig;re %1% 'ponential and linear temperature2/olume relationships .or a gas
!hysical La6s 5
gas decreased 6hen the temperature 6as lo6ered might not ha/e led to the concept o. an
a3solute Kero o. temperature, much less to a /alue .or it7 Changes in physical 0uantities
are .re0uently descri3ed 3y an eponential .unction and in Digure #7# it is sho6n that the
e0uation1
V = V
0
ep!t ,2-," !#.,.2"
gi/es a temperature I /olume relationship 6hich is /ery similar to that gi/en 3y '0ua2
tion (#7272+ in the region o. temperature readily accessi3le to early researchers, i7e7 20
to +#00

C7 But according to '0uation (#7,72+, the /olume o. the gas ne/er reaches Kero,
no matter ho6 lo6 the temperature7 So it 6as /itally important that the accuracy o.
:egnaultGs eperimental measurements sho6ed clearly that the relationship 3et6een the
temperature and the /olume o. a gas 6as a linear rather than an eponential one7
%1( THE AS EQUATI2N 26 VAN 3ER 4AA5S
Attempts to study Gay2LussacGs la6 do6n to /ery lo6 temperatures .ailed 3ecause the
gases all li0ueLed long 3e.ore the a3solute Kero 6as reached7 And, indeed, many gases
6ere .ound to sho6 mar4ed de/iations .rom the pressure I /olume I temperature (PV-
+ 3eha/iour descri3ed 3y Boyle and Gay2Lussac .or 6hat 3ecame 4no6n as ideal
gases 6hich o3eyed the com3ined e0uation1
PV = nR- !#.*.#"
6here R is the ideal gas constant 6hich has a /alue o. %7,# J >
#
mol
#
and n is the
num3er o. moles o. gas in the sample (# mole o. gas contains ?.022 #0
2,
molecules+7 These de/iations o. the PV- 3eha/iour o. real gases .rom the ideal could 3e
represented 3y more comple gas la6s such as that proposed 3y Johannes <ideri4
8an der Waals
(#%,- I #$2,+ in
#%-,1
!P + a, V
2
"!V *" = nR- !#.*.2"
in 6hich a and * respecti/ely are parameters that allo6 .or the attraction 3et6een the
molecules and .or the Lnite /olumes o. the molecules themsel/es7 They ha/e di..erent
/alues .or di..erent gases 6hich are .ound 3y comparing the eperimentally determined
PV- 3eha/iour o. the gas 6ith the '0uation (#7*72+7
But to descri3e 8an der WaalsG e0uation in detail 6ould de/iate too .ar .rom the central
theme o. this 3oo4 and 6e there.ore turn to a summary o. the ans6ers to the 0uestions
a3out physical la6s posed in Section #707
%1) !HYSICA5 5A4S
A physical la6 epresses, either in 6ords or in alge3raic .orm, the result 6hich is to 3e
epected o. a particular eperiment7 Thus, '0uation (#7272+ tells us 6hat /olume o. gas
6e 6ould ha/e at any temperature, t , i. its /olume at 0

C is V
0
7 Drom '0uation
(#727#+
6e can calculate either pressure or /olume, though 6e must Lrst per.orm an eperiment
to determine the /alue o. the constant .or the particular gas7 A. it is an ideal gas then the
constant is nR-, 6here n is the num3er o. moles o. gas in the sample ('0uation (#7*7#++7
? The :ole o. Theory in the !hysical Sciences
La6s arise, are disco/ered or deduced as a result o. eperimental o3ser/ations7 They
are not deri/ed 3y pure mathematical reasoning though they may 3e, and indeed /ery
.re0uently are, epressed in an alge3raic .orm7 At .ollo6s .rom this that since la6s are
.ound as a result o. eperimentation they must also stand or .all 3y the results o. any
other eperiments to 6hich they relate7 Thus the ideal gas la6 ('0uation (#7*7#++ .ailed
the test o. application to all gases, especially in the region o. lo6 temperatures andHor
high pressures7 The la6 is there.ore o. limited applica3ility7 But it is not useless and there
are many circumstances in 6hich it can pro/ide /alua3le results7
A group o. one or more la6s normally underlies a theoretical model o. some aspect
o. the real 6orld as it is seen 3y science7 Thus, the three la6s o. thermodynamics are the
.oundation stones, disco/ered 3y eperiment, 6hich allo6 us to descri3e 0uantitati/ely
the inter2con/ersion o. the /arious .orms o. energyP o. heat into mechanical 6or4 .or
eample7 Together they .orm a mathematical model o. all such processes7 ;e6tonGs three
la6s per.orm the same .unction .or mechanics, the study o. motionP in the net chapter
6e shall eamine them in more detail7
The /alue o. la6s to science and technology applies at /arious le/els7 At the most
simple, 3ut highly signiLcant in applied science, there is the practical use o. a la6 to
predict a 0uantity 6hich cannot 3e readily measuredP the gas pressure in a no/el chemical
plant 6hich is still at the planning stage, .or eample7 A la6 also esta3lishes the .rame6or4
into 6hich eperimental results may 3e Ltted as they 3ecome a/aila3le7 This not only
pro/ides the means o. interpreting the results 3ut also alerts the eperimentalist 6hen a
ne6 result cannot 3e reconciled 6ith the current structure o. the theory7 This may mean
that an eperimental error has 3een made or that the la6 is Oa6ed7 At a deeper le/el,
la6s re/eal ne6 concepts 6hich 6ere not suspected at the time 6hen the measurements
6hich ga/e rise to the la6 6ere made7 We may sa.ely assume that the concept o. an
a3solute Kero o. temperature 6as not the idea 6hich stimulated the Lrst eperiments o.
AmontonsP 3ut it arose directly .rom them7 9ere lies the great importance o. la6s .or the
de/elopment o. the natural sciences7 As the .ull signiLcance o. the 0uantities related in
a la6 is appreciated, scientists are led to a deeper understanding o. their su3@ect and to
the .ormulation o. ne6 eperiments to test the la6 at the more .undamental le/el7 A. the
la6 .ails, such a test it must 3e regarded as Oa6ed and o. limited use, 3ut not necessarily
totally useless7 The important point is that eperiment is the only test o. the /alidity o.
a la67 La6s summarise the results o. a 6ealth o. eperimental data and present them
in a condensed .orm suita3le .or application or .or .urther study7 But they are al6ays
su3ordinate to eperiment7
%1* 5A4S< !2STU5ATES< HY!2THESES< ETC1
The 6aters o. the present discussion are sometimes muddied 3y the /ariety o. terms
used to descri3e the same thing7 We spea4, .or eample, o. the gas la0s, !lanc4Gs 0uan2
tum hy%othesis, the !auli %rinci%le and the %ost1lates o. 0uantum mechanics7 'ach term
highlighted in italics has essentially the same meaningP it is a statement, 6hich 6e ha/e
here called a la6, or a set o. such statements, that summarises the results o. eperimen2
tal measurements7 The di..erent 6ords epress di..erent aspects o. the meaning o. that
statement7 The terms la0 and %rinci%le emphasise the po6er and immuta3ilityP %ost1late
and hy%othesis the .act that this is a suggestion or a proposal 6hich may later re0uire
Theory at the 'nd o. the #$th Century -
modiLcation7 But in this 3oo4 6e shall regard all such epressions, and some others, as
meaning la6s7
%1+ THE2RY AT THE EN3 26 THE %-TH CENTURY
As the #$th century dre6 to a close the theoretical 3asis o. the physical sciences appeared
to 3e /ery mature and po6er.ul7 An particular, the three great structures o. Ca6ellGs
e0uations, 6hich descri3e the 3eha/iour o. electromagnetic radiation, thermodynamics
and mechanics, 6ere remar4a3ly success.ul in interpreting the eperimental .acts then
4no6n7 Three eamples sho6 the range and po6er o. these la6s7
The la6s o. mechanics had 3een .ormulated 3y Asaac ;e6ton (#?*, I #-2-+ to model the
motions o. the planets and descri3ed these motions 6ith remar4a3le accuracy7 <uring the
#%?0s James Cler4 Ca6ell (#%,# I #%-$+ and Lud6ig 'd6ard BoltKmann (#%** I
#$0?+ used ;e6tonian mechanics to descri3e the motion o. molecules in a gas,
de/eloping 6hat 6e no6 call the 4inetic theory o. gases7 The theory is in ecellent
agreement 6ith the etensi/e eperimental data encapsulated in the gas la6s o. Boyle and
Gay2Lussac7 The many de/iations .rom the eperimentally o3ser/ed 3eha/iour o. real
gases are due to the .ailure o. other assumptions in the theoryP that there is no attracti/e
.orce 3et6een the molecules .or eample7 ;e6tonian mechanics 6as thus sho6n to 3e
applica3le to 3odies
ranging in mass 3et6een #0
25
and #0
+25
4g7
An the area o. thermodynamics, the .re0uency o. the chirping o. the tree cric4et, 4ecan+
th1s, has 3een .ound to depend upon the a3solute temperature in strict con.ormity 6ith the
e0uation Lrst put .or6ard 3y S/ante August Arrehnius (#%5$ I #$2-+7
*
The logarithm
o. the .re0uency o. chirping is in/ersely proportional to the a3solute temperature,
sho6ing that the tree cric4etGs chirping is 0uite in/oluntary and is controlled 3y its
3ody chem2 istry 6hich, in turn, is su3@ect to the la6s o. thermodynamics7 The same is
true o. the autonomous .unctions o. the higher mammalsP the human heart 3eat .or
eample, though the temperature range a/aila3le to the eperimentalist is rather small in
this case7
"ur Lnal eample concerns electricity, magnetism and light7 Cichael Daraday (#-$# I
#%?-+ had sho6n that an electric current Oo6ing in a coil produces a magnet and that
6hen polarised light passes through a glass plate surrounded 3y the magnetic coil the
plane o. polarisation o. the light is rotated7 Thus, electricity, magnetism and light are
related7 An electric current can 3e measured 3y determining the magnetism it producesP
the units o. this measurement are called electromagnetic units, emu7 An electric current
can also 3e measured in terms o. the Oo6 o. chargeP the units o. this type o. measurement
are electrostatic units, esu7 An #%5-, Gusta/ >ircho.. (#%2* I #%%-+ sho6ed
eperimentally that the ratio o. the emu to the esu 6as e0ual to the /elocity o. light7 These
relationships 3et6een electricity, magnetism and light and 3et6een the emu and the esu
6ere 3rilliantly and 0uantitati/ely interpreted 3y Ca6ell 6ith his mathematical model o.
electromagnetic radiation pu3lished in #%-,7 Ca6ellGs model, 6hich is al6ays re.erred to
as 5ax0ell6s e71ations, though they might e0ually 6ell 3e called Ca6ellGs la6s,
sho6ed that light and all 6a/elengths o. electromagnetic radiation could 3e descri3ed in
terms o. a magnetic and an electric Leld that are orientated at right2angles to each
other and oscillate 6ith the .re0uency o. the radiation7 This led to the prediction that an
oscillating electric spar4 6ould generate electromagnetic radiation, a prediction 6hich 6as
3eauti.ully conLrmed 3y 9einrich 9ertK (#%5- I #%$*+ in a series o. eperiments reported
in #%%? I #%%%7 We shall
% The :ole o. Theory in the !hysical Sciences
eplore Ca6ellGs description o. electromagnetic radiation and the properties o. polarised
light .urther in Chapter %7
With successes li4e these to its credit it seems scarcely surprising that some physicists
apparently thought that there 6as little more to do in the Leld o. theory other than to dot
some iGs and cross a .e6 tGs7 ;e/ertheless, there 6ere a small num3er o. eperiments the
results o. 6hich deLed interpretation in terms o. the theories, i7e7 la6s, then a/aila3le7 At
6as the search .or solutions to these pro3lems 6hich led to the re/olutionary ideas o. Ca
!lanc4 (#%5% I #$*-+ and Al3ert 'instein (#%-$ I #$55+, and to 0uantum mechanics7 An
the net chapter 6e shall .ollo6 the history o. mechanics to illustrate .urther the role 6hich
theory plays in science and to see ho6, early in the 20th century, some o. the .oundations
o. the structure o. theoretical physics 6ere .ound to 3e 3y no means as secure as they
had once appeared7
%1, 8I85I2RA!HY AN3 6URTHER REA3IN
#7 C7S7 Coon, -he 81nting Peo%les, !enguin Boo4s, 9armonds6orth, =>, #$-?7
27 S7D7 Cason, A 8istory of the Sciences, Collier Boo4s, ;e6 Ror4, #$?27
,7 Lucretius, -he Nat1re of the Universe, Translation 3y :7'7 Latham, !enguin Boo4s, 9armonds2
6orth, =>, #$5#7
*7 D797 Johnson, 97 'yring and J7B7 Sto/er, -he -heory of Rate Processes in /iology and 5edicine,
Wiley, ;e6 Ror4, #$-*7
Chapter 2
6rom Classi#al to Q;ant;m
Me#$ani#s
270 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $
27# The motion o. the planets1 Tycho Brahe and >epler . . . . . . . . . . . . . . . . #0
272 ;e6ton, Lagrange and 9amilton . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##
27, The po6er o. classical mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2
27* The .ailure o. classical physics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2
275 The 3lac423ody radiator and !lanc4Gs 0uantum hypothesis . . . . . . . . . . . . #,
2757# !lanc4Gs solution to the 3lac423ody radiation pro3lem . . . . . . . . . . #5
27572 A 0ualitati/e interpretation o. the .orm o. the 3lac423ody emission
cur/e in the light o. !lanc4Gs hypothesis . . . . . . . . . . . . . . . . . . #?
2757, &uantisation in classical mechanics . . . . . . . . . . . . . . . . . . . . . . #%
27? The photoelectric e..ect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
27?7# 'insteinGs theory o. the photoelectric e..ect conLrmed
eperimentally . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
27- The emission spectra o. atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2,
27-7# BohrGs theory o. the structure o. the hydrogen atom . . . . . . . . . . . 2*
27-72 Comparison o. BohrGs model 6ith eperiment . . . . . . . . . . . . . . . 2?
27-7, Durther de/elopment o. BohrGs theory . . . . . . . . . . . . . . . . . . . . 2?
27% de BroglieGs proposal . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?
27$ The SchroM dinger e0uation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2%
27$7# 'igen.unctions and eigen/alues . . . . . . . . . . . . . . . . . . . . . . . . 2$
27#0 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0
!ro3lems .or Chapter 2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*
&1. INTR23UCTI2N
An this chapter 6e shall Lrst .ollo6 the historical course o. the de/elopment o. ;e6tonian
or classical mechanics7 We do this not only 3ecause classical mechanics is a limiting case
o. 0uantum mechanics, 3ut also 3ecause the story o. ho6 classical mechanics de/eloped
is an ecellent illustration o. ho6 a set o. la6s and the theoretical model 6hich they sus2
tain de/elops as a result o. the interplay 3et6een eperiment and theory7 9a/ing arri/ed
6ith classical mechanics at the end o. the #$th century, 6e shall in/estigate some partic2
ularly important eperimental results 6hich the la6s o. thermodynamics, mechanics and
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
#0 Drom Classical to &uantum Cechanics
electromagnetic radiation that 6ere a/aila3le at that time 6ere 0uite una3le to interpret,
despite their outstanding successes in many other applications7 Dinally, 6e shall see ho6
'r6in SchroM dinger and Werner 9eisen3erg cut the Gordian 4not 6ith the introduction
o. a ne6 mechanics I 0uantum mechanics7
&1% THE M2TI2N 26 THE !5ANETS: TYCH2 8RAHE AN3 =E!5ER
Be.ore there can 3e any theory there must 3e eperimental o3ser/ations to 3e interpreted
3y the theory7 (This proposition is not sel.2e/identP the ancient Gree4s de/eloped theo2
retical concepts almost entirely 6ithout appeal to eperimental e/idence7+ The collection
o. the eperimental data 6hich .ormed the 3asis .or the Lrst theory o. mechanics may 3e
traced 3ac4 to the astronomical o3ser/ations made, 6ithout a telescope, 3y the <anish
no3leman Tycho Brahe (#5*? I #?0#+, 6hose measurements 6ere the most important
and accurate o. early modern times7 Tycho, 6ho is usually 4no6n 3y this latinised
/ersion o. his <anish name, Tyge, 6as reno6ned .or his Lery temperament and .or most
o. his li.e he 6ore an artiLcial sil/er nose to replace the original appendage 6hich had
3een sliced o.. in a duel at the age o. #$7 At is interesting to note that he thought it 6as
not possi3le to ma4e o3ser/ations 6ithout the guidance o. a theoretical system o. the
6orld, and he adopted a modiLed earth2centred system, no6 o. course, 4no6n to 3e
.alse7 But the idea that measurements should 3e made in the light o. a theory 6hich,
it is 3elie/ed, can interpret them and Lt them into the .rame6or4 o. our eisting
4no6ledge, is an important part o. the modern scientiLc methodP a point discussed in
Chapter #7
An #5$$, Tycho Brahe mo/ed .rom Copenhagen to !rague, 6here he 6as @oined 3y
German mathematical astronomer Johannes >epler (#5-# I #?,0+ in #?007 When he
died in #?0#, Tycho 3e0ueathed his collection o. data to >epler 6ho .ound, a.ter many
years o. eacting 6or4, that the o3ser/ations o. the planets could 3e interpreted in terms o.
the .ollo6ing three la6s7
Keplers La!s of Planetary "otion
#7 The or3its o. the planets are ellipses 6ith the sun at one .ocus7
27 The line dra6n .rom the sun to the planet s6eeps out e0ual areas in e0ual times7
,7 The s0uare o. the time re0uired .or a planet to complete its or3it is proportional to the
cu3e o. its mean distance .rom the sun, i7e7 the length o. the semi2ma@or ais o. the
ellipse7
These la6s are illustrated graphically in Digure 27#7
An .ormulating his la6s, >epler 3rought the science o. mechanics .rom the data2
collection phase to the net important stage through 6hich any de/eloped scientiLc theory
must pass7 This is the stage at 6hich the 4no6n eperimental data are uniLed, in that
it is sho6n that the data can 3e interpreted in terms o. a small num3er o. .undamental
concepts1 the la6s7 Clearly, i. the la6s are soundly 3ased they ha/e predicti/e po6er,
i7e7 the results o. eperiments or o3ser/ations not yet made can 3e .oretold7 This is the
only con/incing test o. the la6s7 A set o. la6s constitutes a theory, and 6hen a theory
.ails systematically to predict correctly the result o. eperiments, then that theory must
3e amended or, in etreme cases, a3andoned7
S
;e6ton, Lagrange and 9amilton ##
c
r
d 3
a
p
o
0
Sun
s
pI0 is the ma@or and rIs the minor ais o. the ellipse 6hich the path o.
the planet traces around the sun7 The or3its o. the planets o. our solar
system are much more li4e circles than that sho6n here 6hich more
closely resem3les that o. an asteroid, e7g7 Acarus7
A. the planet ta4es e0ual times to mo/e .rom a to 3 and .rom c to d then
the areas o. the t6o sectors, aIsunI3 and cIsunId, o. the ellipse are e0ual7
6ig;re &1% >eplerGs la6s o. planetary motion
The predicti/e po6er o. >eplerGs la6s is illustrated 3y his ta3les o. astronomical
data, pu3lished in #?2-, 6hich he calculated 3y means o. his three la6s and named the
R1dol%hine -a*les in honour o. his patron, the emperor :udolph AA7 The planets Cercury
and 8enus, 6hich ha/e or3its o. radius less than that o. 'arth, sometimes pass 3et6een
the earth and the sun7 At such times the planet in 0uestion, /ie6ed .rom the earth, can 3e
seen to mo/e across the .ace o. the sun7 This is 4no6n as a transit o. the planet7 With the
aid o. his ta3les, >epler correctly predicted the transits o. Cercury (-th ;o/em3er, #?,#+
and o. 8enus (*th <ecem3er, #?,$ and ?th June, #?-#+ across the sunGs disc7 All these
e/ents actually too4 place as >epler had said they 6ouldP 3ut not 3e.ore he died in #?,07
The net stage in this 3rie. history o. classical mechanics concerns a .urther phase
through 6hich scientiLc theories o.ten passP a phase in 6hich a more .undamental, and
hence more 6idely applica3le, set o. la6s is sought7 >eplerGs la6s descri3ed the motions
o. the planets I 3ut 6hy did they mo/e in that 6ayJ An ans6er to that 0uestion might
re/eal that the motions o. other 3odies 6ere go/erned 3y similar la6s7
&1& NE4T2N< 5ARANE AN3 HAMI5T2N
Asaac ;e6ton (#?*, I #-2-+ 6as not the only man o. his time to grapple 6ith this
pro3lem7 9is ans6er to it, together 6ith accounts o. many o. his other scientiLc and
mathematical achie/ements, appeared in his Philoso%hiae Nat1ralis Princi%ia 5athematica
in #?%-7 The .our la6s upon 6hich he 3ased his analysis 6ere clearly o. a much more
.undamental, and there.ore more general, nature than >eplerGs7
#e!tons La!s of "otion
#7 A particle mo/es 6ith a constant (perhaps Kero+ /elocity (and there.ore in a straight
line+ unless it is acted upon 3y a .orce7
#2 Drom Classical to &uantum Cechanics
=

27 A particle acted upon 3y a .orce (9 + 6ill mo/e 6ith an acceleration (a+ proportional
to that .orce, the constant o. proportionality 3eing the in/erse o. its mass (m+7
a = 9,m !2.2.#"
,7 When t6o particles act upon one another, the t6o .orces acting on the particles are
e0ual and opposite to one another and are directed along the line @oining the t6o
particles7
*7 The gra/itational .orce o. attraction 3et6een t6o 3odies is proportional to the product
o. their masses (m
#
and m
2
+ and in/ersely proportional to the s0uare o. the distance
(r + 3et6een them7 The constant o. proportionality is the gra/itational constant (.+7
9 .

m
#
m
2

!2.2.2"
r
2
The items or postulates # to , constitute the la6s o. 6hat 6e no6 4no6 as classical
mechanics7 <uring the .ollo6ing t6o centuries other .ormulations 3ased on di..erent
postulates 6ere de/eloped, nota3ly 3y Joseph2Louis Lagrange (#-,? I #%#,+ and
William :o6an 9amilton (#%05 I #%?5+7 9o6e/er, these later .ormulations o. classical
mechanics 6ere entirely consistent 6ith ;e6tonGs and 6ith each otherP any one /ersion
could 3e deri/ed mathematically .rom any other7 The Lagrangian and 9amiltonian
.ormulations .ound acceptance 3ecause they 6ere more elegant in certain applications
and the theory as a 6hole scored many truly remar4a3le successes7
&1' THE !24ER 26 C5ASSICA5 MECHANICS
An Section #7- attention 6as dra6n to the 6ay in 6hich Ca6ell and BoltKmann de/eloped
the 4inetic theory o. gases 3y applying ;e6tonGs la6s to the motion o. the molecules
o. a gas, there3y o3taining a deeper understanding o. the gas la6s o. Boyle, Charles
and Gay2Lussac7 The gas la6s 6ere to the study o. gases 6hat >eplerGs la6s 6ere
to mechanicsP the Lrst attempt to uni.y a mass o. eperimental data in a mathematical
.ormalism7 The 6or4 o. ;e6ton, Ca6ell and BoltKmann 3rought these t6o strands
o. theoretical physics together and classical mechanics 6as thus sho6n to 3e largely
applica3le to 3odies ranging in mass .rom #0
25
to #0
+25
4g7 "ther eamples o. the
a3ility o. theory to interpret /ery di/erse eperimental o3ser/ations ha/e 3een cited in
Chapter #7 Theoretical physicists at the end o. the #$th century 6ere .ully @ustiLed in
.eeling that their science, 6hich 6e may term classical theoretical physics, 6as capa3le
o. meeting any challenge the eperimentalist might thro6 do6n7 And yet eperimental
measurements already on record, or soon to 3e made, 6ould 3e sho6n to 3e .undamentally
at /ariance 6ith the la6s o. classical physics and 6ould, in due course, trigger a complete
re/olution in the su3@ect7 What 6ere those measurementsJ
&1( THE 6AI5URE 26 C5ASSICA5 !HYSICS
At goes 6ithout saying that so cogent and success.ul a structure as classical physics did
not .all easily or rapidly7 A. the la6s are thought o. as the 3elt o. the structure then
the 3lo6s that 3rought it do6n .ell 3elo6 that 3elt, stri4ing at .undamental assumptions
The Blac42Body :adiator and !lanc4Gs &uantum 9ypothesis #,
6hich 6ere em3odied in the la6s 3ut ne/er eplicitly stated7 The .act that the structure
needed to 3e replaced rather than simply repaired too4 many years to gain acceptance,
and the replacement 6as scarcely /ia3le until the late #$20s7 The Lrst ,0 years o. the
20th century 6as at one and the same time a period o. turmoil and o. intense ecitement
and creati/ity in the scientiLc 6orld7 At 6itnessed some o. man4indGs most outstanding
intellectual achie/ements7
There 6as one ma@or 3lo6 6hich 6e shall not discuss here7 At .ell in #$05 6hen Al3ert
'instein (#%-$ I #$55+ sho6ed that, 3ecause o. the Lnite /elocity o. light, to say that
t6o e/ents ta4e place simultaneously only has meaning i. the e/ents occur at the same
place, and the concepts o. space and time cannot there.ore 3e separated as they are in
classical physics7 'instein demonstrated that the /elocity o. light 6as a limiting /elocity
and that, although ;e6tonian mechanics 6as 0uite ade0uate .or 3odies mo/ing 6ith
/elocities only a .raction o. that o. light, it 6as not applica3le to 3odies mo/ing at
/elocities approaching that limit7 ;e/ertheless, 6e 6ould not thin4 o. using relati/istic
mechanics to calculate the or3it o. a communications satellite .or eample7 ;e6tonian
mechanics is much easier to apply and, .or such a system, gi/es ans6ers 6hich are in
practice 0uite indistinguisha3le .rom the relati/istic results7 This illustrates a /ery
important pointP although 6e 4no6 that classical mechanics is o. limited applica3ility,
it is still etremely use.ul and /ery 6idely used7
Drom the point o. /ie6 o. the de/elopment o. 0uantum mechanics, a more important
e/ent had ta4en place .our years 3e.ore 'instein proposed his theory o. relati/ity7 An #$0#
Ca >arl 'rnst Lud6ig !lanc4 (#%5% I #$*-+ proposed a similarly radical solution to
a pro3lem that had 3een plaguing theoreticians throughout the #%$0sP the energy
spectrum o. the 3lac423ody radiator7
&1) THE 85AC=9823Y RA3IAT2R AN3 !5ANC=S
QUANTUM HY!2THESIS
Any 3ody at a temperature a3o/e the a3solute Kero emits electromagnetic radiation o/er
a range o. 6a/elengths7 The energy re0uired to produce this radiation, 6hich is 4no6n
as thermal radiation, comes .rom the thermal agitation o. the particles o. 6hich the 3ody
is composed and, i. the temperature o. the 3ody is a3o/e that o. its surroundings, then,
as the radiation is emitted, the 3ody cools do6n7 When the 3ody reaches the temperature
o. its surroundings e0uili3rium is esta3lished and the 3ody a3sor3s and emits radiation
at eactly the same rates7 Both the emission and the a3sorption processes are o. interest
to us7 An #%-$ Jose. Ste.an (#%,5 I #%$,+ disco/ered eperimentally that the total
energy per second (:
-
+ emitted .rom the sur.ace o. a 3ody o/er all .re0uencies is
proportional to the .ourth po6er o. its a3solute temperature (- +1
:
-
-
*
An #%%* BoltKmann deduced the constant o. proportionality .rom thermodynamic prin2
ciples and 6rote the e0uation in the .orm1
:
-
= ' e-
*
!2.5.#" 6here ' is the Ste.an2BoltKmann constant (' = 5.?- #0
%
W m
2
>
*
+
and e is a dimensionless constant called the emissivity, 6hich lies 3et6een 0 and #,
depending upon
the nature o. the emitting sur.ace7
'
n
e
r
g
y

d
e
n
s
i
t
y

p
e
r

m
e
t
e
r

6
a
/
e
l
e
n
g
t
h

i
n
t
e
r
/
a
l

(
J

m

*
+
T
/
i
s
i
3
l
e

r
a
n
g
e
#* Drom Classical to &uantum Cechanics
The a3ility o. a 3ody to a3sor3 electromagnetic radiation is deLned 3y its a*sor%tivity,
a, 6hich is the ratio o. the total radiant energy .alling upon its sur.ace to the total
energy a3sor3ed 3y the sur.ace7 Gusta/ >irchho.. sho6ed 3y a po6er.ul thermodynamic
argument that e 6as e0ual to a, and this e0uality has also 3een su3stantiated 3y eperiment7
Thus, good a3sor3ers o. radiation are also good emitters, and /ice /ersa7 A 3ody 6hich
is 3oth a per.ect emitter and a per.ect a3sor3er, i7e7 one .or 6hich e = a = #.0 is
called
a *lac; *ody and is o. particular interest7 The 3est eperimental realisation o. a 3lac4
3ody sur.ace is a small hole in a ca/ity .urnace 6ith 3lac4ened inner 6alls7 :adiation
passing in through the hole has e..ecti/ely no chance o. 3eing reOected 3ac4 through it,
so a = #.0 and there.ore e = #.0
also7
The reason .or the great interest in the properties o. the per.ectly emitting and a3sor3ing
3lac4 3ody can 3e seen 3y setting e = #.0 in '0uation (2757#+7 The total energy
emitted is .ound to 3e dependent on the Ste.an2BoltKmann constant and the .ourth
po6er o. the
a3solute temperature 3ut not upon any aspect o. the 3ody itsel.7 Clearly, 3lac423ody
radiation is a /ery .undamental phenomenon 6hich demands an interpretation7 Accurate
eperimental data 6ere pro/ided in #%$$ 3y "tto :ichard Lummer (#%?0 I #$25+ and
'rnst !ringsheim (#%5$ I #$#-+7 They used a de/ice not unli4e a spectrometer to
measure the 6ay in 6hich the intensity o. the emitted radiation, : !<", depended upon
the 6a/elength o. that radiation, <, and .ound cur/es such as those sho6n in Digure 2727
The ordinate o. Digure 272 is not : !<" 3ut =!<", the energy density inside the ca/ity,
6hich is e0ual to
*: !<",c 6here c is the /elocity o. light7 Core precisely, =!<" is the energy o. the radiation
in the 6a/elength inter/al < to < + d< in # m
,
o. the ca/ity7 ;ote ho6 the pea4 o. the
cur/e mo/es to shorter 6a/elengths as the temperature is increased7 This phenomenon is
o3ser/ed 6hen the Llament o. an electric Lre goes .rom dull red to almost 6hite as the
Lre heats up7 Dor a particular temperature, the total energy emitted, :
-
, is proportional to
the area under the cur/e and one can see ho6 rapidly this rises 6ith temperature, as is
re0uired 3y the .actor -
*
in '0uation (2757#+7
'/en 3e.ore Lummer and !ringsheimGs accurate data 3ecame a/aila3le, the essential
.orm o. the relationship 3et6een energy and 6a/elength 6as 4no6n and had stimulated
?000
5000
- = 2000 >
=ltra/iolet catastrophe U
*000
,000
- = #-50 >
:ayleigh2Jeans
e0uation - = 2000 >
2000
#000
- = #500 >
- = #250 >
0
0 #000 2000 ,000 *000 5000 ?000
Wa/elength (nm+
6ig;re &1& The emission spectra o. a 3lac423ody radiator
many attempts to eplain it7 A particularly important theoretical study o. 3lac423ody radi2
ation 6as made around #$00 3y John William Strutt, the third Lord :ayleigh (#%*2 I
#$#$+ and James 9op6ood Jeans (#%-- I #$*?+7 At the heart o. this 6or4 lay the
concept that the radiation 6as emitted (or a3sor3ed+ 3y many QoscillatorsG 6hich
.ormed, or 6ere contained 6ithin, the structure o. the 3lac4 3ody7 According to
electromagnetic theory, electric charges oscillating 6ith .re0uency > emit radiation o.
the same .re0uency and .rom this the 6a/elength, <, o. the radiation can 3e readily
calculated since1
>< = c = /elocity o. light
!2.5.2"
9o6e/er, although the e0uation o3tained 3y :ayleigh and Jeans agreed 6ith eperi2
ment at long 6a/elengths it 6as completely at /ariance 6ith eperiment at short 6a/e2
lengths (Digure 272+7 At 6as especially distur3ing that the e0uation predicted that the
intensity o. the emitted radiation rises to inLnity as the 6a/elength approaches Kero7 This
impossi3le result 6as 4no6n as the ultra/iolet catastrophe7
&1)1% !lan#>s sol;tion to t$e ?la#>9?o/0 ra/iation pro?lem
Ca !lanc4 6as a man .or 6hom honour and success in his pro.essional li.e 6ere accom2
panied 3y great personal tragediesP he outli/ed his Lrst 6i.e and all .our o. their children7
9e 3elie/ed deeply that the only proper occupation .or a theoretician 6as attempting to
sol/e the most .undamental and challenging pro3lems o. the time7 At the end o. the #$th
century there 6as no more .undamental a pro3lem than that o. 3lac423ody radiation and in
#$0# !lanc4 had already 3een 6or4ing on it .or a3out si years7 Though he 6as 3y nature
a /ery conser/ati/e man, he .ound himsel. .orced to the conclusion that only an etremely
radical change in the ideas 6hich he and others had applied to the pro3lem hitherto could
lead to a relationship 3et6een =!<" and < 6hich 6ould agree 6ith eperiment in the
short26a/elength region7 9is re/olutionary idea 6as that1
An oscillator 0ith fre71ency > can %ossess only total energies, E
n
, 0hich satisfy the e71ation2
E
n
= nh> !n = 0 # 2 , . . ."
!2.5.,"
6here h is a uni/ersal constant, no6 4no6n as !lanc4Gs constant and n are the integers7
!lanc4 6as proposing that energy came in QpiecesG o. a certain siKe determined 3y the
.re0uency (>+7 Just as the atomic theory re0uires that matter is not inLnitely di/isi3le,
!lanc4Gs suggestion re0uires that the same is true o. energy7 When the possi3le energies o.
the oscillators 6ere restricted in this 6ay, !lanc4 o3tained a result in ecellent agreement
6ith the eperimental data o. Lummer and !ringsheim and a /alue .or h o. ?.55
#0
,*
J s7 !lanc4Gs e0uation may 3e epressed in the .orm1
=!<" d< =
or on a .re0uency scale as1
%( hc
<
5

!ep
%( h>
,
#
{hc, ;<-
#
d< !2.5.*a"
} #"
=!>" d> =
c
,

!ep {h>, ;-
d> !2.5.*3"
} #"
6here ; is BoltKmannGs constant and - the a3solute temperature7
2
2
The 3oldness o. !lanc4Gs hypothesis and the departure 6hich it represented .rom the
/ie6s accepted up to that time cannot 3e eaggerated7 The assumption that energy 6as
inLnitely di/isi3le into portions o. any siKe underlay all .ormulations o. classical mechan2
ics and 6as so .undamental to them that it 6as ne/er e/en stated7 ;o6 that assumption
had 3een sho6n 3y !lanc4 to 3e untena3le7 !lanc4 coined the term 71anta (singular
71ant1m + .or his little pac4ets o. energy (h>+ and systems 6hich can ha/e only certain
/alues o. energy, in this or an analogous manner, are said to 3e 71antised7 The num3er
n in '0uation (2757,+ 6hich gi/es the num3er o. 0uanta in the total energy !E
n
" is called
a 71ant1m n1m*er7
At is interesting to note that the e0uation proposed 3y !lanc4 .or the possi3le total
energies o. an oscillator, '0uation (2757,+, had to 3e modiLed 6hen the .ully de/eloped
0uantum theory o. the harmonic oscillator 3ecame a/aila3le a3out 25 years later7 At 6as
then sho6n that the correct .ormula .or E
n
is1
E
n
= !n +
#
"h> !n = 0 # 2 . . ."
!2.5.5"
and each energy le/el is seen to 3e raised 3y
#
h>, the Kero2point energy (see Chapter #0+7
This uni.orm discrepancy in the energy le/els caused no pro3lem in !lanc4Gs 6or4
and in early applications o. the de/eloping Qold 0uantum theoryG .or 6hich only energy
di..erences 6ere re0uired7 9o6e/er, pro3lems did arise 6hen attempts 6ere made to
eplain certain lo62temperature phenomena, such as the speciLc heats o. solids, and
these di.Lculties 6ere only o/ercome 6hen the .ully2Oedged 0uantum theory re/ealed the
presence o. the Kero2point energy7
&1)1& A @;alitatiAe interpretation o" t$e "orm o" t$e ?la#>9?o/0
emission #;rAe in t$e lig$t o" !lan#>s $0pot$esis
At is not immediately o3/ious that a change .rom a group o. classical oscillators ha/ing all
possi3le energies to a situation in 6hich the energies o. the oscillators are 0uantised can
ma4e such a dramatic di..erence to the predicted graph o. =(<+ /ersus <7 Since this is a
0uestion o. the energy o. the 0uantum and its dependence upon .re0uency, in Digure 27,
the !lanc4 .unction is plotted on a .re0uency rather than 6a/elength 3asis7 ;aturally,
since > is in/ersely proportional to <, the plot loo4s /ery di..erent in .orm though the
essential .eatures remain7 To interpret this .orm 6e Lrst note that in 3oth the classical and
0uantum /ie6 the num3er o. allo6ed .re0uencies in the .re0uency range 3et6een > and
> + d> N !>" d>, is gi/en 3y1
#
N !>" d> =
%(V >
2
d> !2.5.?"
c
,
6here V is the /olume o. the ca/ity7 The reason .or the restriction on the num3er o.
allo6ed .re0uencies 6ithin the ca/ity is that each .re0uency is associated 6ith a standing
6a/e 6hich must ha/e nodes at the ca/ity 6alls7 This re0uirement limits the possi3le
6a/elengths in @ust the same 6ay as the possi3le 6a/elengths o. a /iolin string are
limited7 'nergy no6 enters our discussion since the /alue o. =!>" d> is o3tained 3y
multiplying N !>" d> 3y, ?, the mean energy o. the oscillators7 Thus there 6ould appear
to 3e a strong tendency .or the graph o. =(>+ /ersus > to rise steeply 6ith increasing >7
But there is another .actor to 3e consideredP the 6ay in 6hich the a/aila3le energy is
0

#

'
n
e
r
g
y

d
e
n
s
i
t
y

#
0
#
-

(
J

m

,

9
K

#
+

Dre0uency (T9K+
#00070 %0070 ?0070 *0070 20070 070
50
*0
,0
20
- = ,?2075 >
;- = 570 #0
20
J
#0
'nergy in units o. ;-
0
#270 #070 %70 ?70 *70 270 070
;- VV hn
;- hn ;- WW hn
6ig;re &1' A 0ualitati/e interpretation o. the 3lac423ody emission spectrum
distri3uted o/er the oscillators and, again, classical and 0uantum theories do not di..er in
that 3oth use the BoltKmann distri3ution7 The ratio o. the num3ers o. oscillators (N
0
and
N
#
+ in t6o energy le/els (E
0
and E
#
+ is determined 3y the energy di..erence according
to the e0uation1
N
#
N
0
=

E E

ep
;-

E

ep !2.5.-"
;-
9o6e/er, the crucial di..erence 3et6een the classical and 0uantum /ie6s is re/ealed
6hen 6e determine the mean energy (?+ o. the oscillators7 Classically, 6ith a continuum
o. energy le/els, 6e Lnd1
6hilst the 0uantised energy2le/els gi/e1
? = ;- !2.5.%a"
h>
2.5.%3"
?
=
ep!h>, ;- " #
!
;oting that the eponential .unction may 3e epanded (see Appendi %+ as the series1
ep!h>, ;- " = # + h>, ;- + !h>, ;- "
2
,2U + !h>, ;- "
,
,,U
+
6e see that the 0uantum /alue o. ? tends to the classical /alue 6hen h> ;- and
6e ta4e @ust the Lrst t6o terms in the epansion7 Thus, at the lo62.re0uency end o.
the
2
2
graph (Digure 27,+, 6here there is e..ecti/ely a continuum o. energy le/els, the situation
is almost classical and the classical and 0uantum theory plots are /ery similar7 9o6e/er,
as 6e mo/e to higher .re0uencies the 0uantised spacing o. the energy le/els 3egins to
ma4e itsel. .elt7 A. 6e go immediately to the highest .re0uencies it is o3/ious that, at that
limit, the spacing 3et6een the energy le/els ( E = h>+ is so large that only the
lo6est
energy le/el is occupied7 A. all oscillators are in their lo6est energy state they cannot
emit and =(>+ must .all to Kero7 At .ollo6s, there.ore, that as 6e go .rom lo6 to high
.re0uencies a point is reached 6here the increasing energy2le/el spacing 3ecomes more
important than the increase in the energies o. the oscillators themsel/esP the graph o. =(>+
/ersus > goes through a maimum and 3egins its long .all to Kero7 'is3erg
#
has a /ery
good discussion o. the 3lac423ody pro3lem7
&1)1' Q;antisation in #lassi#al me#$ani#s
A 0uestion arises immediatelyP i. energy is 0uantised, 6hy 6as this not noticed 3e.ore
#$0#J Consider the /i3ration o. a macroscopic oscillatorP an idealised system consisting
o. t6o masses, each o. 07# 4g, @oined 3y a mass2less spring 6hich is #0 cm (07# m+
long at e0uili3rium and can 3e etended or compressedP (Digure 27*+7 A. the spring o3eys
9oo4eGs la6 in 3oth compression and etension then the potential energy, E, produced
3y a change o. length o. r is gi/en 3y1
E =
#
;! r "
2
so .or our particular spring1
E =
#
;!r 0.#0"
2
!Joules"
!2.5.$"
6here ; is the .orce constant measured in ; m
#
and r is the length to 6hich the spring
has 3een etended or compressed7 ; represents the sti..ness o. the spring and i. 6e
pull the masses apart to etend the spring and then release them the model /i3rates7
An our idealised system there 6ill 3e no losses o. energy and the /i3ration 6ill con2
tinue indeLnitely7 As the model /i3rates energy is continually echanged 3et6een 4inetic
and potential7 At the maimum and minimum spring lengths all the energy is poten2
tialP at the point 6hen the spring length is #0 cm all the energy is 4inetic7 The total
energy, potential plus 4inetic, is constant since energy must 3e conser/ed7 This is a suit2
a3le model .or an oscillating, homonuclear diatomic molecule, e7g7 hydrogen (9
2
+ or
oygen ("
2
+7
07# m
m = 07# 4g m = 07# 4g
; = #5 ; m
#
n = 27-? s
#
6ig;re &1( A macroscopic dum323ell oscillator
07000 07005 070#0 070#5 07020 07025 070,0
07000 #7%% -750 #?7%% ,0700 *?7%% ?-750
'
n
e
r
g
y

#
0
*

(
J
+
The potential energy .or a particular etension o. the spring, and hence the total
energy at any time, can 3e calculated .rom '0uation (2757$+7 The results o3tained using
a .orce constant o. #5 ; m
#
are sho6n in Ta3le 27#7 Since the energy is determined
3y !r 0.#0"
2
, the Lgures apply to 3oth etension and compression o. the spring
and they descri3e a para3ola (Digure 275+7 "scillations 6hich arise as a result o. a para3olic
potential energy cur/e are simple harmonic oscillations and the .re0uency o. oscillation
(>+ can 3e calculated 3y means o. the e0uation1
#
> =
2(

2;
!s
#
m
or 9K" !2.5.#0"
6here m is the mass o. each o. the t6o e0ual masses 6hich, in our case is #00 g = 0.#
4g7 We Lnd that the .re0uency is 27-5- 9K, i7e7 the model per.orms 27-5- oscillations
per second7
An this hypothetical model there is no limit on the potential energy 6hich 6e can
gi/e the systemP it simply depends upon the initial etension (or compression+ 6hich 6e
choose to impose upon the spring7 But note that although the energy may 3e di..erent,
the .re0uency o. oscillation is al6ays the same since it depends ('0uation 2757#0+ only
on m and ;7 But according to !lanc4 the energy is 0uantised in units o. h> = ?.?2?

#0
,*
2.-5- J = #.%2- #0
,,
J7 Comparing this result 6ith the Lgures in Ta3le
27#, 6e see that the 0uantum o. energy in this eample is a3out #0
2%
times smaller than
the energy o. the oscillator7 At is such a small 0uantity that there is no 6ay in 6hich 6e
could measure it or detect its presence 3y o3ser/ation o. the /i3rations o. our model7 As
.ar as our model is concerned, energy is e..ecti/ely continuous7
Ta?le &1% The energy o. the macroscopic model o. a diatomic oscillator as a .unction o. the
distance 3et6een the masses
(r 0.#+Hm
E,J
#0
*
%0
-0
?-750 X #0
*
J
?0
50
*?7%% X #0
*
J
*0
,0
20
Simple
harmonic
#0
oscillator
0
0705 0700 0705 07#0 07#5 0720 0725
<istance 3et6een masses (m+
6ig;re &1) The para3olic potential energy cur/e o. the macroscopic dum323ell oscillator
But i. 6e consider a molecule 6e shall Lnd that t6o .actors contri3ute to ma4e 0uan2
tisation a real o3ser/a3le phenomenon in a system o. atomic dimensions7 We ta4e as
our molecular model the hydrogen molecule (9
2
+7 'periment tells us that the mass o.
each atom in the molecule is #.?-,% #0
2-
4g and the .re0uency o. oscillation (>+
is
#.,#-5 #0
#*
9K7 :earranging '0uation (2757#0+ 6e
ha/e1
; = 2(
2
>
2
m
!2.5.##"
6hich, 6ith these data, gi/es a .orce constant o. 5-, ; m
#
7 And the 0uantum o. energy
.or the /i3rating hydrogen molecule is there.ore h> = %.-2? #0
20
J7 This is
much larger than that o. the macroscopic model 3ecause o. the great di..erence in the
/i3rational .re0uencies o. the t6o systems7
The 9I9 3ond length is -*7#- pm (# pm = #0
#2
m+ so, using '0uation (2757$+, a #0
Y etension o. the 3ond de/elops a potential energy o. !5-,,2" !-.*"
2
= #.5-
#0
20
J7 This Lgure is approimately one L.th o. the /alue o. h> .or the hydrogen
molecule cal2 culated a3o/e and 6e must there.ore epect that 0uantisation 6ill play
a much more important role in the /i3rational 3eha/iour o. the hydrogen molecule than it
does in the macroscopic model 6e discussed earlier7 Thus, 6e anticipate that the e..ects
o. 0uantisa2 tion 6ill 3e measura3le in atoms and molecules, 3ut not in macroscopic
systems7
An summary, 6e may say that it is the magnitude o. !lanc4Gs constant (h+ 6hich is the
determining .actor7 "nly 6hen energies are so small or .re0uencies so high that E h>
do the e..ects o. 0uantisation 3ecome /isi3le in our eperimental measurements7 Such
conditions are .ound 6hen 6e study the 3eha/iour o. atoms and molecules7
&1* THE !H2T2E5ECTRIC
E66ECT
!lanc4Gs solution o. the pro3lem o. the energy distri3ution o. 3lac423ody radiation 6as
etremely di.Lcult .or scientists to acceptP not least !lanc4 himsel. 6ho realised that,
i. it 6ere correct, it 6ould re0uire the recasting o. the 6hole o. classical physics7 The
thought that energy, li4e matter, 6as not inLnitely di/isi3le struc4 at the /ery .oundations
o. theoretical physics7 What 6as desperately needed 6as some conLrmation, some other
eperiment 6hich could 3e success.ully interpreted in terms o. a 0uantisation o. energy7
The 6orld o. physics 6aited until #$05 .or such e/idence, 6hich 'instein then pro/ided
6ith 3rilliant insight, though its true /alue 6as not recognised immediately7 The eperi2
mental o3ser/ation 6e shall discuss here is the %hotoelectric effect, 3ut in his #$05 paper
'insteinGs discussion ranged much more 6idely7
An #%%- 9ertK disco/ered that 6hen a 3eam o. ultra/iolet light .alls upon a metal
sur.ace particles capa3le o. conducting electricity are emitted .rom the metal7 An #$00
!hilipp 'duard Anton Lenard (#%?2 I #$*-+ pro/ed that the emitted particles 6ere
elec2 trons and .urther eperiments re/ealed the .ollo6ing salient .acts a3out the
photoelectric e..ect7
There is a threshold o. .re0uency (>
0
+7 Light ha/ing a .re0uency lo6er than >
0
does not e@ect electrons .rom the metal sur.ace, no matter 6hat the intensity o. the light7
But 6hen the .re0uency is increased a3o/e the threshold electrons appear
immediately7
The electrons e@ected 3y radiation o. .re0uency > greater than >
0
ha/e 4inetic energy
and this 4inetic energy increases as the .re0uency di..erence, > >
0
, increases7
The !hotoelectric '..ect 2#
A. the intensity o. the light is increased at a constant .re0uency the 4inetic energy o. the
e@ected electrons remains the same, 3ut they increase in num3er in direct proportion to
the intensity7
These eperimental o3ser/ations are completely at /ariance 6ith classical electromag2
netic 6a/e theory7 A. the energy o. light is spread out in a 6a/e a time delay 6ould 3e
epected, during 6hich the electron accumulates energy .rom the 6a/e, 3et6een the time
at 6hich the light source is s6itched on and the appearance o. the Lrst electrons7 The
delay 6as estimated theoretically to 3e a3out one minute 6hereas a delay o. approi2
mately #0
$
s 6as measured eperimentally7 Durther, since in classical theory energy is
accumulated .rom the light 6a/e, any light should 3e capa3le o. e@ecting electronsP the
process o. accumulation 6ould @ust ta4e longer .or less energetic light and there 6ould
3e no other dependence upon >7 Dinally, .or a gi/en period o. illumination, the 4inetic
energy o. the e@ected electrons is epected to increase 6ith the intensity o. the light, not
6ith its fre71ency7
'instein 3ased his #$05 interpretation o. the .acts o. the photoelectric e..ect on !lanc4Gs
hypothesis, reasoning as .ollo6s7 According to !lanc4, the oscillators in a light source
can only ha/e 0uantised energies gi/en 3y nh> (n = 0 # 2 , . . .+7 There.ore, as
the oscillators change their energies .rom nh> to (n #+h> and emit radiation o.
.re0uency > and energy h> then, at the moment o. emission, this radiation must emerge
as a pulse 6ithin a short period7 A. this pulse o. radiation then mo/es a6ay .rom the
source as a single entity rather than dispersing as a 6a/e, light may 3e considered to 3e a
stream o. pulses o. energy7 (We no6 call these pulses o. energy %hotons, though
'instein did not use that epressionP see Chapter %+7 A. the stream o. photons, each ha/ing
energy h>, .alls upon a metal sur.ace one o. t6o things may then occur7 A. the energy
(h>+ o. the photon is less than the 6or4 .unction (W +, 6hich is the energy re0uired to
e@ect an electron .rom the metal sur.ace, no photoelectron 6ill 3e o3ser/ed7 A. the photon
has more energy than that re0uired to e@ect the electron then the electron 6ill 3e e@ected
and, 3ecause energy must 3e conser/ed, the ecess o. energy 6ill 3e con/erted into the
4inetic energy (@E + o. the e@ected electron7 'instein there.ore proposed the .ollo6ing
e0uations .or the energetics o. the photoelectric e..ect1
h> = W + @E
(27?7#+ h>
0
= W
(27?72+ @E = h> h>
0
= h!> >
0
"
(27?7,+
These e0uations are in ecellent agreement 6ith the eperimental .acts as they are
4no6n today7 But it is not 6idely appreciated that, at the time o. 'insteinGs suggestion,
no 0uantitati/e eperimental data 6ere a/aila3le7 "nly the 0ualitati/e results outlined
a3o/e 6ere 4no6n to him and e/en these 6ere not uni/ersally accepted7 Thus, he 6as
not a3le to calculate a /alue o. !lanc4Gs constant 6ith his ne6 theory and his paper
actually contains /ery .e6 numerical results7 At is concerned solely 6ith descri3ing a
num3er o. eperimental o3ser/ations and interpreting them in terms o. a particle theory
rather than a 6a/e theory o. light7 The impact o. this ne6 hypothesis 6as not immediate,
3ut 6hen its signiLcance 6as recognised it 6on 'instein the #$2# ;o3el !riKe .or !hysics7
The lac4 o. high20uality eperimental data on 6hich to test it 6as an important .actor in
the slo6 appreciation o. 'insteinGs ne6 concept7 'le/en years 6ere to pass 3e.ore such
data 3ecame a/aila3le7
22 Drom Classical to &uantum Cechanics
Sodium
Lithium
:
e
t
a
r
d
i
n
g

p
o
t
e
n
t
i
a
l

(
8
+
&1*1% Einsteins t$eor0 o" t$e p$otoele#tri# e""e#t
#onBrme/ experimentall0
The eperimental 6or4 re0uired to clinch 'insteinGs hypothesis, at least as .ar as the
photoelectric e..ect is concerned, too4 many years to complete and turned out to 3e
etremely di.Lcult7 :o3ert Andre6s Cilli4an (#%?% I #$5,+, 6ho had earlier
achie/ed .ame .or his determination o. the charge on the electron, de/oted a3out ## years
to this pro3lem 3eginning in #$057 An #$#? he reported the deLniti/e summary o. his
6or4 on the photoelectric e..ectP his data .or lithium and sodium are illustrated in Digure
27?7
The horiKontal ais o. the Lgure gi/es the .re0uencies o. the lines o. the mercury
discharge lamp used to ecite the photoemission7 The /ertical ais records the minimum
/oltage re0uired to pre/ent the photoelectrons lea/ing the metal7 This is a measure o. the
4inetic energy o. the photoelectrons7 ;egati/e /alues o. the retarding /oltage indicate that
the electrons lac4ed su.Lcient energy to lea/e the metal sur.ace and had to 3e dra6n a6ay
.rom it7 'ach point is the result o. a series o. eperiments in 6hich the photocurrent .or
a range o. more negati/e /oltages is etrapolated 3ac4 to Kero current7 The slope o. the
graph o. retarding potential against .re0uency, 6hen con/erted to appropriate units, gi/es
the /alue o. h,e and, using the /alue o. e 6hich he himsel. had determined, Cilli4an .ound
/alues o. h = ?.5%* and ?.5?$ #0
,*
J s .rom his lithium and sodium data
respecti/ely7
A.ter a /ery care.ul consideration o. errors Cilli4an concluded that h = ?.5-
#0
,*
6ith an error o. 075 Y7 When he recalculated h using !lanc4Gs original
e0uation .or 3lac423ody radiation 6ith the most recent /alues o. the other physical
constants in/ol/ed,
Cilli4an .ound eactly the same /alue .or h 6ith an estimated error o. 07, Y7 This result
conLrmed 'insteinGs ideas in the most con/incing manner7 At is not surprising that this
3rilliant and eacting eperimental 6or4 6as also cited 3y the ;o3el Committee 6hen
they a6arded the #$2, ;o3el !riKe .or !hysics to Cilli4an, largely, 3ut not eclusi/ely,
.or his determination o. the charge on the electron7
#70
075
070
075
#70
#75
270
275
500 ?00 -00 %00 $00 #000 ##00 #200
Dre0uency (#0
#2
9K+
:eproduced 6ith permission .rom :7A7 Cilli4an, Phys. Rev7, +, ,55 (#$#?+7
The American !hysical Society7
6ig;re &1* Cilli4anGs data .or the photoelectric e..ect in lithium and sodium
We cannot lea/e this su3@ect 6ithout emphasising again @ust ho6 radical 'insteinGs
photon hypothesis 6as and ho6 small 6as the 0uantity o. hard eperimental e/idence
.or it at the time7 An the introduction to his paper, 6hich did more than anything else
to conLrm it, Cilli4an himsel. descri3ed 'insteinGs proposition as a Q. . . *old not to
say rec;less hy%othesis7GP 6ords 6hich 6ere 0uite @ustiLed in /ie6 o. the dominance o.
the 6a/e theory o. light in #$057 But, in spite o. its Oimsy eperimental 3ase and the
.act that 0uantitati/e eperimental conLrmation 6as such a long time coming, 'insteinGs
photon hypothesis 3rought a3out a complete change in our /ie6 o. light7 Throughout the
#%th and #$th centuries the 6a/e theory o. light had 3ecome increasingly dominant and
had etended into the description o. ne6ly disco/ered .orms o. electromagnetic radiation
such as ultra/iolet, in.rared and radio 6a/es7 'insteinGs interpretation o. the photoelectric
e..ect demanded a complete reappraisal o. the 6ay in 6hich light 6as regarded7 9e had
etended !lanc4Gs re/olutionary hypothesis 6hile introducing an e0ually radical concept
o. his o6n7
&1+ THE EMISSI2N S!ECTRA 26 AT2MS
". all the eperimental data 6hich classical theories appeared to Lnd di.Lcult to interpret,
the greatest 0uantity o. highly accurate data 6as contained in the photographs o. atomic
spectral emission7 A. a sample o. li4e atoms is heated to a su.Lciently high temperature,
*000

C say, the atoms a3sor3 energy .rom the .urnace and re2emit it in the .orm
o.
an atomic spectrum (Digure 27-+7 The spectrum consists o. a num3er, many hundreds in
some cases, o. /ery sharp lines o. precise 6a/elength (.re0uency+7 The lines loo4 li4e,
and indeed are, a 3ar code .or the atom and :o3ert Wilhelm Bunsen (#%## I #%$$+
and Gusta/ >irchho.. (6hose 6or4 on the 3lac423ody radiator has already 3een mentioned
in Section 275+ identiLed the pre/iously un4no6n elements caesium (a s4y23lue line
.ound in #%?0+ and ru3idium (a ru3y2red line .ound in #%?#+ 3y measuring the
spectra o. minerals heated to incandescence 3y BunsenGs .amous 3urner7 Later,
>irchho.. sho6ed that measurement o. the a3sorption o. light 3y atoms 6as similarly
characteristic7 Atomic emission and a3sorption spectra are among the most po6er.ul
0ualitati/e and 0uantitati/e analytical tools currently a/aila3le to us7
The lo6est spectrum is that o. copper and the one immediately a3o/e it is iron7 The remainder are the
spectra o. ore samples7 ZThe spectra are printed as [positi/es[ so that the emission lines appear 6hite on a
dar4 3ac4ground7\
6ig;re &1+ Some atomic emission spectra
]
]
Christian, Analytical Chemistry, 5th edn, :eprinted 6ith permission o. John Wiley & Sons, Anc7
But in the Lrst decade o. the 20th century the sharp lines o. the atomic spectrum
constituted a theoretical pro3lem o. great di.Lculty7 Throughout this decade eperimental
e/idence concerning the structure o. the atom 6as accumulating and in #$## 'rnest
:uther.ord (#%-# I #$,-+ proposed a model o. the atom in 6hich almost the 6hole
mass o. the atom 6as concentrated in a /ery small, positi/ely charged nucleus at the centre
6hile the negati/ely charged electrons occupied a much greater region o. space
surrounding the nucleus7 Since atomic spectra 6ere the result o. emission o. radiation 3y
atoms, it should ha/e 3een possi3le to dra6 conclusions a3out the structure o. atoms .rom
their detailed atomic spectra7 But there 6as a pro3lem7 Since the electrons 6ere negati/ely
charged and the nucleus positi/ely charged electrostatics predicted that the electrons
6ould 3e dra6n into the nucleus, destroying the atom immediately7 A 6ay in 6hich
such an e/ent might 3e pre/ented 6ould 3e i. the electrons 6ere to or3it the nucleus, li4e
planets around a sun, 6ith the .orce o. the electrostatic attraction 3et6een electron and
nucleus replacing the gra/itational attraction 3et6een planet and sun7 But e/en this 6as
no solution7 According to classical electromagnetic theory, a negati/e charge or3iting a
positi/e charge constitutes an oscillating dipole 6hich 6ould radiate energy, @ust li4e
9ertKGs spar4s (Section #7-+7 Thus the atom should continuously lose energy until the
electron .ell into the nucleus and the radiation emitted 6ould 3e o. continuously /arying
6a/elength (.re0uency+, not the sharp lines actually o3ser/ed7
&1+1% 8o$rs t$eor0 o" t$e str;#t;re o" t$e $0/rogen atom
The a3o/e 6as the dilemma 6hich .aced ;iels 9enri4 <a/id Bohr (#%%5 I #$?2+ in
#$#,7 9e attac4ed it 6ith that miture o. 3oldness and intuition 6hich had
characterised the 6or4 o. 'instein and proposed .our ne6 la6s7
Bohrs La!s of the $ydrogen %to& 'tructure
#7 The electron in the hydrogen atom or3its the nucleus in a circular path, li4e a planet
around the sun7
27 ". the inLnite num3er o. possi3le or3its, only those are allo6ed .or 6hich the or3ital
angular momentum o. the electron is an integral multiple o. !lanc4Gs constant di/ided
3y 2( 7
,7 Contrary to classical electromagnetic theory, electrons in these allo6ed or3its do not
radiate energy7
*7 When an electron changes its or3it a 0uantum o. energy (photon+ is emitted or a3sor3ed
in accordance 6ith the e0uation E = h>, 6here E is the di..erence in the
energy o. the t6o or3its7
An postulate 2 Bohr 6as .ollo6ing !lanc4Gs lead7 !lanc4 had proposed that the energies
o. the oscillators in a 3lac4 3ody could ha/e only certain 0uantised /aluesP Bohr 6as
suggesting a similar thing .or the electron or3its o. the hydrogen atom7 But instead o.
energy he chose to 0uantise the angular momentum o. the electron7 At is not easy to
say 6hy Bohr chose to 0uantise angular momentum rather than energy, 3ut it may 3e
that it 6as 3ecause the units o. !lanc4Gs constant (J s+ are the same as those o. angular
n = % ? 5 * ,
n
2
AHcm
#
%2 25%7$
AHcm
#
<(o3s7+Hnm <(calc7+Hnm
, $- *$27, #5 2,, ?5?75 ?5?75
* #02 %2,7% 20 5?5 *%?7, *%?7,
5 #05 2$#75 2, 0,, *,*72 *,*72
? #0? ?,272 2* ,-, *#07, *#07,
- #0- **07* 25 #%2 ,$-7# ,$-7#
% #0- $?570 25 -0? ,%$70 ,%$70
$ #0% ,2*7- 2? 0?? ,%,7? ,%,7?
#0 #0% 5%270 2? ,2, ,-$7$ ,-$7$
#0$ ?-%7% 2- *20 ,?*7- ,?*7-
n
2

(
n
2

*
+
Ta?le &1& The Lrst eight Balmer lines (2s n%P n = , * . . . #0+ o.
hydro2 gen BalmerGs .ormula1 <!calc7" = ,?*.-n
2
,!n
2
*"
state energy
]
]
Charlotte '7 Coore, Atomic Energy Levels, 8ol A, =S ;ational Bureau o. Standards,
Circular *?-, Washington <C, #$*$7
momentum7 9o6e/er, .ollo6ing the discussion o. Chapter #, it should 3e clear that, as
6ith the gas la6s o. Boyle and Gay2Lussac, there can 3e only one test o. BohrGs la6s
and that is 6hether they reproduce the eperimental Lndings7
Ta3le 272 lists the 6a/elengths o. a series o. emission lines o. the hydrogen atom
6hich, in #$#,, had 3een 4no6n .or many years7 They are called the Balmer lines 3ecause
Johann Ja4o3 Balmer (#%25 I #%$%+, a S6iss school teacher, had sho6n in #%%5 that
the
6a/elengths o. these lines (in nm = #0
$
m+ Ltted the simple
.ormula1
,?*.-n
2
< =
!n
2
*"
!n
=
, * 5 . . ." !2.-.#"
BalmerGs e0uation, 6hich predicts the 6a/elengths /ery accurately and 6as deduced
.rom the eperimental data alone, is illustrated 6ith a graph in Digure 27%7 Thus, the test
270
#75
#70
075
,50 *00 *50 500 550 ?00 ?50 -00
Wa/elength, l (nm+
6ig;re &1, A graph o. BalmerGs e0uation .or the hydrogen atom spectrum
0
0
0
=
o. BohrGs la6s is their a3ility to interpret '0uation (27-7#+7 The application o. the Bohr
model to BalmerGs e0uation is descri3ed in detail in Bo 27#7 An the net section the
results deri/ed there are used to test the Bohr theory against eperiment7
&1+1& Comparison o" 8o$rs mo/el wit$ experiment
As sho6n in Bo 27#, the Bohr model leads to '0uation (B27#7#,+ .or the 6a/elengths
o. the atomic spectral lines o. the hydrogen atom1
,2?
2
ch
,
<
e
*
m
e

n
2

n
2

*
!B2.#.#,"
"n e/aluating the .actor ,2?
2
ch
,
He
*
m
e
using the /alues .or the .undamental constants
listed in Appendi #, 6e o3tain1
,2?
2
ch
,
e
*
m
e
=
,2 !%.%5*#$"
2
2.$$-$2 !?.?2?0%"
,

#0
##%
!#.?02#%"
*
$.#0$,$ #0
#0-
=
,?*.50- #0
$
m
This is in ecellent agreement 6ith Balmer, i7e7 6ith eperiment, and conLrms the
/alidity o. BohrGs model .or the hydrogen atom spectrum7
&1+1' 6;rt$er /eAelopment o" 8o$rs t$eor0
The ecellent agreement o. BohrGs theoretical result 6ith the eperimental data em3odied
in BalmerGs e0uation 6as most grati.ying and, at the time, it mar4ed a /ery important step
.or6ard7 But la6 2, the ar3itrary imposition o. 0uantisation upon 6hat 6as essentially a
classical solution o. the pro3lem 6as to no oneGs li4ing, least o. all to BohrGs7 Durthermore,
strenuous e..orts 3y Bohr and others, nota3ly Arnold Johannes Wilhelm Sommer.eld
(#%?% I #$5#+, to apply a similar, semi2classical approach to atoms 6ith more than
one electron .ailed to gi/e results in agreement 6ith eperiment and it 6as clear that a .ully
accepta3le theory o. the structure o. the atom 6as yet to 3e .ound7 The search .or a
.orm o. mechanics applica3le to atoms and molecules 6as to last .or a .urther #2 years7
AmaKingly, 6hen a /ia3le theory 6as .ound, t6o apparently /ery di..erent theories 6ere
announced at almost the same time7 >arl Werner 9eisen3erg (#$0# I #$-5+
descri3ed his matrix mechanics in #$25 and 'r6in SchroM dinger (#%%- I #$?#+ his
0ave mechanics in #$2?7 But the t6o approaches 6ere soon sho6n to 3e di..erent
.ormulations o. the same theory (compare the ;e6tonian, Lagrangian and 9amiltonian
.orms o. classical mechanics+, and 6e shall deal only 6ith SchroM dingerGs /ersion here7
But 3e.ore 6e ta4e our Lnal step to 0uantum mechanics 6e must note a suggestion made
in his !h< thesis 3y de Broglie 6hich, though it 6as not su3stantiated 3y eperiment until
a.ter the ad/ent o. 0uantum mechanics, sho6ed /ery clearly that a pro.ound di..erence
6as to 3e epected 3et6een the description o. /ery small particles 3y classical and 3y
0uantum mechanics7 At also had a great inOuence on SchroM dinger 6ho, in his
.amous paper o. #$2?, descri3ed de BroglieGs thesis as QinspiredG7
&1, /e 8R25IES !R2!2SA5
Louis 8ictor !ierre :aymond !rince de Broglie (#%$2 I #$%-+ descended .rom a
no3le .amily 6ho had ser/ed many Drench 4ings7 9e studied history 3e.ore ta4ing up
physics and in his doctoral dissertation (#$2*+ he reasoned as .ollo6s1
de BroglieGs !roposal 2-
According to 'insteinGs theory o. relati/ity1
E = mc
2
!2.%.#"
3ut 'instein, .ollo6ing !lanc4, also suggested that1
E = h> = hc,< !2.%.2"
there.ore, i. the momentum (%+ o. the photon as a particle is mc, then1
% = mc = E,c = h,<
!2.%.,"
and i. this result applies to other particles as 6ell as to photons, then all mo/ing particles
should 3e associated 6ith a 6a/elength (<+ gi/en 3y the e0uation1
< = h,% = h,mv
!2.%.*"
6here m and v are the mass and /elocity o. the particle respecti/ely7
This remar4a3le suggestion 6as conLrmed .or electrons 3y Clinton Joseph <a/isson
(#%%# I #$5%+ and Lester 9al3ert Germer (#%$? I #$-#+ 6ho, in #$2-, demonstrated
that a 3eam o. electrons directed at the sur.ace o. a nic4el crystal 6ere selecti/ely
di..racted at certain angles, @ust as F2rays are di..racted, 3y the regularly spaced layers
o. atoms in a crystal7
A similar eperiment 6as per.ormed independently 3y George !aget Thomson (#%$2 I
#$-5+ in #$2-7 An ThomsonGs eperiment, electrons 6ere accelerated 3y potentials o.
3et6een #0 and ?0 48 as a result o. 6hich, i. de Broglie is correct, their associated
6a/elengths 6ould lie 3et6een #2 and 5 pm respecti/ely7 This 6a/elength range is some
20 to 50 times smaller than the spacing 3et6een atoms in a metal and Thomson Lred a
/ery narro6 3eam o. his accelerated electrons through etremely thin (#0
-
m+ .oils o.
gold and platinum7 9e placed a photographic plate on the .ar side o. the .oil and 6hen
he de/eloped the plate .ound it to sho6 the circular inter.erence pattern 6ell 4no6n
.rom the corresponding eperiments 6ith light 3eams7 Durthermore, measurement o. the
inter.erence pattern and a 4no6ledge o. the /elocity o. the electrons and the spacing o.
the atoms in the metal .oil pro/ided a 0uantitati/e proo. o. de BroglieGs e0uation7 Cany
su3se0uent eperiments 6ith hea/ier particles ha/e conLrmed the early results7
]
The deep signiLcance o. this result is apparent 6hen 6e consider a simpliLed /ersion
o. ThomsonGs eperiment (Digure 27$+ in 6hich a 3eam o. electrons is directed at a screen
containing @ust t6o slits 6ith a photographic plate to o3ser/e the results7 Drom eperiment
6e 4no6 that an inter.erence pattern is o3ser/ed on the plate only i. there are t6o (or
more+ slits in the screen7 With one slit no inter.erence pattern is seen7 Also, 6e can
reduce the intensity o. the electron 3eam to such a le/el that 6e may consider the Lnal
pattern on the plate to 3e the accumulation o. the results o. many eperiments, each 6ith
an indi/idual electron7 But ho6 can this 3e interpreted i. the electron is a particleJ A
particle can only pass through one o. the slits, 3ut the eperiment seems to imply that the
presence o. a .urther slit, through 6hich the electron did not pass, has had an inOuence
on the electronGs tra@ectoryU
We are on /ery treacherous ground here7 'perience has sho6n that 6e cannot spea4
o. the path o. a particle in 0uantum mechanics in the same 6ay as 6e do in classical
mechanics7 We can only spea4 o. those things 6hich 6e can o3ser/e7 An this case 6e can
]
A nice anecdote is told a3out the Thomsons7 The .ather (JJT+ 6on the ;o3el !riKe .or !hysics in #$0? .or sho6ing that the
electron 6as a particle7 The son (G!T+ 6on the same priKe in #$,- .or sho6ing that the electron 6as a 6a/eU
2% Drom Classical to &uantum Cechanics
'lectron source 'lectron source 'lectron source
!hotographic plate !hotographic plate !hotographic plate
A single open slit
produces one 3and
on the photo2plate
A single open slit
produces one 3and
on the photo2plate
When 3oth slits are open
an inter.erence pattern o.
many 3ands is produced
6ig;re &1- An idealised representation o. G7!7 ThomsonGs eperiment
see the spot produced on the photographic plate 3y the electron, 3ut 6e cannot o3ser/e the
QpathG 6hich it has ta4en 3et6een the electron source and the plate and 6e must not ma4e
in.erences a3out 6hat that path might, or might not, ha/e 3een7 A much more detailed
discussion o. this pro3lem has 3een gi/en 3y Deynman
2
and 6e shall return to the su3@ect
o. 6hat 6e can and cannot 4no6 in Chapter ,7 At the moment 6e must continue on our
di.Lcult 3ut 6ell2deLned path Q.rom classical to 0uantum mechanicsG, .or 6e ha/e almost
reached our @ourneyGs end7
&1- THE SCHR2
C
3INER EQUATI2N
The title o. the paper in 6hich SchroM dinger announced his ne6 mechanics 6as
Q31anti+ Bation as an Eigenval1e Pro*lem G and in the Lrst paragraph he 6rote1
Q:n this comm1nication : 0ish to sho0 Crst for the sim%lest case of the non+relativistic and 1n%er+
t1r*ed hydrogen atom that the 1s1al r1les of 71antisation can *e re%laced *y another %ost1late in
0hich there occ1rs no mention of 0hole n1m*ers. :nstead the introd1ction of integers arises in the
same nat1ral 0ay as for exam%le in a vi*rating string for 0hich the n1m*er of nodes is integral.
-he ne0 conce%tion can *e generalised and : *elieve that it %enetrates dee%ly into the tr1e nat1re
of the 71ant1m r1les7
]
The title chosen .or his paper 3y SchroM dinger is /ery signiLcant, and 6e shall
return to it later7 But let us Lrst eamine the opening paragraph 0uoted a3o/e7
SchroM dinger immediately ma4es clear that he is going to deal only 6ith the simple case o.
the hydrogen atom7 9e is not going to include the e..ects o. the theory o. relati/ity in his
discussion, nor 6ill the atom 3e distur3ed (pertur3ed+ 3y any eternal .orces7 The second
hal. o. the Lrst sentence sho6s that it is the ar3itrary imposition o. 0uantisation 6hich is
SchroM dingerGs
]
A ha/e ta4en this 0uotation, ver*atim, .rom Linus !auling and '7 Bright WilsonGs Q:ntrod1ction to 31ant1m 5echanics G,
pu3lished in #$,57
*
Li4e the 3oo4 itsel., the translation o. the original German can scarcely 3e impro/ed upon7
The SchroM dinger '0uation 2$
target and the second sentence re/eals that he has .ound a theory in 6hich 0uantisation
arises naturally7
To illustrate the 6ay in 6hich integers can arise naturally in theoretical models o. phys2
ical phenomena, SchroM dinger re.ers to the /i3ration o. a stretched string, 6hich can
only /i3rate in such a 6ay as to produce the .undamental .re0uency and the Lrst, second,
third,
. . . nth . . . o/ertone, or harmonic, and .or 6hich the string has 0 # 2 , . . . n . . .
nodes
respecti/ely 3et6een the Led points at its ends7 9ere 6e must 3e6are7 SchroM
dingerGs .orm o. the ne6 mechanics has 3ecome 4no6n as 6a/e mechanics and he is here
illustrat2 ing his ne6 results 6ith the 6ell24no6n properties o. 6a/es on stretched strings7
But this does not mean that his e0uation can 3e deri/ed .rom such considerations7 The
SchroM dinger e0uation is not deri/a3le .rom classical mechanics, it is a ne6 postulate
as he himsel. ma4es clear in the 0uotation a3o/e7 So, 6hat is this ne6 postulateJ The
0uestion ta4es us 3ac4 to consider the title o. SchroM dingerGs paper7
&1-1% Eigen";n#tions an/ eigenAal;es
German is a language 6ith a remar4a3le a3ility .or 3uilding compound 6ords such as
Eigenf1n;tion and Eigen0ert7
,
At is easy to translate the second parts o. the a3o/e German
6ords Q91n;tion G = Qf1nction G and QWert G = Qval1eG (German nouns al6ays 3egin
6ith an upper2case letter+, 3ut it is /ery di.Lcult to Lnd a suita3le translation .or the
0uali.ying 6ord QEigen G7 The 6ord QspecialG has occasionally 3een used, 3ut it does
not imply an aspect o. Q3elonging toG 6hich QEigenG also has7 Thus, an eigen/alue is not
only a special /alue it also 3elongs to something, to its o6n special .unction and an
operator in .act (see Bo 272+7 The situation is 3est illustrated 6ith an eample o. an
eigen/alue2eigen.unction e0uation1
D
2
D
D
2
!sin ," =
D
!, cos ," = $ sin ,
This e0uation is a rather unusual one7 The mathematical operator, D
2
,D
2
, operates
on the .unction sin(, + (6e sho6 it in t6o steps to ma4e the process clear+ to gi/e
eactly the same .unction 3ac4 again, 3ut multiplied 3y a num3er, $ in this case7
There are rather .e6 cases 6here an operator, e7g7 +, , , , integrate, di..erentiate,
6hen applied to a .unction gi/es the .unction 3ac4 again multiplied only 3y a num3er7
When this unusual situation does occur the .unction is 4no6n as an eigen.unction o. the
operator and the num3er as the associated eigen/alue7 At is this mathematical phenomenon
6hich lies at the heart o. SchroM dingerGs mechanics7 9e disco/ered a 6ay o.
.ormulating an operator .or the energy o. the electron in the hydrogen atom and then
determined the eigen.unctions and eigen/alues o. that operator7 The eigen/alues are
then the possi3le energies o. the electron in the hydrogen atom, as could 3e tested
immediately 3y a comparison 6ith the eperimental spectral data7 The eigen.unctions are
.unctions 6hich descri3e the possi3le 6ays in 6hich the electron may 3e distri3uted
around the nucleus o. the hydrogen atom, each distri3ution 3eing associated 6ith a
particular energy gi/en 3y the associated eigen/alue7 These hydrogenic eigen/alues and
eigen.unctions 6ill 3e discussed in detail in Chapter 57 At the moment 6e shall Lnd it
easier i. 6e Lrst consider the eigen/alues and eigen.unctions o. some e/en simpler
pro3lems (Chapter ,+7 But simple though they are, 6e shall Lnd that these pro3lems ha/e
solutions 6ith important chemical applications7
,0 Drom Classical to &uantum Cechanics
&1%. 8I85I2RA!HY AN3 6URTHER REA3IN
#7 :7C7 'is3erg, 91ndamentals of 5odern Physics, Wiley, ;e6 Ror4, #$?-7
27 :7 Deynman, Six Easy Pieces, !enguin Boo4s, London, #$$%7
,7 An eample .re0uently 0uoted is1 Eona1dam%fschiffartsgesellschafts;a%it aF nsfra1 = the
6i.e
(fra1 + o. a captain (;a%itaF ns + in the <anu3e (Eona1 + steam2ship (dam%fschiffarts +
company
(gesellschaft +7
*7 L7 !auling and '7B7 Wilson, :ntrod1ction to 31ant1m 5echanics, CcGra629ill, ;e6 Ror4,
#$,57
82D &1% 8o$rs mo/el o" t$e $0/rogen atom in /etail
Motion in a #ir#le
BohrGs model o. the hydrogen atom pictures the electron or3iting the nucleus li4e a
planet around the sun7 The theory appeals to the results o. the classical mechanics o.
motion in a circle so it 6ill 3e use.ul i. 6e deri/e those 6e re0uire 3e.ore 6e start7
Digure B27#7#(a+ sho6s a mass m mo/ing 6ith a constant speed (v+ along a circular
path o. radius r centered at "7 Though the speed is constant, the /elocity, 6hich
is a /ector 0uantity and there.ore has direction as 6ell as magnitude, is not7 The
magnitude o. the /elocity o. the mass is its speed, 6hich is constant, 3ut its direction
is continuously changing7 The /elocity /ector (v+ is al6ays at right angles to the
radial /ector (r+ and Digure B27#7#(3+ illustrates the situation at t6o closely spaced
instants in time during 6hich the mass has mo/ed through a /ery small angle !d^"7
The distance mo/ed along the arc, ds, is e0ual to r _ /E i. /E is measured in radians7
Also, the speed along the arc is v = ds,dt 7 An Digure (c+ the di..erence in the
t6o
/elocity /ectors, dv = v
2
v
#
, is .ound 3y means o. /ector su3traction7 Since
the magnitudes o. v
2
and v
#
are e0ual to the constant v, .or small angles 6here the
arc
o. the circle and its chord are not apprecia3ly di..erent in length, dv = v _ /E7
Thus
6e ha/e1
ds = r _ /E and dv = v _ /E
'liminating /E gi/es1 dv,ds = v,r 7
The acceleration, a, o. the mass can no6 3e .ound 3ecause1
dv ds dv
v v
2
a =
dt
=
dt

ds
= v _
r
=
(B27#7#+
r
2
2
#
#
ds
r r
r
/E
r
"
2
/E d

#
(a+
6ig;re 8&1%1% Cotion in a circle
Boes .or Chapter 2 ,#
ds = r /E
d =
2
I
#
=

/
E
(3+
(c+
At is clear .rom Lgure (c+ that .or /ery small angles !/E", the change in /elocity
!dv" is at right angles to v and there.ore directed along r to6ards "7 Thus, i. the
change in /elocity is directed to6ards " so also must 3e the acceleration7
The angular momentum (l+ generated 3y the counter2cloc46ise motion illustrated
in (a+ is gi/en 3y the /ector product1
l = r p = r mv = rmv
(B27#72+ The last e0uality .ollo6s 3ecause r and v are al6ays at right angles to
each other
and the /ector product o. t6o /ectors is the product o. their magnitudes multiplied 3y
the sine o. the angle 3et6een them7 The direction o. the /ector l is out o. the paper
to6ards the reader7
Ang;lar moment;m an/ energ0
Dor the system descri3ed a3o/e all energy is 4inetic energy 6hich can 3e readily
epressed in terms o. the angular momentum1
mv
2
!mv"
2
!l,r "
2
l
2
E!4inetic energy" =
2
=
2m
=
2m
=
2mr
2
(B27#7,+
T$e 8o$r mo/el
Consider an electron o. mass m
e
and charge e mo/ing 6ith /elocity v in a circular
or3it o. radius r around a much hea/ier nucleus o. charge +e (Digure B27#72+7 The
electron .ollo6s this path 3ecause o. the coulom3ic .orce o. attraction, e
2
,*( ?
0
r
2
, pulling it to6ards the nucleus7 ?
0
is the /acuum permitti/ity7 The electron does
not .all into the nucleus 3ecause o. its /elocity at right2angles to the line 3et6een the
t6o particles, the radial /ector7 But, as sho6n a3o/e, the coulom3ic .orce does
cause an
acceleration o. the electron to6ards the nucleus e0ual to v
2
,r , 6here the negati/e
e
m
e
5 r
)e
6ig;re 8&1%1& BohrGs model o. the hydrogen atom
o
e
=
o
o o
o
e

#
sign indicates that the acceleration, li4e the .orce 6hich causes it, is in the direction
o. decreasing r 7 ;o6, according to ;e6ton, .orce = mass acceleration so1
e
2
*( ?
o
r
2
=
m
e
v
2
r
or r =
e
2
*( ?
o
m
e
v
2
(B27#7*+
The discussion up to this point has 3een 3ased entirely upon classical theory and
there.ore 6e Lnd that no restriction is placed upon the radius o. the electronGs or3it
(r +7 Dor any choice o. r a /elocity can 3e .ound to 3alance the a3o/e e0uation7 BohrGs
second la6 introduces 0uantisation 6ith the postulate that only those or3its .or 6hich
the or3ital angular momentum is an integer multiple o. h,2( are allo6ed7 The angular
momentum is m
e
vr so BohrGs 0uantum condition is1
m
e
vr = nh,2( n = # 2 , . . .
(B27#75+
n = Kero is not permitted 3ecause it 6ould imply either v = 0, gi/ing rise to an
inLnite radius ('0uation (B2727#++ or r = 07 A. the allo6ed or3its satis.y '0uation
(B27#75+ then the allo6ed /alues o. the radius can 3e o3tained 3y using '0uation
(B27#75+ to eliminate v .rom '0uation (B27#7*+ gi/ing1
e
2
r =
*(? m
*(
2
m
2
r
2
e
or m r
n
2
h
2
?
o
n
2
h
2
(B27#7?+
e
2
(
and using '0uation (B27#75+ again1
nh nh
e
2
( e
2
v =
2(m r
=
2(

? n
2
h
2
=
2? nh
(B27#7-+
e o o
To o3tain the total energy, E, o. the atom 6e use1
E = potential energy + 4inetic energy
so that1
e
2
E =
*(? r
+
m
e
v
2
2
2
e
2

e
2
( m
e

m
e

e
2
(B27#7%+
=
*( ?
o
e
*
m
e
?
o
n
2
h
2
+

#

2 2?
o
nh
e
*
m
e
=
*?
2
n
2
h
2
# +
2
=
%?
2
n
2
h
2
The presence o. the 0uantum num3er n on the right2hand side o. '0uation (B27#7%+
.or E sho6s 6hy n cannot 3e Kero and that 6e ha/e 0uantisation o. the total energy
o. the hydrogen atom7 We recognise this 3y 6riting the 0uantum num3er in 3rac4ets1
E!n" =

e
*
m
e

(B27#7$+
n
2
%?
2
h
2
We no6 re0uire to see i. 6e can reproduce BalmerGs '0uation ('0uation (27-7#++7
According to BohrGs .ourth postulate, the energy o. a spectral line is gi/en 3y the
0
2 #
=
di..erence 3et6een t6o o. the a3o/e 0uantised energy /alues o. the hydrogen atom,
i7e7 the energy calculated .or t6o di..erent 0uantum num3ers, n
#
and n
2
say7 Thus1
e
*
m
e

# #

e
*
m
e
!n
2
n
2
"
E!n
2
" E!n
#
" = E =
%?
2 2 2
=
o
n h n
2
n
2
%?
2
n
2
h
2
n
2
n
2
# 2 o # 2
(B27#7#0+
But the .re0uency o. light (>+ and the 6a/elength (<+ are related 3y the /elocity
(c+ in the e0uation c = ><, so that1
E = h> = hc,<
(B27#7##+ There.ore, the 6a/elength o. a line in the Balmer series is1
%?
2
ch
,
n
2
n
2
%n
2
?
2
ch
,

n
2
< =
0

# 2 # 0
=
2
(B27#7#2+
e
*
m
e
n
2
n
2
e
*
m
e

n
2
n
2
2 # 2 #
A comparison o. this e0uation 6ith '0uation 27-7# suggests that n
#
= 2 and n
2
=
n, and i. 6e ma4e these su3stitutions our epression .or < can no6 3e 6ritten1
,2?
2
ch
,
<
e
*
m
e

n
2

n
2

*
(B27#7#,+
The crucial test o. BohrGs la6s is no6 o3tained 3y e/aluating the .actor ,2?
0
2
ch
,
, e
*
m
e
in '0uation (B2727#,+7 This calculation is carried out in Section 27-727
6here ecellent agreement 6ith Balmer, and there.ore 6ith eperiment is .ound7
82D &1& 2perators
We can di/ide the sym3ols used in mathematics into t6o types, the o%erators and the
o%erands7 The operands are the num3ers, or in the case o. alge3ra, the letters 6hich
represent the num3ers7 The operators are the sym3ols 6hich tell us 6hat 6e ha/e
to do 6ith the num3ers7 Thus, in the epression 2 + 5, the operator, +, tells us that
6e are to add the num3er 5 to the num3er 27 Similarly, 2 5 indicates that 5 is
to 3e multiplied 3y 27 The operator

tells us to ta4e the s0uare root o. the
operand7
As eamples o. more complicated operators 6e may ta4e those .or di..erentiation
and integration 6hich, as it happens, occur .re0uently in 0uantum mechanics7 An a
crude analogy 6e might say that the surgeon is the operator and the patient the
operand7
!airs o. operators are lin4ed 3y a /ery important property 6hich is independent
o. the operand7 This may 3e illustrated using the operators .or multiplication 3y y,
y, multiplication 3y K, K, and ta4ing the s0uare root,

7 As the operand 6e
shall
use *y
,
7
Dirst 6e ta4e the operators y and K and apply them to the operand in the
order y K7 We o3tain1
y !K Z*y
,
\" = y !*Ky
,
" = *Ky
*
And i. 6e apply the t6o operators in the re/erse order 6e get the same result, i7e71
K !y Z*y
,
\" = K !*y
*
" = *Ky
*
But i. 6e choose the operator pair y and

, 6e Lnd that the order in 6hich 6e

apply them is important 3ecause1
# ,
But1
!K Z*y
,
\"
=
!*Ky
,
" = 2K
2
y
2
, ,
K Z*y
,
\ = K !2y
2
" = 2Ky
2
We say that the operator pair y and K comm1te, 3ut the pair y and

do
not
commute7 The commutation or non2commutation o. pairs o. operators plays a /ery
important role in 0uantum mechanics as 6e shall see in Chapter ,7
!R285EMS 62R CHA!TER &
#7 Dor the special case o. a planet 6ith a circular or3it, deduce >eplerGs third la6 .rom
;e6tonGs la6s7
27 Calculate the radius o. the circular or3it o. a geostationary satellite, i7e7 a satellite
6hich remains in eactly the same position a3o/e the sur.ace o. the earth7 <etermine
!ro3lems .or Chapter 2 ,5
its altitude and or3ital /elocity7 Assume that the mass o. the earth is 5.$%, #0
2*
4g,
its radius is ?.,-% #0
?
m and the gra/itational constant G = ?.?-, #0
##
m
,
4g
#
s
2
7
,7 'stimate the 6or4 .unctions W(;a+ and W(Li+ .rom Digure 2757
*7 The most po6er.ul tennis players are reputed to ser/e the 3all at a speed o. a3out
200 4mHhour7 A. the mass o. the 3all is 5% g calculate its 6a/elength7
57 ConLrm the range o. 6a/elengths 0uoted in Section 27% .or ThomsonGs accelerated
electrons7
?7 By epanding the eponential in '0uation 2757*3, sho6 that =!>" >
2
6hen h> ;- 7
Chapter ,
T$e Appli#ation o" Q;ant;m
Me#$ani#s
,70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,%
,7# "3ser/a3les, operators, eigen.unctions and eigen/alues . . . . . . . . . . . . . . ,%
,72 The SchroM dinger method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,$
,7, An electron on a ring . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *0
,7,7# The 9amiltonian operator .or the electron on a ring . . . . . . . . . . *0
,7,72 Solution o. the SchroM dinger e0uation . . . . . . . . . . . . . . . . . . . . *#
,7,7, The accepta3le eigen.unctions . . . . . . . . . . . . . . . . . . . . . . . . . *#
,7* 9uM c4elGs (*N + 2+ rule1 aromaticity . . . . . . . . . . . . . . . . . . . . . . . . . . **
,75 ;ormalisation and orthogonality (Bo ,72+ . . . . . . . . . . . . . . . . . . . . . . *?
,7? An electron in a linear 3o . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *?
,7?7# The 9amiltonian operator .or an electron in a linear 3o . . . . . . . *?
,7?72 The accepta3le eigen.unctions . . . . . . . . . . . . . . . . . . . . . . . . . *-
,7?7, Boundary conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . *%
,7- The linear and angular momenta o. electrons conLned 6ithin a
one2dimensional 3o or on a ring . . . . . . . . . . . . . . . . . . . . . . . . . . . . *%
,7-7# The linear momentum o. an electron in a 3o . . . . . . . . . . . . . . *$
,7-72 The angular momentum o. an electron on a ring . . . . . . . . . . . . 50
,7% The eigen.unctions o. di..erent operators . . . . . . . . . . . . . . . . . . . . . . . 52
,7$ 'igen.unctions, eigen/alues and eperimental measurements . . . . . . . . . . 5,
,7#0 Core a3out measurement1 the 9eisen3erg uncertainty principle . . . . . . . . 55
,7## The commutation o. operators (Boes 272 and ,7?+ . . . . . . . . . . . . . . . . 5-
,7#2 Com3inations o. eigen.unctions and the superposition o. states . . . . . . . . 5%
,7#, "perators and their .ormulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5$
,7#,7# !osition or co2ordinate, x . . . . . . . . . . . . . . . . . . . . . . . . . . . 5$
,7#,72 !otential energy, V

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5$
,7#,7, Linear momentum, p

x
. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#,7* >inetic energy, W

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#,75 Angular momentum, L

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#* Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?0
,7#5 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . ?#
!ro3lems .or Chapter , . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -#
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
,% The Application o. &uantum Cechanics
2
'1. INTR23UCTI2N
Consider the hydrogen molecule, 9I97 The hydrogen atoms each ha/e a mass o. #.?-*
#0

2-
4g and their nuclei are separated 3y a 3ond o. length

-*

#0

#2
m7 An actual
.act, this is the e0uili3rium 3ond length o. the molecule, .or this minute entity is in
constant /i3ration 6ith a .re0uency o. #,2 #0
#2
oscillations per second7 Just pause .or
a moment and try to picture the molecule7 An the time it ta4es to 3lin4, .or eample, it 6ill
ha/e completed #,2 million, million /i3rations7 As it permissi3le to descri3e such a motion
as a Q/i3rationG 6hen 6e cannot really e/en imagine such .re0uenciesJ Casses as small as
#0

2-
4g and distances as short as #0

#2
m are indescri3a3ly remote .rom the phenomena
6hich 6e eperience directly 6ith our o6n senses7 &uantum mechanics, 6hich has no6
stood the test o. more than -5 years o. rigorous application, is the mathematical model
6hich has 3een constructed to descri3e atomic and molecular systems and to interpret the
results o. the eperiments 6hich 6e per.orm upon them7 But it should come as no surprise
6hen the picture o. this 6orld o. atoms and molecules, dra6n 3y 0uantum2mechanical
methods, sometimes seems /ery strange to us7
The early pioneers o. the su3@ect soon disco/ered that, in order to 4eep on course in
interpreting o. the results o. 0uantum mechanics, 6e must 3e /ery care.ul to .ocus our
attention upon the 0uantities 6hich can 3e measured in a particular eperimental system
and re.rain .rom speculation a3out those things 6hich cannot7 (:ecall the inter.erence
o. photons discussed in Section 27%7+ Thus, to return to the eample o. the hydrogen
molecule, the e0uili3rium 3ond length o. the molecule can 3e 3oth measured and cal2
culated to high degrees o. accuracy7 But there is no 6ay in 6hich the paths o. the t6o
electrons 6hich .orm that 3ond can 3e .ollo6ed or descri3ed7 We can only gi/e a Lgure
.or the pro3a3ility o. Lnding an electron (6e cannot say 6hich oneU+ at any particular
point in space7
Thus, in this chapter 6e are concerned not only to illustrate the 6ay in 6hich 0uantum
mechanics is applied, 3ut also to ma4e clear @ust 6hat in.ormation can 3e o3tained .rom
0uantum2mechanical calculations or 3y eperiment7 We shall Lnd that, though the in.or2
mation 6hich 6e can o3tain is restricted 6hen compared 6ith that a/aila3le in classical
mechanics, this is not so surprising 6hen 6e consider the .undamental limitations 6hich
must apply to measurements on atomic and molecular systems7
'1% 28SERVA85ES< 2!ERAT2RS< EIEN6UNCTI2NS
AN3 EIENVA5UES
Any phenomenon 6e can o3ser/e, and particularly one 6hich 6e can measure and assign
a numerical /alue to, e7g7 energy or angular momentum, is 4no6n as an o*serva*le7 At
is the primary o3@ecti/e o. 0uantum mechanics to pro/ide a theory 3y means o. 6hich
the /alues o. such o3ser/a3les can 3e calculated7 Just as classical mechanics pro/ides an
e0uation .or determining the 4inetic energy o. a mo/ing mass (47e7
=
#
mv
2
+, so 0uantum
mechanics pro/ides us 6ith an e0uation 3y means o. 6hich the 4inetic energy o. a mo/ing
electron can 3e determined7
An Section 27$ 6e sa6 that, 6hen proposing his ne6 6a/e mechanics, 'r6in SchroM
2 dinger suggested that the mathematical concept o. eigen.unctions and eigen/alues
6ould 3e .ound to lie at the heart o. any theory in 6hich 0uantisation arose naturally,
rather
The SchroM dinger Cethod ,$
than 3eing ar3itrarily imposed7 All su3se0uent 6or4 has demonstrated that SchroM
dingerGs intuition 6as indeed correct and in the application o. 0uantum mechanics
today 6e .ormulate SchroM dingerGs method in terms o. .our entities1 an o*serva*le,
the particu2 lar 0uantum2mechanical o%erator associated 6ith that o3ser/a3le and the
eigenf1nctions and eigenval1es o. that operator7 The operator, eigen.unction and
eigen/alue are related in the e0uation1
4%erator operating on Eigenf1nction = Eigenval1e Eigenf1nction !,.#.#"
The usual mathematical .ormulation o. the relationship is1
:


n
= r
n

n
!,.#.2"
and a speciLc eample is1 D
2
!sin ax",D x
2
= a
2
sin ax7 The operator,
:

(designated as
such 6ith the caret mar4 or circumOeP D
2
,D x
2
in the eample+, operates upon the
eigen2
.unction,
n
(sin ax+, 6hich is a .unction o. the co2ordinate system in 6hich 6e place the
atom or molecule 6e are studying, e7g7 the Cartesian co2ordinates x y and B7 The result is
the eigen.unction multiplied 3y the eigen/alue, r
n
(

a
2
+7 We shall see 3elo6 that the .act
that the eigen.unction is descri3ing a real atomic or molecular system places important
limitations upon the .orm 6hich it may ta4e7 The o3ser/a3le appears in '0uations (,7#7#+
and (,7#72+ as the eigen/alue, r
n
, 6hich is simply a num3er that is the /alue o. the o3ser/2
a3le in the units 6e ha/e chosen .or the calculation, e7g7 an energy in J7 The su3script,
QnG, indicates that there are generally many eigen.unctions o.
:

and an e0ual num3er o.

corresponding eigen/alues, each characterised 3y a di..erent /alue o. n7 We shall Lnd that
n is a 0uantum num3er, or more o.ten a set o. 0uantum num3ers, e7g7 those descri3ing
the electronic state o. an atom7
'1& THE SCHR2
C
3INER METH23
SchroM dingerGs method consists o. three 3asic
steps1
#7 <etermine the operator associated 6ith the o3ser/a3le to 3e calculated7
27 Dind the eigen/alues and eigen.unctions o. the operator7
,7 'nsure that the eigen.unctions are physically accepta3le, in 6hich case the correspond2
ing eigen/alues 6ill 3e the possi3le, 0uantised /alues o. the o3ser/a3le7
At is the process o. choosing the appropriate operator 6here a postulate is made 6hich
can only 3e tested against eperiment7 An .ormulating classical mechanics ;e6ton made
the three postulates descri3ed in Section 2727 To interpret the motion o. the planets he
added a .ourth postulate, gra/itational attraction, and then demonstrated that these postu2
lates 6ere appropriate 3y sho6ing that the data .or the motion o. the planets around the
sun could 3e accurately reproduced 3y a mathematical model o. planetary motion 3ased
upon them7 An @ust the same 6ay, SchroM dinger postulated the .orm o. the operator
that 6ould ha/e as its eigen/alues the possi3le energies o. the electron in a hydrogen
atom and tested his postulate 3y calculating the hydrogen atom spectrum7 At the same
time he sho6ed the 6ay in 6hich the operators re0uired .or all the other 0uantum2
mechanical pro3lems o. interest in chemistry can 3e o3tained (Section ,7#,+7 An order
to illustrate
*0 The Application o. &uantum Cechanics
SchroM dingerGs method 6e shall consider t6o pro3lems 6hich, though they are
idealised and simple, also ha/e interesting chemical applications7 The pro3lems concern
the 0uan2 tum mechanics o. an electron conLned to mo/e 6ithin a one2dimensional 3o
or around a ring7
'1' AN E5ECTR2N 2N A RIN
Dollo6ing SchroM dingerGs method, our Lrst tas4 is to determine the .orm o. the energy
oper2 ator7 This operator is called the 8amiltonian, a.ter William :o6an 9amilton (#%05 I
#%?5+ 6ho de/eloped a .ormulation o. classical mechanics in 6hich the relationship o. the
latter
to 0uantum mechanics can 3e most clearly recognised7 We shall 6rite it as 9

7
'1'1% T$e Hamiltonian operator "or t$e ele#tron on a ring
Consider an electron o. mass m
e
6hich is conLned to mo/e at /elocity v
e
in a circular
path o. radius r (Digure ,7#+7 There is no positi/e charge at the centre o. the circle, as
there is in the Bohr model o. the atom, so the electron has only 4inetic energy7 A. the
electron o3eyed the la6s o. classical mechanics its energy 6ould 3e1
E
=
#
m
e
v
2
=
!m
e
v
e
r"
2
,2m
e
r
2
!,.,.#"
2
e
We 6rite the epression .or the classical 4inetic energy in the a3o/e, more complicated,
6ay 3ecause SchroM dingerGs recipe .or Lnding a 0uantum2mechanical operator
depends upon Lrst 6riting do6n the classical mechanical epression .or the o3ser/a3le in
0uestion, in this case the 4inetic energy, and then trans.orming it to the re0uired operator
3y means o. a set o. rules7 An this case 6e note that the 0uantity !m
e
v
e
r"
2
is the s0uare o.
the angular momentum o. the electron (see Chapter *+ and SchroM dingerGs postulate .or
o3taining the
operator corresponding to angular momentum s0uared, l
2
, is1
l
2
= !m
e
v
e
r"
2
l
2
= !h,2( "
2
D
2
,D $
2
!,.,.2"
That is, 6e .orm the operator 3y replacing the classical epression .or the s0uare o. the
angular momentum 3y h`
2
{h`
h,2( } times the second deri/ati/e o. the 6a/e2
.unction
6ith respect to $, the angle deLning the position o. the electron as it tra/els around the
ring7 :ules .or .orming other operators 6ill 3e gi/en as the need arises7 Thus, 6e re0uire
e
m
r
.
6ig;re '1% An electron on a ring
e
An 'lectron on a :ing *#
the eigen/alues (E
n
+ and eigen.unctions (
n
+ 6hich sol/e the e0uation1
h`
2
9


n

2m r
2

D
2

n
D$
=
E
n

n
!,.,.,"
As a3o/e, the su3script n 6ill 3e used to characterise the eigen.unctions and the
associated eigen/alues, o. 6hich there are usually a large num3er7 At must 3e emphasised
that the .orm o. the operator is a postulate7 Although SchroM dingerGs method ma4es
use o. a .ormula .rom classical mechanics as a stepping stone in o3taining the operator, the
relationship 3et6een the classical epression and the 0uantum operator is %ost1lated 1 the
operator is not derived .rom classical mechanics7 The proo. o. the /alidity o. the postulate
lies in the results 6hich it gi/es and 6hich 6e no6 determine7
'1'1& Sol;tion o" t$e S#$roC /inger e@;ation
An the second o. SchroM dingerGs three steps, 6e no6 see4 a .unction 6hich, i. it is to
3e an eigen.unction, must 3e such that 6hen di..erentiated t6ice 6ith respect to the
/aria3le $ it returns to its original .orm7 T6o .unctions 6ith @ust this property spring
readily to mindP sin(a$+ and cos(a$+, 6here a is a num3er (Bo ,7#+1
D
2
!sin a$",D $
2
= aD !cos a$",D $ = a
2
sin a$
D
2
!cos a$",D $
2
= aD !sin a$",D $ = a
2
cos a$
'ither o. these .unctions is an eigen.unction o. the operator 6ith an eigen/alue o.
a
2
h
`
2
,2m
e
r
2
3ecause1
#

2m
e
r
2
h`
2

D
2
sin!a$"
D
2
$
=
a
2
h`
2
2m
e
r
2
sin!a$" !,.,.*"
6ith a /ery similar result .or the cosine .unction7
There.ore, the energy o. our system is a
2
h`
2
,2m
e
r
2
7 9o6e/er, a momentGs
consideration sho6s that 6e are not yet home and dry7 Though h and m
e
are Led, natural
constants and the radius (r + 6ould 3e Led .or any particular pro3lem, no restriction
has 3een placed
upon the constant a7 Conse0uently, any desired energy can 3e o3tained 6ith a suita3le
choice o. the /alue o. aP i7e7 there is as yet no 0uantisation7 We must no6 proceed to
SchroM dingerGs third step and eamine the eigen.unctions sin(a$+ and cos(a$+ to see
i. they are physically accepta3le7
'1'1' T$e a##epta?le eigen";n#tions
The meaning o. the eigen/alues o. SchroM dingerGs e0uations 6as clear .rom the start
and ne/er appears to ha/e presented the pioneers o. 0uantum mechanics 6ith any
di.Lculties7 The interpretation o. the eigen.unctions, on the other hand, raised many
philosophical pro3lems a3out 6hich argument and discussion still continue more than
-5 years a.ter SchroM dingerGs Lrst pu3lication o. his ne6 mechanics7 9o6e/er, 6e shall
adopt the inter2 pretation Lrst suggested 3y Ca Born (#%%2 I #$-0+ in #$2?7 This is
the /ie6 ta4en in all chemical applications o. 0uantum mechanics7 Born proposed that
*2 The Application o. &uantum Cechanics
the s71are o. the eigen.unction, e/aluated at any point in space, gi/es the %ro*a*ility o.
Lnding the particle
descri3ed 3y that eigen.unction at that particular point7 An interpreting the eigen.unction
in this 6ay Born too4 a /ery .undamental step7 9e a3andoned the classical certainty o. a
precise position .or the particle and introduced in its place the concept o. the pro3a3ility
o. Lnding a particle at any particular point in space7 The signiLcance o. this departure
.rom the certainty o. classical mechanics cannot 3e eaggerated7
Thus, i. a particular /alue o. the angle $ is chosen and the eigen.unctions sin(a$+
and cos(a$+ o. the particle on a ring at that point e/aluated, then the s0uare o. the result
gi/es the pro3a3ility o. Lnding the electron at that point in its endless @ourney around the
ring7 Dor a concrete eample, i. a /alue a = *.% is chosen, the .unctions sin(*.%$+ and
Zsin(*.%$+\
2
plotted against $ .or /alues o. $ .rom 0 to ca7 ,( are sho6n in Digure ,727
We note that the eigen.unction itsel. has regions o. 3oth positi/e and negati/e sign, i7e7
it has the property o. phase7 But the pro3a3ility .unction, the s0uared eigen.unction, is
al6ays positi/e as it must 3e i. it represents pro3a3ility7 =sing Digure ,72 6e can readily
Lnd the /alue o. the eigen.unction .or any /alue o. $ and hence determine the pro3a3ility
that the electron can 3e .ound at that particular position around the ring7 But the linear
$2ais o. Digure ,72 conceals, or rather does not ma4e o3/ious, a .undamental deLciency
in the eigen.unction sin(*.%$+7 Digure ,7, in 6hich the .unction is plotted on a dotted
circle (positi/e /alues outside the circle, negati/e /alues inside+ sho6s that 6hen the
angle $ has reached the /alue o. 2( and the electron 3egins a ne6 circuit o. the ring
another, di..erent /alue o. the eigen.unction is o3tained .or the same position on the ring7
To 3e speciLcP sin!*.%$" = 0.0 .or $ = 0 3ut .or $ = 2( , sin!*.%$" = 0.$5#7 "n the
Born model this 6ould imply that the pro3a3ility o. Lnding the electron at the same place
on the ring is proportional
]
to t6o di..erent num3ers, 070 and !0.$5#"
2
= 0.$0*7 This
#70
075
070
075
#70
sin(*7%.+
0 2 * ? % #0
Angle . (radians+
#70
07%
07?
07*
sin
2
(*7%.+
072
070
0 2 * ? % #0
Angle . (radians+
6ig;re '1& Linear plot o. sin(*.%$+ and Zsin!*.%$"\
2
]
We use the 6ord QproportionalG 3ecause the 6a/e .unction still has to 3e multiplied 3y a .actor 6hich 6e shall eplain and
determine in Section ,757
$0
#20 ?0
#50 ,0
#%0 0
2#0
,,0
2*0
2-0
,00
6ig;re '1' Circular plot o. sin(*.%$+, $ = 0 ca72.5(
$0
#20 ?0
#50 ,0
#%0 0
2#0
,,0
2*0
2-0
,00
6ig;re '1( Circular plot o. sin(*.%$+, no limit on $
cannot 3e so7 9ence, though the eigen.unction is per.ectly accepta3le mathematically, it
is %hysically 0uite unaccepta3le7 To 3e physically accepta3le, an eigen.unction must ha/e
only one /alue (i.e. it m1st *e single+val1ed + at any point7 Another 6ay o. loo4ing at the
result is sho6n in Digure ,7*7 A. 6e plot the eigen.unction against $ 6ith no upper limit
on $, 6e disco/er that a.ter L/e cycles around the ring the /alue o. the eigen.unction
3egins to repeat itsel. and a rather pretty pattern results7 A detailed eamination re/eals
that at any /alue o. $ there are L/e /alues o. the eigen.unction 6hich are such that their
sum is e0ual to Kero7 Thus the phases o. the eigen.unction cancel each other gi/ing a
total o. Kero and hence Kero pro3a3ility7 An the language o. 6a/es, 6e 6ould say that the
.unction has 3een reduced to Kero 3y destructi/e inter.erence7
The only physically reasona3le eigen.unctions are ones .or 6hich the /alue at $ = 0 is
e0ual to the /alue at $ = 2( *( . . . (Digure ,75+7 What does this mean .or our eigen.unc2
tions and eigen/aluesJ 9o6 does this re0uirement restrict the /alue o. aJ We re0uire that1
sin!a$" = sin!aZ$ + 2( \" = sin!a$ + 2a( " = sin!a$" cos!2a( " + cos!a$" sin!2a( "
$0
#20 ?0
#50 ,0
#%0 0
2#0
,,0
6ig;re '1) Circular plot o. sin(5$+
2*0
2-0
,00
Clearly, the e0uality 6ill 3e achie/ed i. cos!2a( " = #.0 and sin!2a( " = 0.0, 6hich
is only true 6hen a = 0 # 2 , . . . There.ore, i. the eigen.unctions are to 3e physically
reasona3le a must 3e Kero or an integer and the corresponding eigen.unctions are gi/en 3y1

sin a
= sin!a$" and
cos a
= cos!a$" !,.,.5"
and the energies 3y1
.or 3oth eigen.unctions7
E
a
= a
2
h`
2
,2m
e
r
2
!,.,.?"
Thus, 0uantisation has arisen in the most natural 6ay, as a result o. the re0uirement that
our eigen.unctions should 3e physically reasona3le on BornGs model7 Digure ,75 sho6s
the .unction = sin!5$" in the circular .orm in 6hich a 6hole num3er o. cycles o.
the .unction Lt eactly into the circular path7 At is no6 natural to interpret our integer
a as the num3er n, 6hich 6e introduced in '0uations (,7#72+ and (,7,7,+ to allo6 .or
the .act that there may 3e many eigen.unctions and eigen/alues o. the same operator7 An
this eample the accepta3ility o. the eigen.unction 6as determined 3y the re0uirement
that it 3e single2/alued7 Since the pro3a3ility must 3e smoothly continuous and Lnite, in
order to 3e physically accepta3le, the Born model also places the general re0uirements
on eigen.unctions that they too must 3e continuous and Lnite e/ery6here7
At is interesting to note that the energy le/els occur in pairs o. e0ual energy (Digure ,75+,
one le/el corresponding to the sine eigen.unction and the other to the cosine eigen.unction7
An 0uantum2mechanical parlance, such le/els are said to 3e degenerate7 An Section ,7-72
6e shall disco/er the .undamental origin o. this degeneracy7 Dor a = 0 there is only
one eigen.unction, the cosine .unction (since sin!0" = 0+, and there.ore only one lo6est
energy le/el o. Kero energy7
'1( HU
C
C=E5S F(# ) &G RU5E:
AR2MATICITY
At 6as stated a3o/e that, although the 0uantum2mechanical pro3lems to 3e discussed in
this chapter 6ere simple ones, they ne/ertheless thro6 /alua3le light upon chemical
pro3lems7 The 0uantum2mechanical description o. the electron conLned to mo/e on a ring
9uM c4elGs (*N + 2+ :ule1 Aromaticity *5
pro/ides a 3asis .or 9uM c4elGs (*N + 2+ rule .or the aromatic hydrocar3ons7 :ecall
that the aromatic hydrocar3ons, e7g7 3enKene, naphthalene, anthracene, phenanthrene etc7,
ha/e
? #0 #* . . . = !*N + 2" con@ugated car3on atoms, 6here N = # 2 , . . . (Digure ,7-+7
At is generally accepted that the particular sta3ility o. these molecules depends upon the
presence o. a ( 2electron system, and that each car3on atom contri3utes one electron to
this system, i7e7 the num3er o. ( 2electrons in an aromatic hydrocar3on is e0ual to the
num3er o. car3on atoms (*N + 2+7 (The 9uM c4el theory o. ( 2electron systems is
discussed
in detail in Chapter #27+ An many o. these molecules, especially the smaller ones, all the
car3on atoms lie on the periphery o. the car3on2atom s4eleton and 6e can approimate
the se0uence o. car3on atoms to a ring around 6hich the delocalised ( 2electrons may
circulate 6hile the remainder o. the 3onding electrons are localised in the CIC and
CI9 3onds7 An this model, the energy2le/el scheme .or the ( 2electrons is that sho6n in
Digure ,7? and i. 6e Lll the le/els 6ith electrons, t6o per le/el (the !auli principle+,
'nergy in units
o. h
2
H%p
2
m
e
r
2
25 n = 5
#?
n = *
$ n = ,
* n = 2
#
0
N cos(n.+ N sin(n.+
n = #
n = 0
6ig;re '1* The energy le/els .or an electron on a ring
BenKene
Anthracene
;aphthalene
!henanthrene
6ig;re '1+ The structures o. some o. the smaller aromatic hydrocar3ons
*? The Application o. &uantum Cechanics
2
starting .rom the lo6est (the au.3au principle+, then it is easy to see that to produce a
sta3le conLguration in 6hich all le/els up to a particular energy are completely Llled
re0uires (*N + 2+ electrons7
This concept goes a long 6ay to6ards eplaining the particular sta3ility o. the aromatic
hydrocar3ons7 An #$*$ the idea 6as ta4en .urther 3y John :7 !latt (#$#% I + 6ho used
the electron2on2a2ring model to account .or and classi.y the electronic spectra o. the
aromatic hydrocar3ons (see !ro3lem ?+7 9is classiLcation is 6idely used 3y
spectroscopists and photochemists7
'1) N2RMA5ISATI2N AN3 2RTH22NA5ITY (B"F ,72+
We ha/e not yet completed the tas4 o. ensuring that our eigen.unctions are physically
reasona3le7 A. the s0uare o. an eigen.unction, e/aluated .or any /alue o. $, gi/es the pro32
a3ility o. Lnding the electron at that position on the ring, then the sum o. all such /alues
around the ring must 3e #70 ( certainty+ since, 3y deLnition, the electron is some6here
on the ring7 Since the pro3a3ility distri3ution is a continuous .unction o. the co2ordinates,
the sum 3ecomes an integral o/er the complete range o. all o. them, in 3rie., over all
s%ace7 The process o. ensuring that an eigen.unction gi/es rise to a total pro3a3ility o.
one is 4no6n as the normalisation o. the eigen.unction7 At is an additional re0uirement to
ensure that the chosen mathematical .unctions are also accepta3le physically7 The Lnal,
normalised .orms o. our t6o types o. eigen.unction 6ith the 0uantum num3er no6 6ritten
as n are (see Bo ,72+1

sn
= !#,

(" sin!n$" and

cn
= !#,

(" cos!n$" !n = # 2 , . . ." !,.5.#"

When n = 0, cos 0 = # and .or this .unction the normalising constant is #H

(2( +7
The eigen.unctions o. a 0uantum2mechanical operator ha/e another interesting prop2
erty, orthogonality, 6hich is closely related to normalisation7 The orthogonality o. the
a3o/e eigen.unctions is also demonstrated in Bo ,727
'1* AN E5ECTR2N IN A 5INEAR 82D
An this section 6e eamine the energy2le/els o. an electron conLned 6ithin a one2
dimensional 3oP an idealised situation 6hich also casts signiLcant light on chemical
pro3lems7
'1*1% T$e Hamiltonian operator "or an ele#tron in a linear ?ox
Suppose that 6e ha/e an electron conLned 3y inLnite potential 3arriers 6ithin a one2
dimensional linear 3o o. length L7 We shall again assume that there is no electrostatic
potential present so that the only energy is 4inetic energy7 To construct the appropriate
operator 6e .ollo6 SchroM dingerGs method and Lrst 6rite do6n the classical
epression .or the 4inetic energy in terms o. the momentum, %1
E =
#
m
e
v
2
= !m
e
v"
2
,2m
e
= %
2
,2m
e
e
2
D
An 'lectron in a Linear Bo *-
The postulate .or the con/ersion o. the classical epression .or the s0uare o. the linear
momentum to the appropriate operator is1
2
%
2 2 2 2
7
=
!m
e
v
7
"

%

7
=
h`

D7
2
!,.?.#"
6here 7 = x y or B, the co2ordinate along the 3o7 Thus, the epression .or the 9amil2
tonian operator is1
9

=
!h
`
2
,2m
e
"D
2
,D x
2
!,.?.2"
:ecalling the discussion o. the pro3lem o. an electron on a ring, 6e can guess that the
.unctions1

s*
=
sin!*x" and
c*
=
cos!*x" !,.?.,"
should 3e in/estigated since 3oth are eigen.unctions o. the operator !h`
2
,2m
e
"D
2
,D
x
2
6ith eigen/alues o. *
2
h`
2
,
2m
e
7
'1*1& T$e a##epta?le eigen";n#tions
But are these .unctions physically accepta3leJ We again consider the 3eha/iour o. the
eigen.unctions and in particular their 3eha/iour at x = 0 and x = L, the t6o ends o. the
3o7 Since the electron is, 3y deLnition, conLned 6ithin the 3o, the pro3a3ility o. Lnding
the electron must .all smoothly to Kero at x = 0 and L7 Cos!*x" = #.0 at x = 0 and is
there.ore unaccepta3le on physical grounds7 The sine .unction, ho6e/er, goes smoothly
to Kero as x goes to 0, and the .unction must 3e such that this is also true at x = L7 Since
sin!n( " = 0 6hen n is an integer 6e can satis.y the .oregoing re0uirement i. 6e choose
* so that *L = n( or * = n(,L7 Thus, our only physically accepta3le eigen.unctions o.
the energy operator are1

sn
= N sin!n( x,L" !n = # 2 , . . ." !,.?.*"
6here N is a normalising constant7 The corresponding eigen/alues o. the energy are1
E
n
=

n
2
(
2
L
2

h
`
2

2m
e
n
2
h
2
=
%m L
2
!n
=
# 2 , . . ." !,.?.5"
;ote that n cannot 3e Kero since sin!0" = 0 and there is there.ore no eigen.unction7
Thus, the system never has an energy of Bero, i7e7 it al6ays has some energy and the
presence o. this Bero+%oint energy is an important point to 6hich 6e shall return in
Section ,7##7
An the eigen.unction, the letter * 6hich pre/iously had no particular signiLcance has
no6 3een replaced 3y the 0uantum num3er n (multiplied 3y (,L+7 To Lnd the normalising
constant (N + 6e simply re0uire that the pro3a3ility o. Lnding the electron at any point
along the 3o, summed up, i7e7 integrated, o/er the complete length o. the 3o, is one,
i7e7 that1
L
{N sin!n( x,L"}
0
dx = #.0
This leads to a /alue o. N o.

!2,L" (Bo ,7,+, so our complete set o. physically

accepta3le eigen.unctions is1

sn
=

!2,L" sin!n( x,L" !n = # 2 , . . ." (,7?7?+

*% The Application o. &uantum Cechanics
#%
#?
#*
#2
#0
%
?
*
2
0
0
L
6ig;re '1, 'nergy le/els and eigen.unctions .or an electron in a linear 3o
These .unctions are illustrated .or n = # to * in Digure ,7%7 The ( 2electron spectra o.
linear con@ugated polyenes can 3e interpreted rather 6ell in the light o. these results
(Bo ,7*+7
'1*1' 8o;n/ar0 #on/itions
An selecting a physically accepta3le eigen.unction .rom the /arious possi3le mathematical
solutions o. the SchroM dinger e0uation .or an electron in a linear 3o, 6e made use
o. the .act that the eigen.unction must 3eha/e in an appropriate manner at the ends (3ound2
aries+ o. the 3o7 This led not only to the complete re@ection o. many eigen.unctions
3ut also to the selection o. particular mem3ers o. the set o. sine .unctions, i7e7 those .or
6hich * = n(,L, 6here n is an integer7 At 6as at this point that 0uantisation entered
the pro3lem7 &uantisation is intimately associated 6ith the 3eha/iour o. eigen.unctions
at the 3oundaries o. the system and 6e say that 3oundary conditions are imposed upon
the eigen.unctions to determine those 6hich are physically accepta3le7 An the case o. the
electron on a ring there 6as no o3/ious physical 3oundaryP 3ut the .act that the eigen.unc2
tions 6ere re0uired to ha/e the same /alue at $ = 0 and 2( 6as the 3oundary condition7
Boundary conditions o. this type 4no6n as %eriodic *o1ndary conditions7
'1+ THE 5INEAR AN3 ANU5AR M2MENTA 26 E5ECTR2NS
C2N6INE3 4ITHIN A 2NE93IMENSI2NA5 82D 2R 2N A RIN
An determining the energy le/els in the t6o idealised models descri3ed a3o/e, 6e ha/e
used the linear or angular momentum o. the electron as an intermediate step in the
construction the re0uired energy operator, the 9amiltonian7 An this section 6e return to
consider the momenta themsel/es, and their corresponding eigen/alues and eigen.unc2
tions7 We ta4e the linear system Lrst7
The Linear and Angular Comenta o. 'lectrons *$
'1+1% T$e linear moment;m o" an ele#tron in a ?ox
An Section ,7?7# 6e used the operator .or the s0uare o. the linear momentum o. the
electron in a linear 3o, h`
2
D
2
,D x
2
, in order to .orm the 9amiltonian operator so
that
the operator .or linear momentum appears to 3e readily a/aila3le as the s0uare root o.
h
`
2
D
2
,D x
2
7 But this presents t6o pro3lems7 Dirstly, 6hat is the s0uare root o. D
2
,D x
2
J
This is not di.LcultP D
2
,D x
2
means di..erentiate the .unction t6ice 6ith respect to x, i7e7
!D,D x"

!D,D x", so a single di..erentiation 6ould represent the s0uare root7 The

h
`
2
poses
a greater pro3lem in that 6e ha/e to Lnd the s0uare root o. a negati/e 0uantityU But 6e
do not allo6 such pro3lems to deter usP 6e simply .ollo6 the lead o. the mathematicians
6ho con.ronted this pro3lem many years ago and sol/ed it 3y in/enting a ne6 num3er,
i, the s0uare root o. #P i7e7 i
2
= # (Appendi %+7 9a/ing done this 6e can epress
the s0uare root o. any negati/e num3er, e7g7 !2i"
2
= *, !5.,i"
2
= 2%.0$7 Such
num3ers are called imaginary num3ers and 6ith their aid 6e can 6rite the operator .or
linear momentum as1
D
%
=
ih`

Dx
!,.-.#"
". the t6o possi3le signs .or the s0uare root 6e choose the negati/e one .or reasons
6hich 6ill 3ecome clear 3elo67
A. 6e apply this operator to our energy eigen.unctions
sn
6e see immediately that
they are not eigen.unctions o. the linear momentum operator 3ecause di..erentiation o.
sine gi/es cosine7 What 6e need is a .unction 6hich does not change 6hen di..erentiated
once7 The eponential .unction, e
nx
or ep!nx" is such a .unction (Bo ,7#+ and1
D

ih`

Dx
{
ep!nx"
} =
ih`

n
{
ep!nx"
}
!,.-.2"
We no6 ha/e a mathematical eigen.unction, 3ut there is a serious pro3lem hereP the
calculated /alue o. our linear momentum, inh` , contains a .actor i and is there.ore
an
imaginary 0uantity7 This is 0uite unaccepta3le .or a 0uantity 6hich 6e can measure in
the la3oratory and 6hich must there.ore 3e realU But this can 3e o/ercome i. 6e 6rite
+in in place o. n as the argument o. the eponential .unction 3ecause then1
D

ih`

Dx
{
ep!
+
inx"
} =
ih`

in
{
ep!
+
inx"
} =
nh`
{
ep!
+
inx"
}
(,7-7,+
since i
2
= #7
Thus, the .unction ep(+in + is an eigen.unction o. the linear momentum operator
6ith an eigen/alue o.
+
nh
`
, and 3y choosing the negati/e sign .or the operator 6e ha/e
the result that the sign o. the momentum is the same as that o. the argument o. the
eponential .unction7 We interpret this .unction as descri3ing the motion o. an electron in
the positi/e x2direction 6ith a positi/e /alue o. %
x
7 Similarly, the .unction ep!inx" is an
eigen.unction o. the linear momentum operator 6ith an eigen/alue o.
nh`
and descri3es
an electron mo/ing in the negati/e x2direction7 Durther, 6e should note that these t6o
eponential .unctions are also eigen.unctions o. the energy operator each ha/ing the same
eigen/alue, i7e7 n
2
h`
2
H2m
e
7
But neither o. the eponential .unctions is physically accepta3le .or a 3o o. Lnite
length L1 3oth .ail to satis.y the re0uirement that they must go smoothly to Kero at x = 0
3ecause ep!0" = #.07 There.ore, since the eigen.unctions o. the linear momentum oper2
ator are not accepta3le eigen.unctions .or a 3o o. Lnite length, no linear momentum can
3e measured .or a particle conLned 6ithin such a 3o7 But i. the 3o is inLnitely long then
there are, in e..ect, no 3oundaries and the t6o eponential .unctions are 3oth physically
accepta3le7 But then no restrictions are placed upon the mathematical eigen.unctions and
there is there.ore no 71antisation7 An such a case the eigen/alues o. linear momentum
corresponding to the t6o types o. eigen.unction are1
eigen.unction eigen/alue

+*
= N ep!+i*x" %
+*
= +*h
`

*
=
N ep!

i*x" %
*
=
*h
`
6here * can ha/e any /alue7 The normalisation o. the eigen.unction o. an electron in
an inLnitely long 3o presents some di.Lculties and 6e shall not enter into that su3@ect
here (see Section #27, 6here periodic 3oundary conditions are used+7 The translational
energy 6hich results .rom this linear momentum is, o. course, also un0uantised7 At is the
.orm o. these .unctions that is responsi3le .or the name 6a/e mechanics 6hich is usually
gi/en to 0uantum mechanics in the SchroM dinger .orm7 The eponential .unctions
descri3e electrons mo/ing along x in a positi/e or negati/e direction and the energy
calculated is the 4inetic energy associated 6ith that mo/ement or momentum7 The sine
.unctions ha/e no associated momentum since they are not eigen.unctions o. the
momentum operator7 Anasmuch as they can 3e .ormed as the sum and di..erence o. the t6o
eponential .unctions (Appendi %+ they are standing 6a/es 6hich descri3e electrons
mo/ing in 3oth directions along x 6ith mutually cancelling momenta7 But the energy
is not Kero 3ecause it is proportional to the s0uare o. the momentum7
'1+1& T$e ang;lar moment;m o" an ele#tron on a ring
Dor an introduction to angular momentum see Chapter *7
Since the electron is mo/ing around the ring it has or3ital angular momentum7 To
o3tain the operator .or angular momentum (l

+ 6e .ollo6 the procedure o. the last section

and Lnd1
l

=
ih`

D,D $
!,.-.*"
Where 6e again choose the negati/e s0uare root .or the same reason as in the linear
case7
9ere also 6e Lnd that eponential .unctions are 6hat 6e re0uire and, in particular,
the .unction ep(+in$+ is an eigen.unction o. the angular momentum operator 6ith an
eigen/alue o. +nh` , 6hile the .unction ep(in$+ is also an eigen.unction o. l

6ith an
eigen/alue o. nh` 7 This loo4s encouraging, 6e epect to Lnd e0ual and opposite
/alues
o. the angular momentum since the electron can circle the ring in a cloc46ise (negati/e
a7m7+ or counter2cloc46ise (positi/e a7m7+ direction7
But are the .unctions physically reasona3le, are they single2/aluedJ As the /alue at
$ = 0, .or eample, e0ual to that at $ = 2( J And are they normalisedJ To ans6er the
Lrst 0uestion 6e note the standard results (Appendi %+1
ep!+in$" = cos!n$" + i sin!n$" and ep!in$" = cos!n$" i sin!n$"
We 4no6 .rom our deli3erations a3o/e that the sine and cosine .unctions are 3oth
single2/alued i. n is an integer or Kero7 There.ore, our eponential eigen.unctions o.
0
the angular momentum operator 6ill also 3e single2/alued i. n = 0 # 2 , . . . When
n = 0 the t6o eigen.unctions are one and the same and they ha/e an eigen/alue o. Kero7
Dor all other /alues o. n the system has paired e0ual and opposite /alues o. the angular
momentum7 'ach /alue is an integral multiple o. !lanc4Gs constant di/ided 3y 2( 7 =nli4e
the energy eigen/alues 6hich are determined 3y n
2
, the angular momentum eigen/alues
are determined 3y n and are e/enly spaced (Digure ,7$+7
To normalise the .unctions 6e must ma4e allo6ance .or the .act that they contain
3oth a real term, cos!n$" and an imaginary term i sin!n$"7 An epression 6hich contains
3oth real and imaginary parts is said to 3e com%lex7 Born allo6ed .or this possi3ility in
deLning the meaning o. a 0uantum2mechanical eigen.unction and proposed that in the case
o. comple eigen.unctions the pro3a3ility 6as gi/en, not 3y the s0uare o. the .unction,
3ut 3y the product o. the .unction and its comple con@ugate7 The comple con@ugate o.
any comple .unction is o3tained simply 3y changing +i to i and i to +i e/ery6here
(Appendi %+7 Thus ep!+in$" is the comple con@ugate o. ep!in$", and vice versa7
There.ore, the pro3a3ility, P !$" o. Lnding the electron at a particular angle, $, around
the ring is gi/en 3y1
P !$" = ep!+in$" ep!in$" = ep!0" = #.0
This result tells us t6o important .acts7 Dirstly, the distri3ution o. the electron does not
depend upon the /alue o. $, it is the same at all points around the ring7 But it also sho6s
that the .unction re0uires normalisation (see Bo ,72+ so that the sum o. the pro3a3ilities
all around the ring add up to #707 We Lnd the normalising constant 3y integrating the
epression a3o/e .rom 0 to 2( 7 We Lnd1
2(
ep!+in$" ep!in$" d$ =
0
2(
ep!0" d$ =
0
2(
# d$ = Z$\
2(
= 2(
0
Angular Comentum
in units o. hH2p
(#H2+ep(+in.+ (#H2p+ep(in.+
*
,
2
#
0
n = *
n = ,
n = 2
n = #
n = 0
6ig;re '1- The angular momentum eigen/alues o. an electron on a ring
e
6hich sho6s that each eigen.unction must 3e multiplied 3y

!#,2( "7 There.ore, our Lnal

normalised 6a/e .unctions are1

+n
=

#
2(

ep!
+
in$" and

n
=

#
2(

ep!

in$" (,7-75+
'1, THE EIEN6UNCTI2NS 26 3I66ERENT 2!ERAT2RS
We ha/e determined the eigen/alues and eigen.unctions o. the operators .or the energy
and angular momentum o. an electron conLned to mo/e on a circle o. radius r 7 An so doing
6e ha/e noted that, although the .unctions
sn
=

!#,( "

sin!n$" and
cn
=

!#,( "

cos!n$", 6ith n an integer, are eigen.unctions o. the energy operator, or 9amiltonian, 9

1
2
9

h` =
2m
e
r
2

D
2
,D
2
$
they are not eigen.unctions o. the angular momentum operator1
l

= ih
`
D,D
$
The reason .or this is 0uite clear, the sine and cosine .unctions return to their original
.orm only 6hen di..erentiated t6ice 6ith respect to the angle $7 Whereas an eigen.unction
o. l

must 3e a .unction such as the eponential, the Lrst deri/ati/e o. 6hich is the
eponential .unction itsel. (Bo ,7#+7 A. 6e di..erentiate the eponential .unctions t6ice
6ith respect to $ 6e Lnd that they are also eigen.unctions o. the energy operator 6ith
the same eigen/alues as the sine and cosine .unctionsP e7g71

#

2m
e
r
2
h`
2

#
2(

D
2
D$
2

n
2
h`
2
{
ep!in$"
} =
2m r
2

#

2(
{ep!in$"}
The results are summarised in Ta3le ,7#7
Drom these results 6e can dra6 the important conclusion that it is possi3le .or a system
o3eying the la6s o. 0uantum mechanics to 3e in a state that is descri3ed 3y a .unction
Ta?le '1% The energy and angular momentum o. an electron
on a ring
"3ser/a3le 'nergy Angular momentum
"perator 9

l

Dunction 'igen/alue 'igen/alue

#
2 2 2

(

sin!n$" n
h
`
,2m
e
r not an eigen.unction
#
2 2 2

(

cos!n$" n
h
`
,2m
e
r not an eigen.unction
#
2 2 2

2(

ep!
+
in$" n h` ,2m
e
r
+
nh
`
#
2 2 2

2(

ep!

in$" n
h`
,2m
e
r

nh
`
a

a
'igen.unctions, 'igen/alues and 'perimental Ceasurements 5,
6hich is an eigen.unction o. one operator, 3ut is not an eigen.unction o. some other
operator7 The system may also 3e descri3ed 3y a .unction 6hich is an eigen.unction o.
more than one operator7 Since the eigen/alues o. operators are the o3ser/a3les 6hich 6e
can measure eperimentally, these results place important restrictions on 6hat 6e can
4no6 a3out a system7 This 0uestion 6ill 3e ta4en up again in Section ,7#07
'1- EIEN6UNCTI2NS< EIENVA5UES AN3 ED!ERIMENTA5
MEASUREMENTS
We ha/e seen that the eigen.unctions and eigen/alues 6hich sol/e SchroM dingerGs
e0uation .or a particular system are, respecti/ely, 6a/e .unctions descri3ing the
distri3utions o. the electron(s+ in/ol/ed in the pro3lem and the /alues o. the 0uantised
o3ser/a3les o. the electrons such as energy and momentum7 There is a direct
correspondence 3et6een the mathematical process o. sol/ing SchroM dingerGs e0uation
to o3tain the /alue o. an o3ser/a3le 3y calculation and the measurement o. that
o3ser/a3le in an eperiment7 But 6e ha/e also seen that it is possi3le .or a 0uantum2
mechanical system to 3e descri3ed 3y a .unction 6hich is an eigen.unction o. one
operator 3ut not o. another7 Dor eample,
the .unction
cn
=
!#,

("

cos!n$" is an eigen.unction o. the energy operator .or an
electron on a ring, 3ut it is not an eigen.unction o. the corresponding angular momentum
operator7 We might as4, there.ore, 6hat 6ould 3e the result o. attempting to measure the
angular momentum o. the electron on a ring 6hen it is in the state descri3ed 3y the a3o/e
cosine .unctionJ &uantum mechanics gi/es a clear ans6er to this 0uestion7
Suppose Lrst that 6e measure an o3ser/a3le (r + in a system 6hich is in a state descri3ed
3y an eigen.unction (
a
+ o. the operator (:

+ that corresponds to this o3ser/a3le7
We
call such a state an eigenstate o. :

7 Then the result o. the (idealised and error2
.ree+
measurement 6ill 3e the eigen/alue (r
a
+ corresponding to that eigen.unction and operator,
i7e7 the solution o. the SchroM dinger e0uation1
:


a
= r
a

a
!,.$.#"
And, 6ith the 0ualiLcations to 3e descri3ed 3elo6, 6e shall get the same ans6er, r
a
,
e/ery time 6e repeat the measurement7
A. 6e no6 attempt to measure the same o3ser/a3le in a system 6hich is not in a
state descri3ed 3y an eigen.unction o. the operator
:

corresponding to the o3ser/a3le

r , then the result o. the measurement 6ill still 3e one o. the possi3le eigen/alues o. :

,
3ut 6e cannot say 6hich7 A. 6e repeat the measurement 6e shall, in general, o3tain a
di..erent resultP another eigen/alue o. :

7 A. the measurement is repeated many times,
the
/alue measured each time 6ill al6ays 3e one o. the eigen/alues o. :

, and there
may
3e repetition o. some /alues, 3ut 6e cannot say 6hat /alue any particular measurement
6ill gi/e7 9o6e/er, as the num3er o. measurements increases, the a/erage result o. the
measurements 6ill tend to a /alue (r + 4no6n as the mean /alue, 6hich can 3e calculated
using the .ormula1

r =
all space

:
a
dv

all space

a
dv !,.$.2"
The di/ision 3y


a

a
dv allo6s .or the use o. un2normalised 6a/e .unctions and
the

indicates that 6e ha/e to ta4e the comple con@ugate o.
a
i. it is a comple
5* The Application o. &uantum Cechanics
2
.unction (see Appendi %+7 The integration o/er Qall spaceG means integration o/er the
.ull range o. co2ordinates a/aila3le to the system, e7g7 .rom to + in x y and B7
'0uation (,7$72+ is an important complement to '0uation (,7$7#+7 At pro/ides us 6ith the
means o. calculating a /alue .or an o3ser/a3le e/en 6hen the
a
Gs are not eigen.unctions
o. the operator :

7 r is then the a/erage o. a large num3er o. measurements7 At is
the
result 6hich 6e 6ould ex%ect to get as the mean o. a large num3er o. measurements and
is accordingly called the ex%ectation val1e o. r 7 9ere pro3a3ility again enters into the
predictions o. 0uantum mechanicsP in such circumstances 6e cannot predict the result o.
an indi/idual measurementP the 3est 6e can do is to gi/e the /alue to 6hich the mean o.
a large num3er o. measurements 6ill tend7
Be.ore proceeding to an eample, 6e note that in 0uantum mechanics the idea o.
repeating an eperimental measurement is not a simple concept7 At is one o. the .oundation
stones o. the philosophy o. 0uantum mechanics that, in general, a system is a..ected 3y
any measurement made upon itP its state, and the 6a/e .unction 6hich descri3es it, may
not 3e the same a.ter the measurement as they 6ere 3e.ore it7 There.ore, a.ter each
measurement the system must 3e allo6ed to return to its original state 3e.ore the net
measurement can 3e made7 This is a point 6hich 6e shall discuss in detail in the net
section7 Since, in chemistry, a sample su3@ected to a measurement usually consists o. a
/ery large num3er (

#0
2,
+ o. identical molecules or atoms, 6e may consider in such
cases that the result o3tained is the mean /alue deLned as a3o/e 3ut that it is o3tained as
the result o. the same measurement made simultaneously upon many identical systems7
By 6ay o. an eample, in Bo ,75 6e use '0uation (,7$72+ to determine the epectation
/alue .or the angular momentum o. an electron on a ring 6hen it is in the cosine .unction
state7 The result o. Kero may at Lrst appear unli4ely, 3ut it is 0uite easy to understand7
According to Appendi %1
cos!n$" =
#
{ep!+in$" + ep!in$"} !,.$.,"
Thus, the cosine .unction is composed o. e0ual parts o. the t6o eponential .unctions
6hich are the eigen.unctions o. the angular momentum operator7 Since the t6o eigen.unc2
tions ha/e e0ual and opposite angular momenta (Ta3le ,7#+ the com3ination o. the t6o
gi/es an epectation /alue o. Kero7 Thus, an eperimental measurement o. the angular
momentum 6hen the electron is in the cosine .unction state may gi/e a /alue o.
+
nh`
or o.

nh
`
7 But i. many measurements are made the t6o /alues 6ill occur 6ith
e0ual
pro3a3ility and the mean result 6ill tend to the /alue o. Kero7 Alternati/ely, as noted
a3o/e, i. the sample is a typical QchemicalG one and contains a /ery large num3er o.
atoms or molecules then the result o. one measurement on the sample as a 6hole, i7e7
simultaneously on many indi/idual atoms (molecules+, may 3e regarded as the a/erage
o. many se0uential measurements on an indi/idual atom (molecule+7
'0uation (,7$72+ is o. particular /alue in pro3lems 6here 6e ha/e di.Lculty in sol/ing
SchroM dingerGs e0uation and o3taining its eigen.unctions7 Because o. the compleity
o. many chemical systems, it is normally impossi3le to sol/e '0uation (,7$7#+ directly7
=nder such circumstances it is use.ul i. 6e can postulate an approimate 6a/e .unction .or
the system and use that to determine an approimation to the o3ser/a3le 0uantities 3y
means o. '0uation (,7$72+7 This type o. calculation plays an essential role in the theory o.
the chemical 3ond as 6e shall see in Chapter ?7
Core A3out Ceasurement1 The 9eisen3erg =ncertainty !rinciple 55
'1%. M2RE A82UT MEASUREMENT: THE HEISEN8ER
UNCERTAINTY !RINCI!5E
An Section ,7$ 6e noted that it is a .undamental 0uantum2mechanical principle that no
measurement can 3e made upon a system 6ithout a..ecting that system7 This should not
really surprise us7 Suppose that 6e 6ish to measure the time at 6hich a locomoti/e passes
a particular point on a rail6ay line, there3y Ling its position at that particular time7 We
might stretch a cotton thread attached to a timing mechanism across the trac47 There
6ould 3e no concern that the collision o. the locomoti/e 6ith the thread 6ould slo6 the
train to any degree 6hich could 3e measured7 This 3eing so, a second de/ice o. the same
type placed a 4no6n distance do6n the trac4 6ould ena3le us to L the position o. the
locomoti/e .or a second time and measure its a/erage /elocity 3et6een those t6o points
on the line and, i. 6e 4no6 its mass, its mean linear momentum7
But 6hat i. the mo/ing o3@ect to 3e timed 6as a OyJ A. the mechanism 6as su.Lciently
delicate 6e might 3e a3le to determine the time at 6hich the Oy struc4 the Lrst timing
de/ice, 3ut 6e certainly could not maintain that the OyGs .urther progress 6ould 3e
una..ected 3y its contact 6ith the thread7 Thus, a measurement o. its mean /elocity or
momentum 6ould 3e in/alidated since it 6ould not 3e independent o. the measurement
itsel.7 An the case o. the Oy, the pro3lem could 3e o/ercome 3y using 3eams o. light and
photocells in place o. the mechanical timing de/ices7
But 6hat i. the o3@ect to 3e studied 6as an electronJ 'lectrons are not indi..erent to
photonsP as 6e sa6 in Section 27?, electrons can 3e e@ected .rom metals 3y photons7 Thus,
6e could not 3e sure i. the impact o. the QmeasuringG photon had changed the position o.
the electron, its /elocity, or 3oth7 There are no means 3y 6hich e/ents at the atomic and
molecular le/el can 3e o3ser/ed in such a 6ay that those e/ents are not inOuenced 3y the
5? The Application o. &uantum Cechanics
act o. o3ser/ation itsel.7 Just as in sociology, 6here merely to as4 a particular 0uestion
has an inOuence upon the respondentGs attitude to that su3@ect, there is no uninOuential
o3ser/ation in 0uantum mechanics7
-o o*serve a system is to interact 0ith it and change it.
An .act, the pro3lem o. the accuracy o. measurement is e/en more su3tle than the
a3o/e discussion suggests7 An #$2- 9eisen3erg sho6ed that, in systems o3eying the la6s
o. 0uantum mechanics, there are pairs o. related properties 6hich cannot 3e measured
eactly at the same time (Bo ,7?+7 This situation is .undamental to 0uantum2mechanical
systems and 9eisen3erg epressed the result in the .orm o. his uncertainty principle, an
eample o. 6hich is1
%
x

x

h,*(
!,.#0.#"
%
x
is the uncertainty in the result o. a measurement o. the linear momentum o. a
particle along x and x is the uncertainty in the measurement o. the x co2ordinate,
and their product has to 3e greater than !lanc4Gs constant di/ided 3y *( 7 "ther pairs o.
o3ser/a3les lin4ed 3y an uncertainty relationship are gi/en in Bo ,7?7 At is important
to note that this uncertainty o. measurement has nothing to do 6ith the 0uality and
precision o. the e0uipment a/aila3le .or the measurement, nor 6ith the a3ility o. the
eperimentalist7 The limitation on the measurement is .undamental and '0uation (,7#07#+
assumes that per.ect eperimental de/ices are used 3y per.ect eperimentalists7 Thus, to
return to the pro3lem o. the Oy, the pro3lem o. getting the Oy to hit the timing de/ice is
0uite irrele/ant to the argument here7
The magnitude o. !lanc4Gs constant and its presence in '0uation (,7#07#+ eplains 6hy
the conse0uences o. the uncertainty principle 6ere ne/er noticed in classical mechanics7
Since the product o. the t6o uncertainties is a3out one order o. magnitude less than
!lanc4Gs constant it is so small that the indi/idual uncertainties in the /alues o. position
and momentum are much too small to 3e o3ser/ed in an eperiment 6ith macroscopic
3odies7 A. 6e di/ide 3oth sides o. '0uation (,7#07#+ 3y, m, the mass o. the particle
concerned, 6e o3tain1
v
x

x

h,*(m !,.#0.2"
The Commutation o. "perators 5-
6hich sho6s clearly ho6 the product o. the t6o uncertainties 3ecomes smaller as the mass
o. the particle increases, i7e7 as 6e go .rom systems 6hich re0uire a 0uantum2mechanical
description to those to 6hich classical mechanics applies7 ;ote that the 0uantity on the
right2hand side o. the ine0uality (,7#07#+ is not al6ays gi/en as h,*( , it is 0uite common
to Lnd h,2( .or eample7 These di..erences are a conse0uence o. the di..erent 6ays in
6hich the uncertainties %
x
and x can 3e deLned, 3ut this in no 6ay in/alidates the
.undamental uncertainty principle 6hich 9eisen3erg Lrst enunciated7 The particular /alue
o. h,*( applies to the case 6here the uncertainties are assumed to .ollo6 the Gaussian
distri3ution la67
'1%% THE C2MMUTATI2N 26 2!ERAT2RS (B"F'S 272 A;< ,7?+
An Section ,7#0 6e recognised that there are important limitations on 6hat 6e can 4no6
a3out a system 6hich o3eys the la6s o. 0uantum mechanics7 An particular 6e sa6 that the
accuracy 6ith 6hich the t6o properties, momentum in the x direction and x co2ordinate,
could 3e simultaneously measured, 6as restricted 3y the 9eisen3erg uncertainty principle7
We discussed the matter .rom an essentially eperimental point o. /ie6P no6 6e loo4 at
the pro3lem .rom the theoretical standpoint7
According to Section ,7$, e/ery o3ser/a3le 0uantity has an associated operator 3y
means o. 6hich either the eact /alue o. the o3ser/a3le or a mean /alue can 3e calculated
using '0uations (,7$7#+ or (,7$72+ respecti/ely7 9o6 6ould the pro3lem o. calc1lating t6o
properties 3e .ormulatedJ At seems natural to suggest that, in direct correspondence 6ith
eperimental measurement, 6e Lrst calculate the one and then the other7 Thus, i. 6e ha/e
a system in the state
a
.or 6hich 6e 6ish to 4no6 the simultaneous /alues o. t6o
properties P and 3 6e could per.orm the calculation1
P

3


a
= P

7
a

a
= 7
a
P


a
= 7
a
%
a

a
or
3

P


a
= 3

%
a

a
= %
a
3


a
= %
a
7
a

a
And since %
a
and 7
a
are simply num3ers 6e o3tain the same result, regardless o.
the order o. application o. P

and 3

7 But these t6o calculations assume that
a
is
an eigen.unction o. 3oth P

and
3

6hich is 3y no means al6ays the case7 This can 3e

illustrated using the momentum and position operators and the eigen.unction .or a electron
in an inLnitely long 3o .rom Section ,7-7#1
+
*
= N ep!+i*x"7
The operator .or linear momentum along x is

ih
`
D,D x and the operator .or the x
co2ordinate is x itsel. and 6e in/estigate the e..ect o. applying these t6o operators
consecuti/ely to the a3o/e eigen.unction7 We ha/e either1
D D
x

!

ih` "
Dx

+
*
=
ih` N x
Dx
ep!
+
i*x"
=
ih` N xi* ep!
+
i*x"
=
h` *x
+
*
or
D D

ih`
Dx
x


+
*
=
ih` N
Dx
x ep!
+
i*x"
=
ih` N
{
ep!
+
i*x"
+
xi* ep!
+
i*x"
}
=
ih
`

+*
+
h
`
*x
+*
The results are not the same, in .act1
!x %
x
%
x
x "
+
*
= ih`
+
*
!,.##.#"
5% The Application o. &uantum Cechanics
When the t6o results .or the consecuti/e operation o. t6o operators are not e0ual
6e say that the operators do not commute and the root o. the pro3lem lies in the .act
that it is not possi3le to Lnd a .unction 6hich is simultaneously an eigen.unction o.
3oth operators7 As a conse0uence, it is not possi3le to 4no6, simultaneously, 3oth the
o3ser/a3les associated 6ith the operators7 Thus, 9eisen3ergGs uncertainty principle is a
mani.estation o. the .act that the operators corresponding to the t6o o3ser/a3les in/ol/ed
do not commute7
We can see some o. the e..ects o. 9eisen3ergGs uncertainty principle in relation to
position and momentum along the x co2ordinate using, once more, our pair o. eponential
6a/e .unctions .or the electron in a linear 3o7 The pro3a3ility, P !x

+, o. Lnding an
electron at a point ha/ing the co2ordinate x

is proportional to the product o. the 6a/e
.unction and its comple con@ugate e/aluated at that point, i7e71
P !x

" = N
2
ep!i*x

" ep!+i*x

" = N
2
ep!0" = N
2
6here N is the normalising constant7 The important point here is that the pro3a3ility is the
same at e/ery point along the 3o, since it does not depend upon x7 Thus, .or an inLnitely
long 3o the uncertainty in our 4no6ledge o. the position o. the electron is inLnite since it
can 3e any6here in the 3o7 But it is only .or a 3o o. inLnite length that the momentum
has the eact /alues o. *h,2( 7 Thus, .or the inLnitely long 3o the linear momentum
o. the electron is 4no6n eactly 3ut the uncertainty in its position is inLnite7 Dor any 3o
o. Lnite length the uncertainty in our 4no6ledge o. the position o. the electron is Lnite,
since then it must lie 3et6een 0 and L7 There.ore, there must also 3e a Lnite uncertainty
in our 4no6ledge o. the momentum o. the electron7 Durther, since there is no potential
energy term in the pro3lem, the energy is all 4inetic energy and there.ore proportional to
the s0uare o. the momentum so that the energy o. the electron must also 3e uncertain7
There could 3e no uncertainty i. the energy 6as Kero, so the .act that there is a Kero2point
energy (Section ,7?72+ is in accord 6ith the 9eisen3erg uncertainty principle7
'1%& C2M8INATI2NS 26 EIEN6UNCTI2NS
AN3 THE SU!ER!2SITI2N 26 STATES
An Section ,7$ 6e sa6 that a .unction 6hich 6as not an eigen.unction o. the angular
momentum operator .or the electron on a ring could 3e 6ritten as a sum o. t6o eigen2
.unctions o. that operator ('0uation (,7$7,++7 This is an important result 6hich may 3e
generalised .urther7 Any .unction 6hich o3eys the 3oundary conditions (Section ,7?7,+ o.
a pro3lem can 3e epressed as a sum o. the eigen.unctions o. that pro3lem7 The /alue
o. this result lies in the 6ay in 6hich it allo6s us to address the .ollo6ing pro3lem7 We
4no6 that an atom (or molecule+ may eist in an electronic eigenstate o. the 9amiltonian
operator7 An this state it has a precisely measura3le energy7 We also 4no6 that i. light o.
an appropriate .re0uency stri4es the atom it may a3sor3 a photon and ma4e a transition
to an eigenstate o. higher energy and that this process ta4es a Lnite time7 'stimates o. the
time re0uired are discussed in Chapter %, 3ut 6e may say here that it is o. the order o.
#0

#%
s7 But 6hat is the appropriate description o. the atom during the time in 6hich it
has le.t the initial eigenstate, G
i
, 3ut has not yet arri/ed in the Lnal eigenstate, G
f
J Since
3oth G
i
and G
f
are eigen.unctions o. the same 9amiltonian operator, any other state o.
the atom, 6hich is not an eigenstate, may 3e descri3ed as a sum, suita3ly normalised,
"perators and their Dormulation 5$
o. these t6o states plus contri3utions .rom all the other eigenstates o. the 9amiltonian
operator .or the atom7 The technical term .or such a description is a s1%er%osition of
states7 An this particular pro3lem it is reasona3le to assume that the contri3utions .rom
the other eigenstates are /anishingly small so that at any moment during the transition
the atom is in the state H , 6here H can 3e approimated as a superposition o. @ust t6o
states, i7e71
H
=
c
i
G
i
+
c
f
G
f
!,.#2.#"
And, assuming that the .unctions G
i
and G
f
are orthogonal and normalised, H 6ill 3e
normalised i.1
c
2 2
i
+
c
f
=
#.0 !,.#2.2"
Be.ore the photon stri4es the atom, c
i
= #.0 and c
f
= 0.07 When the process o. a3sor32
ing the photon is complete, c
i
= 0.0 and c
f
= #.07 At any point in time during the
a3sorption process, c
i
is decreasing and c
f
increasing, su3@ect al6ays to the normalisa2
tion condition ('0uation (,7#272++7 Thus the system undergoing a spectroscopic transition
does not enter some .orm o. lim3o a3out 6hich 6e 4no6 nothingP 6e ha/e a description
o. the system throughout the process7 This description o. the a3sorption or emission o. a
photon is eamined in more detail in Section %7?7
'1%' 2!ERAT2RS AN3 THEIR 62RMU5ATI2N
At has 3een emphasised a3o/e that the .orm o. the operator .or any particular o3ser/a3le
is a postulate 6hich has 3een tested against its success in calculations o. measura3le
0uantities using that operator7 Since classical mechanics is a limiting case o. 0uantum
mechanics, 6e might epect that relationships 3et6een operators thus deri/ed 6ould
reOect the relationships 3et6een the corresponding classical 0uantities7 This is indeed the
case and use can 3e made o. that .act in the construction o. operators7 As .ar as the usual
chemical applications o. 0uantum mechanics are concerned, the operators .or position
(co2ordinate+, potential energy, 4inetic energy, linear momentum and angular momentum,
play 3y .ar the most important roles7 The relationships 3et6een these operators mirror
the relationships o. the corresponding classical 0uantities as the .ollo6ing 6ill sho67
'1%'1% !osition or #o9or/inate< ()
The operator .or the position o. a particle, x or r say, is simply x
or r7 Where the
caret mar4 (+ is used to distinguish the operator .rom the o3ser/a3le7 There.ore, the
epectation /alue (x+ o. the x co2ordinate o. a particle descri3ed 3y the normalised 6a/e
.unction G is1

x =
all space
G x G dx dy dB G |x |G
using the notation introduced 3y <irac7
'1%'1& !otential energ0< *
)
Since potential energy is in/aria3ly epressed in terms o. the position o. a particle in
some Leld o. .orce, e7g7 the distance o. the electron .rom the nucleus in the hydrogen
?0 The Application o. &uantum Cechanics
x x x
Dx
2
atom or the angle 3et6een a nuclear magnet and an applied magnetic Leld, the essential
operator in potential energy is the position operator7 There.ore, using the result a3o/e, the
classical epression .or the potential energy (V + o. t6o charges o. +e and e separated
3y a distance r is replaced 3y the operator V

in the .ollo6ing 6ay1

V = e
2
,r V

= e
2
,r
'1%'1' 5inear moment;m< p)
(
We ha/e already seen that linear momentum in the x direction is replaced in the operator
.ormalism 3y di..erentiation 6ith respect to x multiplied 3y ih,2( , i7e71
p = mv p = ih`

DG
'1%'1( =ineti# energ0< W
)
We deduce the .orm o. the 4inetic energy operator 3y epressing 4inetic energy as the
s0uare o. the momentum di/ided 3y mass and using the last result, i7e71
W
=
#
mv
2
=
!mv
x
"

W
h
`
2
=
D
2
G

2 x
2m 2m Dx
2
'1%'1) Ang;lar moment;m< L
)
The angular momentum (see also Chapter *+ o. a particle o. mass m rotating a3out a
centre is the /ector product o. the distance o. the particle .rom the centre (r+ and its linear
momentum (p+7 A. the rotation ta4es place in the xy2plane (B
=
0 %
B
=
0+, then resol/ing
the /ectors r and p into their Cartesian components, 6e ha/e our angular momentum
operator as1
DG DG

L
=
r

p
=
x%
y

y%
x

L

=
ih
`
x

Dy

y

Dx
'1%( SUMMARY
An this chapter 6e ha/e studied the application o. 0uantum mechanics to simple pro3lems
and ha/e 3een particularly concerned to eamine the eact details o. the description o.
the 6orld o. atoms and molecules 6hich the method pro/ides7 This di..ers .rom the
description o. the macroscopic 6orld gi/en 3y classical mechanics in a num3er o. /ery
important 6ays and, on the .ace o. it, 6e appear to ha/e less in.ormation a/aila3le to us
6hen 6e use 0uantum mechanics than 6e ha/e 6hen 6e use classical mechanics7 With
this in mind, it is essential that 6e .ocus our attention upon things 6hich can 3e measured
and do not attempt to grapple 6ith pro3lems .or 6hich 0uantum mechanics pro/ides no
ans6ers7 At is no more meaning.ul, .or eample, to attempt to calculate the %ath o. an
electron than it is to discuss its colo1r7
Bi3liography and Durther :eading ?#
Thus, 6e can1
<etermine precise /alues o. physical o3ser/a3les 6here the system concerned is in an
eigenstate o. the appropriate operator7
<etermine a mean /alue o. an o3ser/a3le 6here the system is not in an eigenstate o.
the appropriate operator7
<escri3e a system 6hen it is not in an eigenstate in terms o. appropriate superpositions
o. the set o. eigenstates o. the rele/ant operator7
With these theoretical methods, some o. 6hich are illustrated in a discussion o. the
properties o. polarised light in Bo ,7-, 6e can interpret almost all the eperiments 6hich
are o. interest to chemistry7 Where such theoretical methods .ail to gi/e us a 0uantitati/ely
accurate ans6er, as they .re0uently do, it is 3ecause o. the di.Lculties 6hich 6e ha/e in
sol/ing the SchroM dinger eigen/alue2eigen.unction '0uation (,7$7#+, or in e/aluating
the integral in '0uation (,7$72+ in order to determine an epectation /alue, and not
3ecause o. a .ailure o. the 3asic theory7 Dortunately, as 6e shall see in Chapters ? and -,
approimate solutions are .re0uently 0uite su.Lcient .or our purpose7
'1%) 8I85I2RA!HY AN3 6URTHER REA3IN
At is not easy to recommend 3oo4s on 0uantum mechanics, there is a /ery 6ide choice
and many o. the classic tets are no6 /ery old, though their comprehensi/e treatment o.
the su3@ect remains as rele/ant as it e/er 6as7
There are t6o use.ul and comparati/ely recent introductory tets 3y Green1
#7 ;7J7B7 Green, 31ant1m 5echanics I, ".ord =ni/ersity !ress, #$$-7
27 ;7J7B7 Green, 31ant1m 5echanics J, ".ord =ni/ersity !ress, #$$%7
And an additional /olume in the same series7
,7 !7A7 Co, :ntrod1ction to 31ant1m -heory and Atomic Str1ct1re, ".ord =ni/ersity !ress,
#$$57
Cuch more ad/anced 3ut 6ith many ecellent, .ully26or4ed applications is1
*7 :7C7 Golding, A%%lied Wave 5echanics, 8an ;ostrand, London, #$?$7
"ne o. the great classics, not .or the 3eginner is1
57 !7A7C7 <irac, 31ant1m 5echanics, *th edn, ".ord =ni/ersity !ress, #$?-7
;o6 also a/aila3le .rom <o/er !u3lications7
The .ollo6ing three also deser/e the accolade QclassicG7 They are all /ery comprehensi/e tets
particularly aimed at chemists and they pro/ide an in/alua3le source o. re.erence a3out most o.
the 0uantum2mechanical pro3lems and methods o. interest to chemists7
?7 L7 !auling and '7B7 Wilson, :ntrod1ction to 31ant1m 5echanics, CcGra629ill, ;e6 Ror4,
#$,57
?2 The Application o. &uantum Cechanics
-7 97 'yring, J7 Walter and G7'7 >im3all, 31ant1m Chemistry, Wiley, London, #$**7
%7 W7 >auKmann, 31ant1m Chemistry, Academic !ress, London, #$5-7
Core modern 3oo4s 6ith chemists in mind are1
$7 !7W7 At4ins and :7S7 Driedman, 5olec1lar 31ant1m 5echanics, ".ord =ni/ersity !ress,
#$$-7
#07 A7;7 Le/ine, 31ant1m Chemistry, 5th edn, !rentice29all Anc7, ;e6 Jersey, 20007
The .ollo6ing are aimed more at physicists, 3ut all present rather di..erent approaches to the
su3@ect than the preceding /olumes7
##7 L7<7 Landau and '7C7 Li.shitK, 31ant1m 5echanics, 'nglish 2nd edn, !ergamon !ress, ".ord,
#$?*7
#27 J7J7 Sa4urai, 5odern 31ant1m 5echanics, Ben@aminHCummings, Cenlo !ar4, #$%57
#,7 A7S7 <a/ydo/, 31ant1m 5echanics, Addison2Wesley !u3lishing Company Anc7, :eading,
#$?57
#*7 ;7 Nettili, 31ant1m 5echanics Conce%ts and A%%lications, Wiley, Chichester, 200#7
82D '1% T$e sine< #osine an/ exponential ";n#tions
We ma4e .re0uent use o. the sine, cosine and eponential .unctions, and their deri/a2
ti/es, in this chapter7 The particular results 6hich 6e re0uire can 3e readily deri/ed
i. 6e recall that each o. these .unctions can 3e epressed as a po6er series1
sin!ax " = ax !ax "
,
,,U + !ax "
5
,5U !ax "
-
,-U +

cos!ax " = # !ax "

2
,2U + !ax "
*
,*U !ax "
?
,?U +

ep!ax " e
ax
= # + ax + !ax "
2
,2U + !ax "
,
,,U + !ax "
*
,*U +
ep!ax " e

ax
= # ax + !ax "
2
,2U !ax "
,
,,U + !ax "
*
,*U +

nU = n!n #"!n 2"!n ," # is called factorial nP e7g7 5U = 5 * , 2 # =

#207
<i..erentiating sin!ax" term23y2term 6ith respect to x 6e ha/e1
d Zsin!ax "\,dx = a ,a !ax "
2
,,U + 5a !ax "
*
,5U -a !ax "
?
,-U +
= aZ# !ax "
2
,2U + !ax "
*
,*U !ax "
?
,?U + \ = a cos!ax "
Similarly
and
d Zcos!ax "\,dx = a sin!ax "
d Zep!ax "\,dx = a ep!ax "
d Zep!ax "\,dx = a ep!ax "
G
2
0
82D '1& T$e Normalisation an/ ort$ogonalit0 o" eigen";n#tions
Normalisation
The s0uare o. an eigen.unction (G + e/aluated at any point in space gi/es the pro32
a3ility that the particle descri3ed 3y that eigen.unction 6ill 3e .ound at that point7
Since the pro3a3ility o. Lnding the particle some6here 6ithin the 6hole o. the region
o. space in 6hich it is allo6ed to mo/e must 3e one (certainty+, it .ollo6s that the
sum o. the /alues o. G
2
e/aluated at e/ery point in space must 3e one .or a physi2
cally accepta3le eigen.unction7 This re0uirement is represented mathematically 3y an
integration o/er all space1

all space
G
2
dv = #.0
We can illustrate the normalisation process using the eigen.unctions 6hich 6e
ha/e .ound .or the electron conLned to a ring7 Dor the cosine .unctions .or eample1
G
ca
= N cos!a$"
Where a = 0 # 2 . . . and N is the normalising constant 6hich 6e ha/e to Lnd7
An this particular pro3lem the Q6hole o. spaceG, as .ar as the electron is concerned, is
a complete circuit o. the ring, i7e7 all /alues o. $ .rom 0 to 2( 7
Dor the special case 6here a = 0 cos!a$" = #.0 and 6e ha/e1
2(

2
ca
d$
=
N
0
2(
# d$ = N
0
2
Z$\
2(
= 2(N
2
There.ore, .or a normalised eigen.unction 6e must ha/e N = #,

2( 7 We al6ays
ta4e the positi/e sign, 3ut the choice o. sign can ha/e no e..ect upon the calculation
o. any property 6hich 6e can measure7
When a is not Kero 6e ha/e1
2(

G
2
2(
2

2
2(
N
2

ca
d$
=
N
0
{cos!a$"}
0
d$ =
2
{
#
+
cos!2a$"
}
d$
0
N
2

=
2
$
+
sin!2a$"

2(
2a
0
=
N
2
2
2

2(
=
N (
Thus, .or these .unctions N = #,

( and the correctly normalised eigen.unctions

are 6ritten1
#
G
ca
=
(
cos!a$"
The sine .unctions can 3e normalised in the same 6ay and the normalising constant
is .ound to 3e

!#,( " .or these also7

2rt$ogonalit0
The eigen.unctions 6hich sol/e SchroM dingerGs e0uation also ha/e the property
o. orthogonality, i7e7 6hen the product o. t6o di..erent eigen.unctions is
integrated
2
2
0
0
Qo/er all spaceG the result is Kero7 Thus, .or t6o cosine eigen.unctions1
2(
#

(
cos!a$"

cos!*$" d$
=
0 i. a
=
*
0
This is a /ery important property 6hich epresses the .act that any one eigen.unc2
tion cannot 3e 6ritten in terms o. the other eigen.unctions o. the same SchroM
dinger operator7 This is eactly the same as saying that a coordinate on the x2
ais o. a graph cannot 3e epressed in terms o. a co2ordinate, or co2ordinates, on
the y2ais o. the same graph7 This is 3ecause the t6o aes are orthogonal, 6hich
is another 6ay o. saying that they are at right angles to each other7 We can
demonstrate the orthogonality o. t6o cosine .unctions simply 3y carrying out the
re0uired integration1
2(
#

(
cos!a$"

cos!*$" d$
=
0
2(
#

(
{
cos!Za
+
*\$"
+
cos!Za

*\$"
}
d$
0
#

sin
{
!a
+
*"$
}
sin
{
!a

*"$
}

2(
=
( !a + *"
+
!a *"
0
=
Both terms are Kero at $ = 0 and 2( 3ecause a and * are integers7
82D '1' Normalisation an/ ort$ogonalit0 o" t$e eigen";n#tions "or an ele#tron in a
linear ?ox
Normalisation (See also Bo ,72+
The normalisation integral is1
L
{N sin!n( x,L"}
0
dx = #.0
3ut sin
2
# =
#
!# cos 2#" and the integral can there.ore 3e 6ritten as1
L
N
2

N
2

L

L
2
{
#

cos!2n( x,L"
}
dx
=
2
0
N
2
x

2n(

sin!2n( x,L"
since sin!2n( " = sin!0" = 07
=
2
!L

0

0

0"

There.ore, N
2
L,2 = # or N
2
= L,2 and N = !2,L"7
We may ta4e either sign .or the s0uare root since the phase o. the 6a/e .unction
has no e..ect upon any 0uantity 6hich 6e can measure7
e
2rt$ogonalit0 (See also Bo ,72+
The 6a/e .unctions corresponding to t6o di..erent /alues o. the 0uantum num3er, n,
are orthogonal, i7e7 the integral o. their product o/er the length o. the 3o is Kero7
We can pro/e this 3y integrating the product o. t6o 6a/e .unctions ha/ing 0uantum
num3ers n and m 6ith normalising constants N and 5 respecti/ely1
L
2 N5

L
sin!n( x,L"

sin!m( x,L" dx
0
L
N5

(x

(x

=
L
cos
0
Zn

m\
L
cos
Zn
+
m\
L
dx
N5

sin!Zn

m\( x,L"
sin!Zn
+
m\( x,L"

L
=
L Zn m\(,L

Zn + m\(,L
0
= 0 3ecause n and m are integers.
82D '1( Ele#troni# spe#tra o" #onH;gate/ pol0enes
According to the theory o. the chemical 3onding in con@ugated polyenes (Chapter ?+,
the ( 2electrons o. these molecules occupy or3itals 6hich are delocalised o/er the
6hole o. the car3on2atom chain7 These electrons should there.ore 3eha/e rather li4e
electrons in a linear 3o and, in particular, the electron2in2a23o model should pro/ide
approimate /alues .or their energy le/els7 There is no dou3t that the a3sorption 3and
o. longest 6a/elength, 6hich mo/es into the /isi3le spectral region as the length o.
the chain increases, is due to an electronic transition .rom the highest occupied to
the lo6est unoccupied ( 2electron energy le/el and the energy o. this 3and has 3een
correlated 6ith the gap 3et6een these energy le/els in many 0uantum2mechanical
treatments o. polyene spectra7 (See, .or eample, S7D7 Cason, 31arterly Revie0s of
the Chemical Society, %), 2%-, #$?#7+ Theory and eperiment may 3e related in the
.ollo6ing manner7
Consider a cyanine, a linear polyene, 6hich has the general .ormula sho6n in
Digure B,7*7#7 There are 2; + 2 3onds in the con@ugated system 3et6een the t6o
nitrogen atoms, 3ut it is 6ell 4no6n that methyl groups etend the con@ugated system7
We there.ore allo6 .or this (hypercon@ugati/e+ e..ect 3y adding one 3ond .or each o.
the t6o 9
,
CI;IC9
,
groups gi/ing a total o. 2; + * 3onds in the con@ugated system7
The length, L, o. the con@ugated system can no6 3e 6ritten as !2; + *"l, 6here l
is the mean 3ond length7 'ach car3on atom contri3utes one ( 2electron and the t6o
nitrogen atoms contri3ute three 3et6een them (# .rom ;+, 2 .rom ;1+, so that 6e
ha/e a total o. 2; + *( 2electrons7
The energy le/els o. an electron in a 3o are gi/en 3y the .ormula1
n
2
h
2
E
n
=
%m L
2
!n
=
# 2 , . . ."
;
9
,
C
77
+
C9
,
9
,
C
; (IC9 C9 +
;
C9 ;
C9
,
9
,
C
9
,
C
+



C9 ( C9
77
C9
,
C9 +
;
;
C9
,
6ig;re 8'1(1% The resonance structures o. cyanine dyes
Since the electrons occupy the energy le/els in pairs, the 0uantum num3er (n
hol
+
o. the highest occupied le/el is !2; + *",2 = ; + 2 and the 0uantum num3er o. the
lo6est unoccupied le/el, n
lul
, is ; + 2 + # = ; + ,7 Thus, using the a3o/e .ormula the
energy di..erence ( E+ 3et6een the lo6est unoccupied and highest occupied le/els is1
E = E
lul
E
hol
=
{
!; + ,"
2
!; + 2"
2
}h
2
%m
e
!2;
+
*"
2
l
2
!2; + 5"h
2
=
%m
e
!2;
+
*"
2
l
2
and 6e there.ore epect that a graph o. E against !2; + 5",!2; + *"
2
6ill 3e a
straight line o. gradient h
2
,%m
e
l
2
7 To calculate the gradient 6e re0uire an estimate
o. the mean 3ond length (l+7 Because o. the resonance 3et6een the t6o cyanine
tautomers, there is no 3ond alternation as in the polyenes and all the CIC 3onds
are e0ual in length7 There are /ery .e6 hydrocar3ons .or 6hich this is the case,
3ut 3enKene is one such 6hich suggests that 6e set l
=
#.,$

#0

#0
m, so that the
theoretical gradient is1
h
2
!?.?2? #0

,*
"
2
,#2

#0

20
J
%m
e
l
2
=
% $.#0$ #0

,#
!#.,$ #0

#0
"
2
=
Dor comparison 6ith eperiment 6e use the data .or the cyanines ta4en .rom
CasonGs re/ie6 and gi/en in Ta3le B,7*7#7 The data are plotted in Digure B,7*727
The eperimental slope o. ,#,

#0

20
J is in remar4a3le agreement 6ith the
simple model o. the electron in a 3o7 But it must 3e noted that .or other polyenes,
6here all CIC 3onds are either .ormal dou3le 3onds, C
=
C, or .ormal single 3onds,
CIC, the resulting alternation o. 3ond length and the conse0uent alternation o. the
electric Leld o. the ' 2electrons, in 6hich the ( 2electrons mo/e, ma4es the simple
theory less applica3le7 These additional e..ects are discussed 3y Cason7 ;e/ertheless,
this eample sho6s that e/en the most simple 0uantum2mechanical model is capa3le
Ta?le 8'1(1% The electronic spectra o. the cyanines
;
#
!2; + 5",!2; + *"
2
07#$**
<
ma
,nm
,#275
E,J #0

20
?,755
2 07#*0? *#?70 *-7-*
, 07##00 5#$70 ,%72?
* 070$0, ?2570 ,#7-%
5 070-?5 -,*75 2-70*
? 070??* %*%70 2,7*2

'

(
J

#
0

2
0
+
%0
-0
?0
50
*0
,0
20
#0
0
0700 0705 07#0 07#5 0720 0725
(2; + 5+H(2; + *+
2
6ig;re 8'1(1& E vers1s chain2length parameter .or cyanine dyes
o. gi/ing a 0uantitati/e interpretation o. real chemical data and there3y enhancing
our understanding o. the .undamental properties o. con@ugated molecules7
82D '1) Cal#;lation o" t$e expe#tation Aal;e o" t$e ang;lar moment;m o"
an ele#tron on a ring
We consider the electron in the state ha/ing the 6a/e .unction1
#
G
a
=
(
cos!a$"
6hich is not an eigen.unction o. the angular momentum operator, ih` D,D $7
The
epectation /alue o. the angular momentum, l, .or this eigen.unction is calculated as
.ollo6s1
2(

# ih
`
D

#
l
=
(
cos!a$"
0
2(

D$

(
cos!a$" d$
ih
`

=
(
0
cos!a$"
D
cos!a$" d$
D$
2
iah` =
(
iah
`
2(
cos!a$" sin!a$" d$
0
2(

iah` #
2(
=
2(
0
sin!2a$" d$ =
2(

2a
Zcos!2a$"\
0
=
0.
Bearing in mind (Appendi %+ the .act that1
cos!ax" =
#
{ep!+iax" + ep!iax"}
6e see that the cosine .unction is a sum o. the t6o angular momentum eigen.unctions,
ep!+iax" and ep!iax"7 Thus, i. 6e measured the angular momentum o. the system
6e 6ould epect to Lnd /alues o. +ah` and
ah`
in e0ual num3ers 6hich 6ould lead
to a mean /alue o. Kero as the num3er o. measurements increased7
82D '1* Heisen?erg ;n#ertaint0 relations$ips
The 3est 4no6n o. these, and the most important as .ar as chemistry is concerned,
are those in/ol/ing momentum and position along the same coordinate1
%
x
x h,*( %
y
y h,*( %
B
B h,*(
and those in/ol/ing t6o components o. angular momentum, i7e71
l
x
l
y
h,*( l
y
l
B
h,*( l
B
l
x
h,*(
An these relationships it is assumed that there is a Gaussian distri3ution o. the
uncertainties, i7e7 p is the root2mean2s0uare o. the )p o. the indi/idual measurements1

% =

!)%
i
"
2
i
As 6e ha/e seen in this chapter, the uncertainty relationships are intimately related
to the non2commutation o. the operators in/ol/ed7 An the case o. the angular momen2
tum operators, this is epressed in the .ollo6ing use.ul e0ualities deri/ed in Bo *7#1
Zl

x
l

y
\ = ih` l

B
P Zl

y
l

B
\ = ih` l

x
P Zl

B
l

x
\ = ih` l

y
6here Za *\ a * * a7
There is also an uncertainty relationship 6hich connects energy and time1
E t
h,*(
At is /ery /alua3le and 6e use it in Chapter %7 9o6e/er, it must 3e clearly under2
stood that, since time is not an o3ser/a3le, the relationship has an origin and signiL2
cance 0uite di..erent .rom the others 0uoted here7 The distinction is discussed in more
ad/anced tets, e7g7 J7J7 Sa4urai, 5odern 31ant1m 5echanics, Ben@aminHCummings,
Cenlo !ar4, #$%57
There is a /ery good discussion o. the 9eisen3erg uncertainty principle in C7
Born, Atomic Physics, Blac4ie & Son, ,rd 'dn, London #$**, Appendi FFAA7
82D '1+ !olarise/ lig$t an/ @;ant;m me#$ani#s
We can use 6ell24no6n results .rom classical optics to illustrate se/eral o. those
aspects o. 0uantum mechanics 6hich appear puKKling 6hen 6e Lrst encounter them7
The eperiments and their interpretation ha/e 3een discussed 3y <irac in Q-he Princi+
%les of 31ant1m 5echanicsG7 The Lrst edition o. this .amous 3oo4 appeared in #$,0
and 6as one o. the most important contri3utions to the mathematical and philosophical
.oundations o. 0uantum mechanics7 The eperiments in 0uestions are the .ollo6ing7
(See Chapter % .or .urther in.ormation a3out polarised light7+
A 3eam o. light propagating in the B direction and polarised in the xB plane is
directed onto a polariser7 The latter is an optical de/ice 6hich transmits incident light
i. the light is polarised along a particular direction 6hich 6e here call t t

, 3ut
6hich a3sor3s all the incident light i. it is polarised along a a

, the direction at
right angles to t t

(Digure B,7-7#+7 We assume the polariser to 3e per.ect7
Both a a

and t t

are perpendicular to the direction o. propagation o. the
light7 When the incident light is polarised at some intermediate angle, K , to t t
,
eperiment sho6s that i. :
0
is the intensity o. the incident polarised light and :
t
the
intensity o. the transmitted light then1
:
t
= :
0
cos
2
K and :
a
= :
0
sin
2
K
6here :
a
= :
0
:
t
, the intensity o. the light lost 3y a3sorption7 The transmitted light
is also polarised 3ut along t t

and not along its original direction o. polarisation
at an angle o. K to t t

7
=sing a techni0ue 4no6n as photon counting, the eperiments descri3ed a3o/e
can 3e carried out 6ith a 3eam o. light o. such a lo6 intensity that the photons
passing through the polariser can 3e indi/idually recorded7 Dor light polarised along
t

t

e/ery photon is transmitted 6hile .or light polarised along a

a

e/ery photon
is a3sor3ed and this presents us 6ith little conceptual di.Lculty7 But 6hat o. the
eperiments 6ith light polarised at an angle o. K to t t

J A. 6e no6 consider the
.ate o. each indi/idual photon 6e are una3le to say deLnitely 6hether it 6ill 3e
transmitted or a3sor3ed 3y the polariser7 We can only say that there is a pro3a3ility
o. cos
2
K that it 6ill 3e transmitted and a pro3a3ility o. sin
2
K that it 6ill 3e a3sor3ed
t
3
a
t
6ig;re 8'1+1% !lane o. polarisation o. incident light 6ith respect to directions o. transmission,
t

t

, and a3sorption, a

a

since this 6ill gi/e us the 4no6n eperimental result i. a large num3er o. photons
are su3@ected to the polarisation test7 We Lnd that 6e can only ma4e statements a3out
pro3a3ilities in respect o. the results o. a measurement on a single particle 6hich
o3eys the la6s o. 0uantum mechanics7 Thus, the Lrst aspect o. 0uantum mechanics
illustrated 3y the a3o/e eample is the statistical nature o. our 4no6ledge concerning
the 3eha/iour o. indi/idual particles and the results o. indi/idual measurements7
The second important point 6hich emerges a3o/e is that the ma4ing o. the mea2
surement has a pro.ound inOuence upon the particle su3@ected to that measurement7
The eperimental result is that all the photons 6hich pass through the polariser are
polarised along t

t

6hereas those 6hich are a3sor3ed must 3e polarised along
a

a

7 But all the incident photons 6ere polarised at an angle o. K to t

t

so
that the polarisation o. e/ery photon su3@ected to measurement has 3een changed7
There.ore, i. 6e ma4e a .urther measurement on the photons 6hich pass through the
polariser the o3@ects o. the second measurement are not eactly the same as the o3@ects
o. the Lrst measurement, their o3ser/a3le property o. polarisation has 3een changed7
The photons ha/e 3een Q.orcedG into eigenstates o. the operator 3y the measurement
process7 An general, there is no such thing as an eperimental measurement 6hich has
no e..ect upon the system measured, though there 6ould 3e no apparent e..ect i. each
incident photon 6as polarised along t

t

7
The concept o. polarisation as an o3ser/a3le property leads us to as4 6hat the
corresponding operator, eigen/alues and eigen.unctions are7 There are t6o eigenstates
o. polarisation in the a3o/e eperiment7 A. a photon is in eigenstate G
t
then it is
transmitted 3y the polariser, i. it is in the eigenstate G
a
then it is a3sor3ed7 A. 6e call
the Qpolarisation analysingG operator A

then1
A

G
t
= # G
t
and A

G
a
= 0 G
a
and .or a 3eam o. light polarised along t t

e/ery measurement gi/es the same
result1 photon transmitted7 Dor light polarised along a a

6e al6ays get the result1
photon a3sor3ed and annihilated7
A. 6e no6 consider the case o. photons polarised at an angle o. K to t

t

then, according to 0uantum mechanical principles, this state o. polarisation may 3e
descri3ed as a linear com3ination o. the possi3le eigenstates o. polarisation, i7e71
G
K
= C
t
G
t
+ C
a
G
a
6here the coe.Lcients C
t
and C
a
gi/e the contri3utions o. each o. the t6o eigenstates
to the state G
K
7 The coe.Lcients must 3e normalised so that1
C
t
2
+ C
a
2
= #.0 !B,.-.#"
3ecause the 6a/e .unction G
K
descri3es a single photon and the total pro3a3ility o. it
3eing either a3sor3ed or transmitted must 3e #707 Durthermore, and again according to
0uantum2mechanical principles, the outcome o. the determination o. the polarisation
o. a photon in the state G
K
must 3e such that the pro3a3ility that the photon is
polarised along t t

and is transmitted is C
t
2
and the pro3a3ility that the photon is
polarised along a a

and is a3sor3ed is C
a
2
7 But 6e 4no6 these pro3a3ilities .rom
eperiment to 3e cos
2
K and sin
2
K respecti/ely, so that1
C
t
= cos K and C
a
= sin K
!ro3lems .or Chapter , -#
and the .act that sin
2
K + cos
2
K = #.0 is eactly 6hat is re0uired to satis.y the nor2
malisation condition '0uation (B,7-7#+7 This last point illustrates ho6 the concepts
o. the superposition o. states and epectation /alue allo6 us to etract use.ul in.or2
mation .rom measurements on systems 6hich are not, at the time immediately 3e.ore
the measurement, in eigenstates o. the operator corresponding to the o3ser/a3le prop2
erty 6hich 6e are measuring7 At also sho6s that eigen.unctions (eigenstates+ and
eigen/alues are .undamental 3ut not immuta3le thingsP they are determined 3y the
measurements 6hich 6e choose to ma4e7 A. 6e rotated the polariser 3y
o
then a ne6
pair o. eigenstates 6ould 3e appropriate .or a discussion o. the eperiment a3o/e7
!R285EMS 62R CHA!TER '
#7 ConLrm the entries in columns three and .our o. the .ollo6ing ta3le7
"perator, P

D
2
Dunction, As an eigen.unction
o. P

J
A. QyesG, 6hat is
the eigen/alueJ
D#
2
D
D#

D
Dx
+
L

xD
sin # yes #
sin
2
# no
ep(ax+ yes a + L
2
Dx
+
L x yes 2 + L

xD
yD

Dx
+
Dy

D D

xy yes 2
xy
Dx
+
Dy
xy no
27 Sho6 that the .unctions ep!+inx" and ep!inx" are eigen.unctions o. the energy
operator .or an electron in a linear 3o, each ha/ing the same eigen/alue o. n
2
h`
2
,2m
e
7
,7 A deeper understanding o. the .ollo6ing pro3lem should 3e possi3le a.ter Chapters *
and 5 ha/e 3een studied7 But no 4no6ledge o. the material co/ered there is re0uired
to complete the present eercise7
The .ollo6ing, normalised .unctions are .unctions o. the polar coordinate, # , only,
apart .rom G
s
6hich is simply a constant1
G
s
=

!#,2" G
d
=

!5,%"!, cos
2
# #"
G
%
=

!,,2" cos # G
f
=

!-,%"!5 cos
,
# , cos #"
-2 The Application o. &uantum Cechanics
#
#
Sho6 that these .unctions are eigen.unctions o. the angular momentum operator L
2
1
L

2 2 2
#
=
cot #

D,D #
+
D ,D #
The eigen/alues o. L
2
gi/e the s0uare o. the or3ital angular momentum in
units o. !h,2( "
2
7 Sho6 that the eigen/alues are l!l + #", 6here l = 0, #, 2 and
, .or s % d and f respecti/ely7
*7 The .unctions
a
= N
a

x!L x" and

*
= N
*
x!L x", 6here N
a
and N
*
are nor2
malising constants, are not eigen.unctions .or the electron in a one2dimensional 3o
o. length L, 3ut they do satis.y the 3oundary conditions o. that system7
a+ Sho6 that N
a
= 2

,,L
2
, N
*
=

!,0,L
5
" and that the .unctions are not ortho2
gonal7
3+ =sing the position operator (Section ,7#,7#+ and the epression .or an epectation
/alue ('0uation (,7$72++ calculate the epectation /alue o. x, x, .or 3oth 6a/e
.unctions,
a
and
*
7 S4etch graphs o. the t6o .unctions Zset L
=
#.0\ to eplain
the di..erence in the t6o /alues o. x 7
c+ Sho6 that !
*
|x|
*
"
2
=
*
|x
2
|
*
7 This is e0ui/alent to saying that the s0uare
o. the mean o. a set o. num3ers is not e0ual to the mean o. the s0uares o. those
num3ers7
57 Calculate the epectation /alue .or the energy, E
*
, using the .unction
*
.rom 0uestion
*, the 4inetic energy operator ('0uation (,7?72++ and the epression .or an epectation
/alue ('0uation (,7$72++7 Write do6n the lo6est eact energy eigen/alue, E
#
, .or the
electron2in2a23o pro3lem ('0uation (,7?75++ and sho6 that E
*
= #.0#,2E
#
7 The .act
that the epectation energy calculated 6ith the approimate 6a/e .unction is greater
than the eact lo6est energy is an eample o. the /ariation theorem (Appendi 2+7
Note1 Be care.ul to distinguish 3et6een h and h`
= h,2( P '0uation (,7?75+ uses
the
.ormer and '0uation (,7?72+ the latter7
?7 =se '0uation (,7,7?+ to dra6 0uantitati/e energy2le/el schemes .or the ( 2electrons o.
3enKene (C
?
9
?
+, naphthalene (C
#0
9
%
+ and anthracene(C
#*
9
#0
+7 'stimate the radius
o.
the ring 3y assuming that its circum.erence is the num3er o. peripheral CIC 3onds
#,$ pm7 !lace the a/aila3le electrons in the lo6er energy le/els o. your energy2le/el
schemes and calculate the energy re0uired .or a transition .rom the highest occupied
to the lo6est unoccupied le/el .or each molecule7 Compare your results 6ith the
eperimental data .or the %ara23and 6hich is .ound in the electronic spectra o. these
molecules at $755, ?7%- and 5.2*

#0

#$
J .or 3enKene, naphthalene and anthracene
respecti/ely7
The agreement o. theory and eperiment is good, considering the simplicity o. the
model7 Among the most important aspects o. the pro3lem 6hich 6e ha/e neglected are
the e..ects o. the 3onds across the ring in naphthalene and anthracene and the strong
conLguration interaction (see Chapter ##+ 3et6een the .our possi3le ecited states o.
the same energy7
Chapter *
Ang;lar Moment;m
*70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -,
*7# Angular momentum in classical mechanics . . . . . . . . . . . . . . . . . . . . . . -,
*72 The conser/ation o. angular momentum . . . . . . . . . . . . . . . . . . . . . . . . -5
*7, Angular momentum as a /ector 0uantity . . . . . . . . . . . . . . . . . . . . . . . -5
*7* "r3ital angular momentum in 0uantum mechanics . . . . . . . . . . . . . . . . . -?
*7*7# The /ector model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . --
*75 Spin angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -%
*7? Total angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
*7?7# The addition and conser/ation o. angular momentum in 0uantum
-%
mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . -$
*7?72 The la6s o. 0uantum2mechanical angular momentum . . . . . . . . . . %#
*7- Angular momentum operators and eigen.unctions . . . . . . . . . . . . . . . . . %2
*7-7# The raising and lo6ering, shi.t or ladder operators . . . . . . . . . . . . %2
*7% ;otation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %,
*7$ Some eamples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . %*
*7#0 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . %?
!ro3lems .or Chapter * . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $,
(1. INTR23UCTI2N
An the application o. the 0uantum theory to chemistry, angular momentum is argua3ly
as important as energy7 At plays a /ital part in spectroscopy and in the theory o. atomic
structure7 At has e/en 3een suggested that angular momentum plays a more important
role than energy in determining the outcome o. intermolecular collisions7
#
Be.ore con2
sidering the 0uantum theory o. angular momentum 6e shall descri3e the phenomenon in
classical terms7
(1% ANU5AR M2MENTUM IN C5ASSICA5 MECHANICS
Consider a mass (&+ mo/ing 6ith /elocity (v+ in a circular path (radius r+ (Digure *7#+7
At any moment in time the /elocity o. the 3ody is directed at right angles to a line @oining
the 3ody to the centre o. the circle7 By deLnition, the linear momentum (p+ o. the 3ody
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
-* Angular Comentum
m
0
r
"
6ig;re (1% Angular momentum generated 3y an or3iting mass, m
is the product o. the mass and the /elocity1
p = & v !*.#.#"
and the angular momentum (a+ is the /ector product o. p and r,1
a = r p = rp sin # = r& v !*.#.2"
6here # is the angle 3et6een r and p7 The 0uantities in 3old type, r, v, p and a are all
/ector 0uantities, i7e7 they ha/e 3oth magnitude and direction7 The /ector a is located
at the centre o. the circle a3out 6hich the mass m rotates and, 3ecause it is the /ector
product o. r and p, its direction is at right angles to the plane containing r and p7 An
order to deLne a positi/e and negati/e direction .or a 6e Lrst deLne a right2handed co2
ordinate system (Digure *72+, 6hich is one 6here a rotation .rom +x to +y ad/ances a
right2handed scre6 along the positi/e direction o. the B2ais7 Then, i. v is directed .rom
+x to6ards +y the resulting angular momentum is positi/e, 6hereas i. the direction o.
motion is .rom +y to +x a is negati/e7 Thus, 3y rotating a 6heel on an ale 6e can
generate either positi/e or negati/e angular momentum, depending upon the direction
o. rotation7 The angular momentum so generated is represented 3y a /ector 6hich lies
along the ale7 A. the rotating 6heel is /ie6ed .rom +K, cloc46ise (Digure *7,(a++ and
N
R
F
An a right2handed co2ordinate system, a rotation
.rom +F to +R ad/ances a right2handed scre6
in the positi/e N2direction
6ig;re (1& <eLnition o. a right2handed co2ordinate system
Angular Comentum as a 8ector &uantity -5
N
N
a
p = m p M m
a
(a+ (3+
6ig;re (1' Angular momenta produced 3y cloc46ise and counter2cloc46ise rotations
counter2cloc46ise (Digure *7,(3++ rotations produce negati/e (a directed a6ay .rom the
o3ser/er+ and positi/e (a directed to6ards the o3ser/er+ angular momentum respecti/ely7
(1& THE C2NSERVATI2N 26 ANU5AR M2MENTUM
Li4e energy, angular momentum is a conser/ed 0uantity and, 3eing a /ector 0uantity, 3oth
the magnitude and direction o. a are maintained i. they are not inOuenced 3y eternal
.actors7 The constancy o. direction is eploited in the gyroscope 6hich, prior to satellite
technology, 6as 6idely used in na/igational e0uipment7 At is the property 6hich 4eeps
a spinning top upright and is surprisingly strong7 Ta4e a cycle 6heel, hold the spindle,
one end in each hand, and start the 6heel rotating gently7 ;o6 mo/e the 6heel /ertically
up and do6n or horiKontally .rom side to side7 Rou should .eel no resistance to these
mo/ements since you are not attempting to change the direction o. the angular momentum
/ector7 ;o6 try to tip the 6heel 3y raising one hand and lo6ering the otherP the resistance
to this mo/ement arises 3ecause the direction o. the angular momentum is conser/ed7 A.
you do this 6hile seated on a s6i/elling o.Lce chair you 6ill Lnd that the angular
momentum is conser/ed 3y a rotation o. the chair7
The conser/ation o. angular momentum ma4es the spinning 3ullets .rom a gun 6ith a
riOed 3arrel much more sta3le in Oight than those .rom a smooth23ored 6eapon, greatly
increasing the range o. accuracy and hence lethality7 The introduction, 3y the =nion,
o. the SpringLeld riOed23ore mus4et into the American Ci/il War (#%?# I #%?5+
caused the Con.ederacy dread.ul losses 3e.ore they adopted ne6 tactics and o3tained
similar 6eapons themsel/es7 This e..ect on pro@ectiles 6as 4no6n to the ancient
Gree4s 6ho, around 500 BC, used 6ooden @a/elins 6ith a length o. string 6ound
around the centre in athletic competitions7 When the @a/elin 6as thro6n the athlete
6ould hold on to the string, causing the @a/elin to rotate there3y increasing the length
o. his thro67
(1' ANU5AR M2MENTUM AS A VECT2R QUANTITY
Since it is a /ector 0uantity, angular momentum has a component in any direction in
space 6hich 6e choose to speci.y7 At is use.ul to 3e a3le to speci.y the components along
the x, y and B aes o. a Cartesian co2ordinate system and this can 3e easily done7 A. 6e
-? Angular Comentum
2(
4no6 the angles L, K and N 3et6een the angular momentum /ector (a+ and the x, y, and
B aes respecti/ely, then the re0uired e0uations are1
a
x
= a cos L a
y
= a cos K a
B
= a cos N (*7,7#+
The classical angular momentum 6hich has 3een descri3ed a3o/e is also called or3ital
angular momentum since it arises as a result o. a mass eecuting an or3it around a
Led point7
(1( 2R8ITA5 ANU5AR M2MENTUM IN QUANTUM MECHANICS
"r3ital angular momentum is also .ound in 0uantum mechanics (Bo *7#+ 3ut the 0uantum
and classical or3ital angular momenta di..er in t6o aspects related to 0uantisation7 Dirstly,
in 0uantum mechanics the total angular momentum is 0uantised 6ith possi3le magnitudes
gi/en 3y the e0uation1
a =

d!d + #"
h


d!d + #"
h`
!*.*.#"
6here h is !lanc4Gs constant and d is a 0uantum num3er 6hich can ta4e all positi/e
integer /alues, including Kero, i7e7 d = 0 # 2 , . . . A molecule rotating .reely in space
has angular momentum o. this type7 ;ote that the 0uantity h,2( occurs so .re0uently and
is so important that it has its o6n sym3ol (h` + 6hich is spo4en Qh2crossG7
Secondly, though the x, y and B components o. a classical angular momentum /ector
can al6ays 3e speciLed as in '0uation (*7,7#+, 0uantum mechanics places /ery important
restrictions on the components o. angular momentum 6hich can 3e speciLed7 The Lrst o.
these restrictions is that the component in only one direction in space may 3e speciLed7
Thus, i. the B component is gi/en, no or y components may 3e speciLed7 Durthermore,
the components in the direction 6hich can 3e speciLed, and there is no restriction in
our choice o. this one direction, are 0uantised7 Whiche/er the direction chosen, B in
'0uation (*7*72+, the allo6ed 0uantised components are gi/en 3y the e0uation1
a
B
= m
d
h,2( m
d
h`
!*.*.2"
6here m
d
is a 0uantum num3er 6hich can ta4e all integer /alues .rom d to +d 1
m
d
= d !d #" !d 2" . . . # 0 +# . . . + !d #" +d (*7*7,+
gi/ing 2d + # /alues .or m
d
7 The results epressed in '0uations (*7*7#+, (*7*72+ and (*7*7,+
are deduced .rom the angular momentum commutation relationships in Bo *7#7
Thus, .or d = 0 m
d
= 0
d = # m
d
=
# 0
+
#
d = 2 m
d
=
2

# 0
+
#
+
2 etc7
An '0uation (*7*72+, the B ais has 3een selected as the one .or 6hich the components
o. angular momentum are speciLed7 This is purely a matter o. choice 3ut it is a con/ention
6hich has 3een uni/ersally adopted7 The sym3ol, m
d
, .or the 0uantum num3er a3o/e 6as
chosen 3ecause o. the close relationship 3et6een this 0uantum num3er and the magnetic
properties o. atoms7 The origins o. this relationship 6ill 3e descri3ed in Chapter #27
"r3ital Angular Comentum in &uantum Cechanics --
O
m
d
= +2
m
d
= +#
m
d
= 0
m
d
= #
m
d
= 2
0 = ,57,
0 = ?57$
0 = $070
0 = ##*7#
0 = #**7-
6ig;re (1( The L/e B2components o. an angular momentum characterised 3y an angular momen2
tum 0uantum num3er o. 2
Thus, in 0uantum mechanics, or3ital angular momentum is descri3ed 3y t6o 0uantum
num3ers, d 6hich gi/es the /alue o. the 0uantised total angular momentum through
'0uation (*7*7#+ and m
d
6hich gi/es the allo6ed components o. the angular momentum in
the B direction through '0uation (*7*72+ and is restricted in its /alues 3y '0uation (*7*7,+7
This .orm o. 0uantisation is 4no6n as space 0uantisation 3ecause the spatial orientation o.
the angular momentum 6ith respect to the B2ais is restricted 3y the 0uantisation o. its B
component7 ;ote that the maimum component, a
B
is d
h`
and is there.ore al6ays smaller
than the total angular momentum,

Zd!d + #"\h
`
7 This means that the 0uantised component
(a
B
+ ne/er lies eactly along the total angular momentum /ector (a+ (Digure *7*+7 This is
a .urther conse0uence o. the uncertainty principle7 A. a
B
6ere aligned along a 6e 6ould
4no6 not only the /alues o. a and a
B
, 3ut also those o. a
x
and a
y
, 3ecause they 6ould
3oth 3e Kero7 Thus, 6e 6ould 4no6 e/erything that there is to 4no6 a3out the angular
momentum o. the system and in 0uantum mechanics that is not permitted, as 6e ha/e
seen in Section ,7#07 Digure *7* illustrates this point7
(1(1% T$e Ae#tor mo/el
We ha/e a situation in 6hich the length o. a /ector and its pro@ection on the B ais are
deLned, 3ut nothing more a3out its orientation can 3e said7 Since there is no reason to
treat the and y aes di..erently, 6e must assume that the pro@ection o. the /ector in
the y2plane points in all possi3le directions 6ith e0ual pro3a3ility7 This concept .orms
the 3asis o. the vector model o. angular momentum in 6hich the /ector d is en/isaged
as precessing a3out the B ais so that it descri3es a cone a3out that ais in 6hich the
hal.2angle at the ape o. the cone (# + is gi/en 3y '0uation (*7*7*+1
m
d
cos #
=
d!d
!*.*.*"
+ #"
We should not lea/e this aspect o. angular momentum 6ithout ta4ing ad/antage o.
the opportunity it pro/ides o. illustrating the 6ay in 6hich classical mechanics may
3e regarded as a limiting case o. 0uantum mechanics7 The .act that there is al6ays a
Lnite angle (# + 3et6een the total 0uantum2mechanical angular momentum /ector and its
-% Angular Comentum
=
maimum B component is a non2classical result7 Since the maimum /alue o. m
d
is d ,
cos(# Zmin\+ is gi/en 3y1
m
d
Zma\ d

d
cos!# Zmin\"
=
d!d
+ #"
=
d!d + #"
=
d + #
(*7*75+
Thus, as d 3ecomes /ery large cos!# Zmin\" tends to #, # Zmin\ tends to Kero and
the maimum possi3le B component o. the angular momentum approaches the /alue o.
the total angular momentum, 6hich is 6hat it 6ould 3e in classical mechanics7
(1) S!IN ANU5AR M2MENTUM
As 6e ha/e seen in Section 27-, in his model o. the hydrogen atom Bohr 0uantised
electronic or3ital angular momentum thirteen years 3e.ore the 3irth o. 0uantum mechanics7
An #$25, .urther studies o. the spectra o. atoms and the e..ect o. magnetic Lelds upon them
led Samuel A3raham Goudsmit (#$02 I #$-%+ and George 'ugene =hlen3ec4 (#$00 I
#$%%+ to postulate that, in addition to its or3ital angular momentum, an electron also
possesses another type o. angular momentum 6hich they called spin angular momentum7
Li4e the or3ital angular momentum, the spin angular momentum also plays a role in the
magnetic properties o. atoms, though the relationship 3et6een the angular momentum and
the magnetism is not eactly the same in 3oth cases (see Section #272+7
Wol.gang !auli (#$00 I #$5%+, 6ho had used the concept o. electron spin to
.ormulate his eclusion principle in #$25, introduced spin into the ne6 0uantum
mechanics t6o years laterP 3ut in a phenomenological manner7 An #$2% <irac placed
the concept on a much Lrmer .ooting 6hen he .ound that the electron2spin 0uantum
num3er arose natu2 rally 6hen the 0uantum mechanics o. the hydrogen atom 6as made
compati3le 6ith the theory o. relati/ity7 <etailed study then re/ealed that the spin angular
momentum o3eyed '0uations (*7*7#+, (*7*72+ and (*7*7,+ eactly as or3ital angular
momentum did, 3ut 6ith one important di..erence7 Dor spin the 0uantum num3er d could
ta4e positi/e hal.2integer as 6ell as integer /alues7 Thus, in addition to the d and m
d
/alues gi/en a3o/e, .or spin 6e can also ha/e1
d
=
#
P m
d
#

+
#
2 2 2
, # # ,
d
=
,
P m
d =

+ +
2 2 2
5 ,
2 2
# # , 5
d
=
5
P m
d =

+ + + etc7
2 2 2 2 2 2 2
(1* T2TA5 ANU5AR M2MENTUM
The total angular momentum o. an atom or molecule is usually composed o. 3oth spin
and or3ital parts and 3oth o. these contri3utions may arise .rom se/eral sources7 Dor
eample, the spin angular momentum may 3e electron spin, 3ut the spins o. the nuclei
are also important in many 3ranches o. atomic and molecular spectroscopy7 "r3ital angular
momentum may 3e due to or3ital motion o. electrons7 At may also arise as a result o.
the rotation in space o. the molecule as a 6hole7 These /arious angular momenta are not
independentP they interact 6ith each other 3y mechanisms o. 6hich 6e shall gi/e some
eamples in the chapters on atomic structure and spectroscopy7 At is important there.ore
that 6e ha/e a 6ay o. adding angular momenta together7
(1*1% T$e a//ition an/ #onserAation o" ang;lar moment;m in
@;ant;m me#$ani#s
An classical mechanics the addition o. t6o angular momenta is 0uite straight.or6ard7 The
tails o. the t6o /ectors are 3rought to the same point and the addition parallelogram
constructed to gi/e their sum7 An Digure *75a, a + b = c 7 Thus, .or any pair o. /ectors a
and b, each o. Led magnitude (length+ and direction (orientation+, there can 3e one, and
only one, resultant (c+7 Angular momentum is conser/ed and c must 3e the /ector sum
o. a and b7 Digure *753 sho6s an alternati/e .orm o. the addition diagram7
The addition o. angular momentum in 0uantum mechanics is not as simple 3ecause all
contri3utions to the total angular momentum are themsel/es 0uantised and the addition
process, also 4no6n as co1%ling, must ensure that the sum itsel. and also its components
are 0uantised7 At can 3e sho6n (Bo *72+
2
that i. t6o angular momenta characterised 3y
the angular momentum 0uantum num3ers d
#
and d
2
are added to .orm a total angular
momentum characterised 3y the 0uantum num3er d , then d can ta4e all the /alues gi/en
3y the '0uation (*7?7#+P also 4no6n as the Cle3sch I Gordan series1
d = d
#
+ d
2
d
#
+ d
2
# d
#
+ d
2
2 . . . |d
#
d
2
| (*7?7#+
e7g7 d
#
=
, d
2
=
# 1 d
=
* , 27 d
#
=
2 d
2
=
,
1 d
=
-

5

,

#
7
2 2 2 2 2
(;ote ho6 the series terminates at the modulus o. the di..erence 3et6een d
#
and d
2
7+
Although d
#
and d
2
are deLned as completely as is possi3le in 0uantum mechanics,
according to '0uation (*7?7#+ 2d
P
+ #, 6here d
P
is the smaller o. d
#
and d
2
, resultants
o. the addition o. d
#
and d
2
are permissi3le, rather than the single resultant 6hich 6e
6ould ha/e in classical mechanics, (Digure *75+7 At is tempting to attempt to dra6 t6o
/ectors ha/ing lengths characterised 3y their /alues o. d
#
and d
2
and orientations 6ith
respect to the B ais determined 3y their /alues o. m
d #
and m
d 2
and to add these in the
classical manner, compara3le to Digure *75, to o3tain a /ector characterised 3y d and m
d
gi/en 3y the rules .or the addition o. 0uantum2mechanical angular momentum 0uoted
a3o/e7 This is not possi3le 3ecause the plane containing the B ais and d
#
cannot 3e
assumed to 3e coincident 6ith that containing the B ais and d
2
7 The rules apply to the
0uantum num3ers and the angular momentum /ectors constructed using them cannot 3e
added as in classical mechanics7 But the B components o. d
#
and d
2
3oth lie along the
B ais and can 3e directly added and each component o. the com3ined /ector,
|
d m
d

,
is a sum o. the components o. the com3ining /ectors,
|
d
#
m
d #

and
|
d
2
m
d 2

,
6hich
includes all those 6hich satis.y the re0uirement that m
d
=
m
d #
+
m
d 2
7 Dor eample, one
can sho6 using the raising and lo6ering operators (Section *7-7# and Bo *7#+ that in the
a c
a
*
*
c
(a+ (3+
6ig;re (1) The addition o. angular momenta in classical mechanics
2
d
#
case o. the second o. the a3o/e eamples the resultant /ector
|
5

+
#

6ith d
=
5
and
m
d
= +
#
, is1
2 2 2
|
2

+
2
=
,

!,,-0"
|
2

#
|
2

+
2
+

!?,-0"
|
2 0
|
2

+
2

5 # , , , #

5,

!-0"
|
2
+
#
|
,


#

2

!,,-0"
|
2
+
2
|
,


,
2 2 2 2
The numerical coe.Lcients in the a3o/e sum are 4no6n as Cle3sch I Gordan
coe.Lcients and .ormulae .or calculating them .rom d , m
d
d
#
m
d #
d
2
and m
d 2
can 3e
.ound in many sources7
2I5
They are also etensi/ely ta3ulated7
?
An spite o. the o3/ious di.Lculty o. illustrating the 0uantum2mechanical addition o.
/ectors, one .re0uently encounters diagrams o. that type and they are /ery help.ul in
understanding comple coupling processes such as are .ound in molecular electronic
spectroscopy7 The 3asic situation is illustrated in Digure *7?7 An Digure *7?(a+ the t6o
/ectors, d
#
and d
2
, are not coupled7 'ach precesses a3out the B ais, independently 6ith
constant B components (&
#
and &
2
+ 3ut not in phase7 d
#
, d
2
, m
#
and m
2
are good
71an+ t1m n1m*ers and the corresponding angular momenta and B components are
separately o3ser/a3le7 An Digure *7?(3+ d
#
and d
2
, are coupled to .orm d, a3out 6hich
they precess together and in phase7 They no longer ha/e constant B componentsP d
#
, d
2
,
m
#
and m
2
are not good 0uantum num3ers and the corresponding angular momenta and
components are not o3ser/a3le7 d precesses a3out B 6ith a constant B component, &, the
0uantum num3ers d and m are good 0uantum num3ers and the corresponding angular
momentum and its B component are eperimental o3ser/a3les7 This point is illustrated
6ith an eample in Section *7?727
"ne other conse0uence o. the .act that, in 0uantum mechanics, there can 3e more
than one result .or the sum o. t6o /ector 0uantities should 3e mentioned here7 We
shall in/estigate it .urther in Chapter % 6hen 6e consider the 0uestion o. the con2
ser/ation o. angular momentum in connection 6ith spectroscopic selection rules7 At
this point 6e need only say that i., 3e.ore a particular e/ent, a system consists o.
t6o angular momenta characterised 3y the angular momentum 0uantum num3ers d
#
and d
2
and i., a.ter the e/ent, the system has an angular momentum characterised
3y d then i. d satisLes any o. the 2d
P
+
# '0uations (*7?7#+, angular momentum has
3een conser/ed7
N N
d
d
# m
# m
m
2
d
2
d
2
(a+ (3+
6ig;re (1* The addition (coupling+ o. t6o angular momenta
(1*1& T$e laws o" @;ant;m9me#$ani#al ang;lar moment;m
"nce 6e ha/e a .ormula .or the addition o. t6o angular momenta 6e can add any num3er
o. contri3utions 3y repeated applications o. the .ormula7 (But note ho6 rapidly the num3er
o. possi3le /alues .or the total angular momentum risesU+
And although there may 3e many contri3utions to the total angular momentum o. a
molecule, 6e can ma4e three general statements a3out angular momentum 6hich each
indi/idual contri3ution to the total and the total itsel. must o3ey7 They are1
#7 The s0uare o. the angular momentum, a
2
, is gi/en in terms o. the 0uantum num3er d
in the .orm o. '0uation (*7*7#+1
a
2
= Zd!d + #"\h`
2
6here d can ta4e any positi/e integer or hal.2integer /alue, including Kero7
27 The components o. the angular momentum, a
B
, in any speciLed direction (con/ention2
ally the B2ais+ are gi/en 3y '0uation (*7*72+1
a
B
= m
d
h`
6here the 0uantum num3er m
d
can ta4e all 2d + # /alues .rom d to +d in unit
steps, '0uation (*7*7,+7
,7 A. the angular momentum is purely or*ital angular momentum the 0uantum num3er d ,
and hence m
d
, can ta4e only integer /alues7 When spin is in/ol/ed hal.2integer /alues
are also possi3le7
These three statements might 3e termed the la6s o. 0uantum2mechanical angular
momentum and t6o important points a3out them should 3e made7 Dirstly, it is rare
to o3ser/e the angular momentum directly, usually it is the transitions 3et6een states
o. angular momentum 6hich gi/e rise to o3ser/a3le eperimental data7 Secondly, in
cases 6here t6o or more angular momenta are com3ined, or co1%led (Section *7?7#+,
the o3ser/a3le eperimental data are related to changes in the total angular momentum
and must 3e interpreted in terms o. the corresponding total 0uantum num3ers7 But the
indi/idual 0uantum num3ers .or the contri3uting angular momenta play an important role
in descri3ing the system theoretically and it is in that sense that 6e can say that the
indi/idual contri3utions to the total angular momentum o3ey the a3o/e la6s, e/en 6hen
they are not eperimentally o3ser/a3le7
At might 3e help.ul to ma4e this point clear 6ith an eample7 An a hea/y atom,
the or3ital angular momentum o. an electron (0uantum num3er l+ may couple 6ith
the spin angular momentum o. the same electron (0uantum num3er s+ to gi/e a total
angular momentum characterised 3y the 0uantum num3er & 7 (See Section 57% .or more
details on this phenomenon 6hich is called s%in+or*it co1%ling7+ 'perimental o3ser2
/ations are interpreta3le in terms o. & 6hich is said to 3e a good 0uantum num3er7
The or3ital and spin angular momenta corresponding to the 0uantum num3ers l and s
only .eature in the theoretical description o. the atom, they are not o3ser/ed directly
in the eperimental measurements and, conse0uently, l and s are not good 0uantum
num3ers7
(1+ ANU5AR M2MENTUM 2!ERAT2RS AN3 EIEN6UNCTI2NS
An Chapter , 6e discussed the 3asic application o. SchroM dingerGs theory o.
o3ser/a3les, operators, eigen.unctions and eigen/alues using eplicit mathematical
.unctions .or the operators .or energy and angular momentum in our eamples7 We
consider these ideas again here 3ecause, .or angular momentum, the concept ta4es an
etremely simple .orm in 6hich, .or many applications, 6e do not need to gi/e .ull
mathematical epressions .or either the operators or the eigen.unctions7 This is /ery
.ortunate, not only on account o. the resulting simplicity 3ut also 3ecause the operators
.or spin angular momentum cannot 3e o3tained .rom the corresponding classical
epressions 3ecause there is no classical analogue o. 0uantum2mechanical spin7
An Bo *7# eigen.unction2eigen/alue e0uations .or the Lrst t6o la6s o. Section *7?
('0uations (B*7#722a+ and (B*7#7223++ are deri/ed7 We repeat those e0uations here 6ith
d

as the operator .or total angular momentum and d

B
that .or its K
component1

and
d

|
d m
d
=
d!d
+
#"

h
`
|
d m
d

!*.-.#"
d

B
|
d m
d
=
m
d

h`
|
d m
d

!*.-.2"
9ere 6e are adopting a notation, Lrst suggested 3y <irac, in 6hich 6e speci.y the eigen2
.unction |d m
d
, solely 3y gi/ing the 0uantum num3ers 6hich deLne it and determine
its eigen/alues7 Angular momentum eigen.unctions are characterised 3y t6o 0uantum
num3ers7 The Lrst (d + gi/es the total angular momentum, in units o. hH2( , according
to '0uation (*7-7#+7 The second (m
d
+ gi/es the B component o. that angular momen2
tum, also in units o. hH2( , according to '0uation (*7-72+7 The corresponding eigen.unc2
tion is eactly identiLed, as .ar as its angular momentum properties are concerned,
i. the /alues o. these t6o 0uantum num3ers are gi/en, and that is .re0uently su.2
Lcient .or our purposes7 The sym3ol
|
d m
d

is there.ore all that 6e need to 6rite
'0uations (*7-7#+ and (*7-72+, 6hich satis.y the re0uirement that the operator operating
on the eigen.unction is e0ual to the eigen.unction multiplied 3y a num3er, the eigen/alue7
The eigen/alues o. the angular momentum operators are the o3ser/a3le, 0uantised /al2
ues o. the total angular momentum and its B component gi/en in units o. h,2( 3y the
0uantum num3ers7
(1+1% T$e raising an/ lowering< s$i"t or la//er operators
Since 6e cannot 4no6 the /alues o. the and y components o. the angular momentum i.
6e already 4no6 the B component, 6e cannot 6rite eigen.unction2eigen/alue e0uations
li4e '0uation (*7-72+ .or d

x
and d

y
7 9o6e/er, there are t6o operators deri/ed .rom d

x
and
d

y
6hich 6e use in Bo *7#7 Although they are not eigen.unction2eigen/alue
e0uations,
they are o. great /alue to us7 The operators are the raising and lo6ering operators, d

+
and d

deLned 3y the e0uations1
and
d

+
= d

x
+ id

y
!*.-.,"
d

= d

x
id

y
!*.-.*"
;otation %,
An these t6o e0uations, i =

! #"P .or more in.ormation a3out i see Appendi %7 The

t6o operators ha/e /ery important properties 6hich are deduced in Bo *7# ('0uations
(*7#7,#a+ and (*7#7,#3++ and repeated here as '0uations (*7-75+ and (*7-7?+1

d

+
|
d m
d
=
Zd!d
+
#"

m
d
!m
d
+
#"\

h
`
|
d m
d
+
#

(*7-75+
d

|d m
d
= Zd!d + #" m
d
!m
d
#"\ h`
|d m
d
# (*7-7?+
The application o. either operator does not change the /alue o. the total angular
momentum (the 0uantum num3er d remains the same+ 3ut each changes the /alue o.
the B component o. the angular momentum 3y one unit o. h,2( 7 d

+
raises the /alue o.
d
B
, i7e7 (m
d

m
d
+
#+, and d

lo6ers it (m
d

m
d

#+7 Dor eample1

d

+
|
2 #
=
Z!2

,"

!#

2"\

h`
|
2 2
=
2h`
|
2 2

|
2 #
=
Z!2

,"

!#

0"\

h`
|
2 0
=
?h`
|
2 0

These are not eigen.unction2eigen/alue e0uations 3ecause the .unctions on the le.t2
and right2hand sides o. '0uations (*7-75+ and (*7-7?+ are not the same7 :ather, these t6o
operators ta4e us up (d

+
+ and do6n (d

+ a set o. m
d
/alues, one step at a time7 They are
there.ore 4no6n as the raising and lo0ering ladder or shift operators7 ;ote that i. 6e
try to raise an m
d
/alue 6hich is already at its maimum, i7e7 m
d
= d , 6e get a result o.
Kero7 The same is true i. 6e try to lo6er a /alue o. m
d
6hich is already at its minimum
/alue, i7e7 m
d
= d 7
(1, N2TATI2N
The 0uantum num3ers d and m
d
in the a3o/e la6s represent any .orm o. angular momen2
tum7 At has 3ecome customary to denote the /arious types o. angular momentum 6ith
a particular choice o. sym3ols .or d as the 0uantum num3er and this practice is so
6idespread and consistent that it should 3e stated here7
The or3ital angular momentum o. an electron in an atom1 l and m
l
7
The spin angular momentum o. an electron1 s and m
s
7
The com3ined spin and or3ital angular momentum o. an
electron in an atom1
Where the angular momentum results .rom more than
one electron this is indicated 3y using the upper case
letters1
& and m
&
7
L, 5
L
, S, 5
S
, Q , 5
Q
7
The spin angular momentum o. an atomic nucleus1 : and 5
:
7
The or3ital angular momentum o. a rotating diatomic
molecule1
The or3ital angular momentum o. a molecule rotating in
space1
Q and 5
Q
7
R and 5
R
7
(An the last three cases the upper case letter is al6ays used, e/en .or one nucleus or
one molecule7+
%* Angular Comentum
=
2
2
,
2
2 2
# ,
" "
2
=
2
2
=
2
#
2
2
= = +
2 2 2
2
(1- S2ME EDAM!5ES
A single electron has s
=
#
and there.ore m
s
#
and +
#
7 Thus, a single electron can
2 2 2
3e .ound in t6o di..erent spin states7 When t6o electrons occupy the same or3ital (spatial
# #
region+ in an atom or molecule one has m
s
=
2
and the other m
s
= +
2
7 They are said
to 3e spin2paired or, simply, paired7
The s, %, d , . . . atomic or3itals o. atoms (see Chapter 5+ ha/e or3ital angular momen2
tum 0uantum num3ers, l = 0 # 2 . . . respecti/ely7 Associated 6ith these there are m
l
/alues o. 0 .or s, #, 0, +# .or % and 2, #, 0, +#, +2 .or d , etc7 Thus, there is @ust
one s or3ital, 3ut there are three % or3itals, L/e d or3itals, se/en f or3itals, . . . 7 The
element 3oron consists o. t6o isotopes, #$7? Y o.
#0
B and %07* Y o.
##
B7 The nuclear
spin 0uantum num3ers o. the t6o isotopes are , and
,
respecti/ely and 6e there.ore
ha/e1
#0
/: = , 5
:
= , 2 # 0 +# +2 +,
##
/: =
,
5
:
=
2


2

+
#
+
,
The rigidity and simplicity o. the rules o. 0uantum2mechanical angular momentum
ma4e more comple systems 0uite easy to handle, in principle, though .re0uently tedious
in practice7 Suppose that 6e ha/e one electron in a % or3ital7 Then, s =
#
and the possi3le
m
s
/alues are
#
and +
#
, 6hile l = # and the possi3le m
l
/alues are #, 0 and +#7
:ecall that the m
s
and m
l
/alues gi/e the components o. the angular momenta along the
B ais7 There.ore, adding the B components o. the or3ital and spin /ectors 6e ha/e si
possi3ilities .or the B component o. the com3ined momenta, m
&
1
m
l
m
s
m
&
# + ! " =
m m
s
m
&
0
+
!

# #
m
l
m
s
m
&
+
#
+
!

# #
2 2 2 2 2 2
# # # # ,

#
+
!
+
#
"
=
0 + !+ " = +
+# + !+
" = +
2 2 2 2 2 2
The result o. adding the B components o. or3ital and spin angular momenta are si
m
&
/alues 6hich represent the B components o. the com3ined angular momenta7 And 6e
4no6 .rom the a3o/e la6s, 6hich angular momentum al0ays o3eys, that the /alues o.
these components must go .rom m
&
to +m
&
in unit steps7 There.ore, i. there is an m
&
/alue o.

,
it must 3e associated 6ith .urther m
&
/alues o.

#

+
#
and
+
,
7 Durthermore,
2 2 2 2
6e also 4no6 that the maimum m
&
/alue 6ill 3e the same as the & /alue .or the total
angular momentum, so 6e ha/e disco/ered that our single % electron can ha/e a state o.
angular momentum characterised 3y the 0uantum num3ers1
& =
,
and m
&
,
#

+
# +
,
We remo/e these .our /alues .rom our list a3o/e (it does not matter 6hich o. the t6o
# #
+
2
and

2
/alues 6e chooseP this is merely a 3oo424eeping eercise+ and there remain
@ust t6o m
&
/alues,

#
and
+
#
7 Clearly, there is a second angular momentum state .or
2 2
our p electron 6hich is characterised 3y the 0uantum num3ers1
& =
#
and m
&
#
+
#
These results .or the possi3le /alues o. & should 3e compared 6ith those o3tained 3y
adding the spin and or3ital angular momenta according to the rule gi/en in Section *7?7#7
#
2
=
2
=
2
#
2 2
7
2
Some 'amples %5
We can apply a similar method to determine the spin states o. a t6o2electron system7
We Lrst ta3ulate all the possi3le com3inations o. m
s#
and m
s2
and their total 5 1
m
s#
m
s2
5 m
s#
m
s2
5 m
s#
m
s2
5
# # # # # #
+
2
+
2
+
#
+
2

2
0

2

2

#

2 2
0
Clearly, the /alue 5 = +# must 3e associated 6ith t6o other components, 5 = 0
and 5 = #7 Thus, there is a state 6ith a total spin o. S = # 6hich, 3ecause it has three
components |# +# |# 0 and |# # , is called a tri%let7 A singlet, |0 0 , 6ith S = 0
and 5 = 0 remains7
To Lnd the eigen.unctions 6e Lrst use the lo6ering operator (S

+ on the com3ined
spin .unction |# +# 1

|
#
+
#
=
#!# + #" #!# #"|# +# = 2|# 0
We no6 apply the lo6ering operators (s

!#" and s

!2"+ to the spin .unctions o.

the indi/idual electrons1
# # # # # #
{
s

!#"
+
s

!2"
}| +
2
!#"
+
2
!2"
=
s

!#"
| +
2
!#"
+
2
!2"
+
s

!2"
| +
2
!#"
+
2
!2"

# # # #
'0uating the t6o results1
= |
2
!#"
+
2
!2"
+ | +
2
!#"

2
!2"


# # # # #
|# 0 =
2
{|
2
!#"
+
2
!2"
+ | +
2
!#"

2
!2"
}
Durther lo6ering operations on 3oth sides o. the a3o/e e0uation gi/e1
|
#

#
= |
#
!#"

#
!2"
2 2
The singlet state, |0 0 , must ha/e 5 = 0 and 3e orthogonal to the state |# 0 7 These
t6o conditions determine its eigen.unction to 3e1

# # # # #
|0 0 =
2
{|
2
!#"
+
2
!2"
| +
2
!#"

2
!2"
}
As a Lnal eample 6e consider the spin properties o. the hydrogen atom 6hich ha/e
some interesting applications7 The nucleus o. the hydrogen atom, the proton, has a spin
o. : =
#
and 5
:
#
and +
#
7 The single electron has s =
#
and m
s
#
and +
#
There.ore, there are .our possi3le spin states o. the hydrogen atom1
5
:
m
s
5 5
:
m
s
5
# # # #

2
+
!

2
"
=
#

2
+
2
=
0
# # # #
+
2
+
!

2
"
=
0
+
2
+
2
= +
#
As al6ays, 6e note that 6e ha/e /alues o. 5
:
+ m
s
6hich run .rom # to +# in
unit steps and 6e pic4 out these as the three components o. a state characterised 3y
a total angular momentum 0uantum num3er o. #7 A spin state o. Kero total angular
momentum remains7 ;o6, 3ecause the spins o. the nucleus and the electron are each
associated 6ith a magnetic moment (see Chapter 5+, the t6o particles 3eha/e as i. they
6ere minute 3ar magnets and the energy o. the atom depends upon the relati/e orientation
o. the t6o magnets7 The energy o. the state in 6hich the t6o spins are aligned parallel,
%? Angular Comentum
# #
e7g7 5
:
= +
2
m
s
= +
2
is greater than that in 6hich the t6o spins are aligned anti2
# #

,0
parallel, e7g7 5
:
=
2
m
s
= +
2
, and the energy di..erence is 0.$*#2

#0 J7 Some
.urther discussion o. the nature o. this interaction can 3e .ound in Section $7?7 =sing
the Bohr2'instein e0uation, E = h>, (Section 27-7#+ this energy di..erence corresponds
to electromagnetic radiation o. .re0uency #*207* C9K or 6a/elength 072### m7 Thus,
i. the higher energy state should change into the lo6er energy state, i7e7 i. the relati/e
orientations o. the t6o spinning particles 6ere to change .rom parallel to anti2parallel,
then electromagnetic radiation o. the a3o/e .re0uencyH6a/elength 6ould 3e emitted7
An #$*2, 9endri4 8an de 9ulst (#$#% I + suggested that, although this e/ent
6ould
occur only /ery in.re0uently (approimately once e/ery ## million years in any one
hydrogen atom+, since there are /ast amounts o. hydrogen distri3uted as atoms throughout
space, one might epect to detect this radiation i. a su.Lciently sensiti/e recei/er 6as
a/aila3le7 Dollo6ing World War AA, the technological ad/ances achie/ed in pursuit o.
military o3@ecti/es made the rapid de/elopment o. radio astronomy possi3le and the
Qsong o. hydrogenG 6as detected and used to map the galay7
Later, in the #$?0s, 6hen it 6as proposed that 6e might listen .or radio transmissions
.rom intelligent 3eings in outer space the 0uestion naturally arose as to 6hat .re0uency
o. signal the listening de/ice should 3e tuned to recei/e7 At 6as persuasi/ely argued that,
since hydrogen is the most a3undant element in the uni/erse, the emissionHa3sorption o.
hydrogen atoms 6ould 3e 4no6n to all intelligent li.e and that this 6as there.ore the
.re0uency 6hich should 3e used7 The search has no6 occupied more than #0 000 hours
o. radio2telescope time 6ith the star systems E%silon Eridani and -a1 Ceti (## and #2
light years distant respecti/ely+ as the main targets7 All results to date ha/e apparently
3een negati/e7
An #$$* the 072### m emission o. hydrogen atoms 6as used to disco/er a ne6 galay,
<6ingeloo #, 6hich is a3out #0
-
light years .rom earth and lies in the plane o. our o6n
galay, the Cil4y Way7 Star systems 6hich lie 6ithin the Cil4y Way are /ery di.Lcult
.or us to see 3ecause 6e ha/e to loo4 through the plane o. the galay and the scattering
o. light 3y dust particles 6ithin the plane o3scures the image7 But the scattering o. light
is in/ersely proportional to the .ourth po6er o. the 6a/elength (:ayleighGs La6+ so that
the scattering o. the long26a/elength hydrogen emission is scarcely a..ected 3y the dust7
By searching .or the 072### m 6a/es .rom 6ithin the galactic plane, astronomers in the
;etherlands 6ere a3le to detect the emission .rom <6ingeloo # and pin2point its position7
When this had 3een done it 6as possi3le to conLrm the disco/ery 3y means o. a rather
poor image o3tained 6ith an optical telescope7 The search .or 072### m emission .rom
other galaies 6ithin the Cil4y Way continues7
(1%. 8I85I2RA!HY AN3 6URTHER REA3IN
#7 A7J7 CcCa..ery, N7T7 Al6aha3i, C7A7 "s3orne and C7J7 Williams, Q. Chem. Physics, -,, *5%?,
#$$,7
The comparati/ely recent 3oo4 3y Nare
2
co/ers a /ery large area o. angular momentum theory
and highlights many applications in physics and chemistry7 At can 3e highly recommended to
those 6ho 6ish to study angular momentum theory and to apply it to the interpretation o. physical
measurements7 'arlier, classic tets on the su3@ect are those 3y :ose,
,
'dmonds
*
and 3y Brin4
and Satchler7
5
Bouten
-
has pointed out that there are, un.ortunately, some inconsistencies in the
treatment o. rotations 3y 3oth :ose and 'dmonds, 3ut one has to 3e an ad/anced user o. the
theory to appreciate or 3e a..ected 3y this pro3lem7
27 :7;7 Nare, Ang1lar 5oment1m, Wiley, ;e6 Ror4, #$%%7
,7 C7'7 :ose, Elementary -heory of Ang1lar 5oment1m, Wiley, ;e6 Ror4, #$5-7
*7 A7:7 'dmonds, Ang1lar 5oment1m in 31ant1m 5echanics, !rinceton =ni/ersity !ress, #$5-7
57 <7C7 Brin4 and G7:7 Satchler, Ang1lar 5oment1m, 2nd 'dn, ".ord =ni/ersity !ress, #$?27
?7 :7<7 Co6an, -he -heory of Atomic Str1ct1re and S%ectra, Cali.ornia =ni/ersity !ress, Ber4eley,
#$%#7
-7 C7 Bouten, Physica, (&, 5-2, #$?$7
82D (1% Ang;lar moment;m operators an/ #omm;tation r;les
The or3ital angular momentum (L+ o. a single particle a3out an origin is the /ector
product o. the distance .rom the origin (r+ and the linear momentum (p+1
L = r p (B*7#7#+
An Cartesian co2ordinates the components o. L are1
L
x
= y%
B
B%
y
(B*7#72a+
L
y
= B%
x
x%
B
(B*7#723+
L
B
= x%
y
y%
x
(B*7#72c+
;ote ho6 the successi/e components can 3e o3tained 3y a cyclic permutation o.
x y B x . . .
A. 6e replace the %Gs 3y the corresponding 0uantum2mechanical operators 6e
o3tain the operators .or angular momentum in units o. h,2( h` 1
L

x
= ih`
{yD,D B BD,Dy} (B*7#7,a+
L

y
= ih`
{BD,D x xD,D B} (B*7#7,3+
L

B
= ih`
{xD,Dy yD,D x} (B*7#7,c+
These three operators do not commute 6ith each other, .or eample1
L

x
L

y
= h`
2
{yD,D B BD,Dy}{BD,D x xD,D B}
= h
`
2
{yD,D BZBD,D x\ yD,D BZxD,D B\ BD,DyZBD,D x\ + BD,DyZxD,D B\}
The terms in s0uare 3rac4ets must 3e di..erentiated as products so that 6e ha/e1
= h
`
2
{yD,D x + yBD
2
,D BD x yx D
2
,D B
2
B
2
D
2
,DyD x + BxD
2
,DyD B}
Similarly1
L

y
L

x
= h`
2
{BD,D x xD,D B}{yD,D B BD,Dy}
= h
`
2
{BD,D xZyD,D B\ BD,D xZBD,Dy\ xD,D BZyD,D B\ + xD,D BZBD,Dy\}
= h`
2
{ByD
2
,D xD B B
2
D
2
,D xDy xy D
2
,D B
2
+ xD,Dy xBD
2
,D BDy}
The co2ordinates x, y and B commute 6ith each other and so do the operators
.or partial di..erentiation 6ith respect to those co2ordinates7 There.ore, yBD
2
,D BD x =
ByD
2
,D xD B etc7 and1
{L

x
L

y
L

y
L

x
} = h`
2
{yD,D x xD,Dy} = ih`
ih`
{xD,Dy
yD,D x}
= ih` L

B

Thus1
{L

x
L

y
L

y
L

x
} ZL

x
L

y
\ = ih
`
L

B

!B*.#.*a"
and similarly1
and1
{
L

y
L

B

L

B
L

y
}


ZL

y
L

B
\
=
ih
`
L

x

{L

B
L

x
L

x
L

B
} ZL

B
L

x
\ = ih` L

!B*.#.*3"
!B*.#.*c"
These are the commutation relationships 3et6een the operators .or the Carte2
sian components o. angular momentum7 The sym3ol Za *\ = a* *a, is called the
commutator o. a and *7
But L

2
=
L

2
+
L

2
+
L

2
commutes 6ith each o. its components, e7g7
Zdropping
x y B
the eplicit inclusion o. the operand, , to simpli.y the notation\1
L

2
L

B

L

B
L

2
=
L

2
L
B
+
L
2
L
B
+
L
,

L
B
L
2

L
B
L
2

L
,
x

y

B

x

y

B
= L

x
L

x
L

B
L

x
L

B
L

x
+ L

x
L

B
L

x
L

B
L

x
L

x
+ L

y
L

y
L

B
L

y
L

B
L

y
+ L

y
L

B
L

y
L

B
L

y
L

y
= L

x
!ih` L

y
" + !ih` L

y
"L

x
+ L

y
!ih` L

x
" + !+ih` L

x
"L

y
= 0
An the second line a3o/e 6e ha/e su3tracted and then added L

x
L

B
L

x
and L

y
L

B
L

y
7
An summary1
ZL

2
L

x
\ = ZL

2
L

y
\ = ZL

2
L

B
\ = 0
(B*7#75+ ZL

also commutes 6ith each o. its components 3ut it is simpler to 6or4
6ith L
2
\7
Drom '0uations (B*7#75+ 6e 4no6 (Section ,7##+ that there is a set o. .unctions
6hich are simultaneously eigen.unctions o. 3oth L

B
and L
2
7 A. 6e use the
correspond2
ing 0uantum num3ers, 5 and L, to characterise these .unctions 6riting them in the
.orm |L 5 , 6e ha/e the .ollo6ing t6o eigen/alue2eigen.unction e0uations, 6here
@
L
and @
5
are the eigen/alues .or the s0uare o. the total angular momentum, in
units o. h`
2
, and its B component, in units o. h` , respecti/ely1
L
2
|L 5 = @
L
|L 5 !B*.#.?"
and
L

B
|L 5 = @
5
|L 5 !B*.#.-"
Starting .rom these e0uations 6e can no6 deduce the most important properties
o. the angular momentum eigen/alues1
L

2
|
L 5
= {
L

2
+
L

2
+
L

2
}|
L 5
=
@
L
|
L 5

!B*.#.%"
x y B
and L

B
L

B
|L 5 = L

B
@
5
|L 5 = !@
5
"
2
|L 5 !B*.#.$"
Su3tracting '0uation (B*7#7$+ .rom '0uation (B*7#7%+ 6e o3tain1
{
L

2
+
L

2
}|
L 5
= {
L

2

L

2
}|
L 5
= {
@
L

!@
5
"
2
}|
L 5

(B*7#7#0+
x y B
Thus, the .unctions
|
L 5

are also eigen.unctions o. L

2
+
L

2
and the eigen/alues
x y
o. the sum o. the s0uares o. t6o angular momentum components must 3e positi/e so
that1
@
L
!@
5
"
2
(B*7#7##+
B
+
We no6 deLne t6o ne6 operators, the raising and lo6ering, ladder or step
operators1
and
and
L

+
= L

x
+ iL

y
!B*.#.#2a" L


= L

x
iL

y
!B*.#.#23"
=sing the commutation rules B*7#7* one can readily sho6 that1
L

B
!L

x
+ iL

y
" = !L

x
+ iL

y
"!L

B
+ h` "
!B*.#.#,a" L

B
!L

x
iL

y
" = !L

x
iL

y
"!L

B
h` "
!B*.#.#,3"
A. the Lrst o. these t6o se0uences o. operations is applied to the .unctions |L 5
6e ha/e1
L

B
!L

x
+ iL

y
"|L 5 = !L

x
+ iL

y
"!L

B
+ h
`
"|L 5 = !L

x
+ iL

y
"!@
5
+ h
`
"|L 5
= !@
5
+ h` "!L

x
+ iL

y
"|L 5 = !@
5
+ h` "L

+
|L 5
(B*7#7#*a+
Thus, !L

x
+ iL

y
"|L 5 is .ound to 3e an eigen.unction o. L

B
6ith an
eigen/alue
o. (@
5
+ h
`
+7 Since L
2
commutes 6ith L

x
and L

y
it also commutes
6ith L

and the
eigen.unction !L

x
+
iL

y
"
|
L 5

remains an eigen.unction o. L
2
6ith eigen/alue @
L
7
Similarly, 6e Lnd that !L

x

iL

y
"
|
L 5

is an eigen.unction o. L

B
6ith an eigen/alue
o. (@
5

h` + 6hile remaining an eigen.unction o. L

2
6ith eigen/alue @
L
1
L

B
!L

x
iL

y
"|L 5 = !@
5
+ h
`
"!L

x
iL

y
"|L 5 = !@
5
h
`
"L


|L 5
(B*7#7#*3+
There.ore, 6e ha/e a series o. eigen.unctions o. L
2
and L

B
, all 6ith the
eigen/alue
o. >
L
.or L
2
3ut 6ith the .ollo6ing se0uence o. eigen/alues o. L

B
1
. . . !@
5
,h` " !@
5
2h` " !@
5
h` " @
5
!@
5
+ h` " !@
5
+ 2h` " !@
5
+ ,h` " . . .
The series must terminate at 3oth ends 3ecause @
L
!@
5
"
2
7 Thus, i. 6e denote
the highest /alue 3y @
5

and the lo6est 3y @
5

the .ull se0uence is1
@
5

. . . !@
5
2h` " !@
5
h` " @
5
!@
5
+ h` " !@
5
+ 2h` " . . . @
5

(B*7#7#5+ There.ore, i. the corresponding eigen.unctions are |L 5

and |L 5


6e must
ha/e1
and
L

+
|L 5

= 0 !B*.#.#?a"
L

|L 5

= 0 !B*.#.#?3"
Applying L


to '0uation (B*7#7#?a+ 6e ha/e1
L

L

+
|L 5

= !L

x
iL

y
"!L

x
+ iL

y
"|L 5


= {
L
2
+
L
2
+
i!L
x
L
y

L
y
L
x
"
}|
L 5

= {
L
2
+
L
2

h
`
L
B
}|
L 5


x y x y
= {L
2
L
2
h
`
L

B
}|L 5

= {@
L
!@
5

"
2
h
`
@
5

}|L 5

= 0
Thus, @
L
= !@
5

"
2
+ h` @
5

!B*.#.#-a"
By operating 6ith L

+
on '0uation (B*7#7#?3+ 6e can also sho6 that1
@
L
= !@
5

"
2
h
`
@
5

(B*7#7#-3+
An order to satis.y '0uations (B*7#7#-a+ and (B*7#7#-3+ and to 3e consistent
6ith the assumption that @
5

P @
5

6e must ha/e @
5

= @
5

7 Durthermore,
the se0uence ('0uation (B*7#7#5++ re0uires that @
5

3e greater than @
5

3y an inte2
gral num3er o. units o. h
`
7 Thus, @
5

must 3e o. the .orm
nh
`
6here n is an integer,
including 0, or a hal.2integer7 Thus .ar 6e ha/e attached no particular signiLcance to
L7 There.ore, since @
5

depends only on L 6e may set n
=
L and 6e ha/e1
@
5

= Lh
`
=sing '0uation (B*7#7#-a+ @
L
= !Lh
`
"
2
+ h
`
Lh
`
!B*.#.#%"
or @
L
= L!L + #"h
`
2
!B*.#.#$"
;o6, the possi3le /alues o. >
5
are1
Lh
`
!L #"h
`
. . . !L
#"h
`
Lh
`
(B*7#720+
And 5 , to 6hich 6e ha/e attached no particular signiLcance yet, can 3e used to
characterise this se0uence o. >
5
/alues1
@
5
= 5 h` L 5 L
(B*7#72#+
A. L is an integer 5 is an integer, i. L is hal.2integral so too is 5 7
'0uations (B*7#7?+ and (B*7#7-+ may no6 3e 6ritten1
L
2
|L 5 = L!L+#"h`
2
|L 5 !B*.#.22a"
and
L

B
|L 5 = 5 h
`
|L 5 !B*.#.223"
These results ha/e 3een deri/ed solely .rom the commutation relationships and
they there.ore apply to any properties .or 6hich the corresponding operators ha/e the
same commutation rules7 At is .ortunate that they also apply to the property 6hich 6e
call QspinG7 Since spin is a non2classical 0uantity, there 6as no reason to assume that
the rules deduced here, 3ased on the classical mechanics o. or3ital angular momentum,
6ould apply7 9o6e/er, it can 3e sho6n using a method 6hich does not depend on
classical mechanics that the commutation rules deduced a3o/e also apply to spin7
Treatments o. this type are 3ased on the theory o. inLnitesimal rotations and can
3e .ound in any o. the re.erences 2 I 5 cited in the 3i3liography o. Chapter *7
The mathematics used is not as daunting as the 6ords QinLnitesimal rotationsG may
ma4e it appear7
The primary tas4 o. this Bo, the deduction o. the commutation rules .or or3ital
angular momentum and .rom them '0uations (B*7#722a+ and (B*7#7223+, has no6
3een accomplished7 But in the process 6e ha/e also Qdisco/eredG the raising and
lo6ering operators, L

+
and L

, 6hich 6e Lnd etremely use.ul throughout this

3oo47
We are no6 in a position to eamine their properties a little more closely7 We .ound
that, in units o. h` , 6hen L

+
is applied to |L 5 6e o3tain an eigen.unction o. L

B
6ith an eigen/alue o. (5 + #+ 6hich is still an eigen.unction o. L
2
6ith the same /alue
o. the 0uantum num3er L7 Similarly, 6e .ound that L

|
L 5

is an eigen.unction
o.
2
2
2
2
L
2
, 6ith the same /alue o. L, and o. L

B
6ith an eigen/alue o. (5 #+7 '0uations
(B*7#72,a+ and (B*7#72,3+ summarise these statements1
L

+
|L 5 = C
+
|L 5 + # (B*7#72,a+
L

|L 5 = C

|L 5 # (B*7#72,3+
C
+
and C

are num3ers 6hich may result .rom the operation 3y L

+
and L


on
|L 5 7 The statements immediately a3o/e 6ould not 3e in/alidated i. the resulting
eigen.unctions 6ere multiplied 3y such constants and 6e need to determine their
/alues7 The comple con@ugate (Appendi %+ o. '0uation (B*7#72,a+ is1
{L

+
|L 5 }

= {C
+
|L 5 + # }

(B*7#72*+ But
{L

+
}

= L

, |L 5

= L 5 | and |L 5 + #

= L 5 + #|, and '0uation
(B*7#72*+ can 3e 6ritten1
L 5 |L


= C
+

L 5 + #| (B*7#725+ A.
6e no6 multiply the right2 and le.t2hand sides o. '0uation (B*7#72,a+, on the
le.t, 3y the same sides o. '0uation (B*7#725+ 6e o3tain '0uation (B*7#72?+1
L 5 |L

L

+
|L 5 = C
+
C
+

L 5 + #|L 5 + # = C
+
C
+

(B*7#72?+
The right2hand side reduces to C
+
C
+

3ecause L|K means integrate the product
LK o/er all space and there.ore L 5 + #|L 5 + # = # i. the eigen.unctions are
normalised, 6hich 6e certainly re0uire them to 3e7 The operator product L

L

+
can
3e e/aluated using '0uations (B*7#7*+ and (B*7#7#2+ and 6e Lnd, in units o. h
`
, that1
There.ore1
L

L

+
=
L

L

B
L

B
(B*7#72-+
L 5 |L

L

+
|L 5 = L 5 |
L

L

B
L

B
|L 5
= L 5 |L!L + #" 5
2
5 |L 5 = L!L + #" 5!5 + #"
(B*7#72%+
since L 5 |L 5 = # .or normalised eigen.unctions7 Dinally, comparing '0ua2
tions (B*7#72?+ and (B*7#72%+ 6e ha/e1
C
+
C
+

= L!L + #" 5!5 + #"
There.ore, since there is no reason to assume that C
+
is anything other than real1
#
C
+

=
C
+
= {
L!L
+
#"

5!5
+
#"
} 2
(B*7#72$+
An analogous de/elopment starting .rom '0uation (B*7#72,3+ gi/es1
#
C

=
C

= {
L!L
+
#"

5!5

#"
} 2
(B*7#7,0+
and the complete .orms o. '0uations (B*7#72,a+ and (B*7#72,3+ are1
#
L

+
|
L 5
= {
L!L
+
#"

5!5
+
#"
} 2 |
L 5
+
#

(B*7#7,#a+
#
L

|
L 5
= {
L!L
+
#"

5!5

#"
} 2 |
L 5

#

(B*7#7,#3+
:eaders may ha/e 6ondered 6hy the positi/e sign 6as chosen .or the s0uare root
in '0uation (B*7#72$+7 There is deLnitely an element o. choice here and, since the
raising and lo6ering operators lin4 all the 2L + # eigen.unctions o. the mani.old o. 5
/alues ha/ing the same /alue o. L, it is important7 This choice o. phase does not a..ect
the calculation o. any measura3le physical property, 3ut it does a..ect intermediate
alge3raic results 6hich can 3e /ery important 6hen these results ha/e 3een ta3ulated
.or general use, as many ha/e 3een7 The positi/e sign 6as Lrst chosen 3y Condon
and Shortley
#
and is no6 e..ecti/ely uni/ersal7
An the light o. the a3o/e a reader might 6ell as4, QA. 6e can Lnd out so much a3out
angular momentum simply 3y studying the commutation properties o. the associated
operators can 6e not approach other 0uantum2mechanical pro3lems in the same 6ayJG
The short ans6er to that 0uestion is QyesG, the procedure is sometimes called second
71antisation7 The 3est24no6n eample o. it is the deduction o. the energy le/els o.
the harmonic oscillator7
2
An that pro3lem the raising operator is 4no6n as the creation
operator 3ecause each application generates an additional /i3rational 0uantum7 The
lo6ering operator, each application o. 6hich remo/es a /i3rational 0uantum, is called
the annihilation operator7 These concepts ha/e /ery 6ide applica3ility and .orm the
3asis o. the description o. photons in the theory o. 0uantum electrodynamicsP see
Section %7$ and re.erence 27 Some less 6ell24no6n applications ha/e 3een descri3ed
3y ;e6march and Golding7
,
#7 '7=7 Condon and G797 Shortley, -he -heory of Atomic S%ectra, Cam3ridge =ni/ersity !ress,
#$,57
27 ;7 Nettili, 31ant1m 5echanics Conce%ts and A%%lications, Wiley, Chichester, 200#7
,7 J7<7 ;e6march and :7C7 Golding, American Q. Phys., (*, ?5% I ??0 #$-%7
82D (1& T$e Cle?s#$ I or/an series
The mathematical proo. o. the Cle3sch I Gordan .ormula .or the addition o.
angu2 lar momenta in 0uantum mechanics is really only a rigorous argument
along the .ollo6ing, more descripti/e, lines7
Suppose that the t6o angular momenta to 3e added are characterised 3y total
angular momentum 0uantum num3ers d
#
and d
2
7 We 6ish to sho6 that the 0uantum
num3ers o. the resulting /ectors, d , are gi/en 3y the Cle3sch I Gordan series1
d = d
#
+ d
2
d
#
+ d
2
# d
#
+ d
2
2 . . . |d
#
d
2
|
The B2components o. the resulting /ectors, characterised 3y their m
d
/alues, must
simply 3e sums o. the B2components o. d
#
and d
2
and there are !2d
#
+ #" !2d
2
+ #"
such sums7 We Lrst arrange the possi3le sums in a rectangular array7
d
#
d
#
# d
#
2 d
#
, d
#
+ # d
#
d
2
d
#
+ d
2
d
#
+ d
2
# d
#
+ d
2
2 d
#
+ d
2
, d
2
d
#
+ # d
2
d
#
d
2
# d
#
+ d
2
# d
#
+ d
2
2 d
#
+ d
2
, d
#
+ d
2
* d
2
d
#
d
2
d
#
#
d
2

2 d
#
+
d
2

2 d
#
+
d
2

, d
#
+
d
2

* d
#
+
d
2

5

d
2

d
#

# d
2

d
#

2
. . . . . . .
d
2
+ # d
#
d
2
+ # d
#
d
2
d
#
d
2
# d
#
d
2
2 d
2
d
#
+ 2 d
2
d
#
+ #

d
2
d
#

d
2
d
#

d
2

# d
#

d
2

2 d
#

d
2

,

d
2

d
#
+
#

d
2

d
#
!ro3lems .or Chapter * $,
2
2 2
2
We no6 go through a procedure 6hich is repeated se/eral times in the eamples
in Section *7$7 At the top le.t corner o. the array 6e Lnd the maimum possi3le
m
d
/alue o. d
#
+
d
2
6hich means that there must 3e a /alue o. d e0ual to d
#
+
d
2
6ith 2!d
#
+
d
2
"
+
# B2components running in unit steps .rom d
#
+
d
2
to

!d
#
+
d
2
"7
We can Lnd this se0uence o. m
d
/alues along the top ro6 and do6n the .ar right
column o. our array and 6e tic4 them o..7 The maimum m
d
/alue remaining in
the array is no6 d
#
+ d
2
#, again in the top le.t corner, and 6e can tic4 o.. the
other 2!d
#
+ d
2
#"m
d
/alues 6hich 6e Lnd in the second ro6 o. the array and the
column second .rom the right7
This process can 3e repeated until 6e ha/e one o. t6o possi3le scenarios7 A. d
#
=
d
2
the last element remaining in the array is the 3ottom le.t corner, d
#
d
2
, 6hich
clearly corresponds to a /ector 6ith d = 0 and m
d
= 07 A. d
#
R d
2
and d
#
d
2
= n
the num3er o. colums eceeds the num3er o. ro6s 3y 2d
#
+ # !2d
2
+ #" = 2!d
#

d
2
" = 2n7 Then the Lnal situation is that 2n + # elements remain at the le.t2hand
end o. the last ro6 o. the array, d
#
d
2
3eing the Lrst o. these and d
#
d
2
2n =

!d
#

d
2
" the last7 These are the m
d
/alues o. a /ector 6ith d
=
d
#

d
2
7
!R285EMS 62R CHA!TER (
#7 :ead Bo *72 and, .ollo6ing the general description o. the addition o. t6o angular
momenta, 6or4 through the speciLc eample d
#
= 2 and d
2
=
,
7
27 =se '0uation (*7#72+ to deri/e an e0uation .or the angular momentum o. a rotating
diatomic
#?
" molecule in terms o. the mass o. the
#?
" atom (2?.5?0#$ #0

2-
4g+,
the 3ond length (#.20-52 #0

#0
m+ and the .re0uency, >, o. the rotation7 The angular #
momentum (L+ must 3e 0uantised according to the e0uation L
=
!h,2( "!Q ZQ
+
#\"
2
7
Dind the rotational .re0uency .or Q = #7
,7 =se '0uations (*7-75+ and (*7-7?+ to determine the e..ects o. the raising and lo6ering
operators on the se/en .2or3ital .unctions, |, m
d
, m
d
= , to +,7
*7 The three e0ui/alent protons o. a methyl group couple to gi/e eight (2 2 2+ nuclear
spin .unctions7 =se an etension o. the method descri3ed in Section *7$ to sho6 that
the coupled spins .orm a state ha/ing S =
,
and t6o states ha/ing S =
#
7 Why do
you thin4 that these states are sometimes descri3ed as Qa 0uartet and t6o dou3letsG J
:epeat the eercise using successi/e applications o. '0uation (*7?7#+7
57 An pro3lem * the spin states, |S 5
S
, o. three e0ui/alent coupled protons ha/e 3een
determined7 A more detailed description o. the system re0uires the eact com3inations
o. the eight nuclear spin .unctions 6hich .orm a particular spin state7 The raising and
lo6ering operators may also 3e used to sol/e this pro3lem7
a+ Starting 6ith the eigen.unction
|
,

+
,

, apply the lo6ering operator, S

, succes2
2 2

si/ely to o3tain the other three eigen.unctions 6ith S

=
,
, e7g71
, ,

, #
S

|
2

+
2
=
,
|
2

+
2

!#"
2
The multiplying .actors 6hich arise 6hen each eigen.unction is generated .rom the
one a3o/e are important7
The only 6ay in 6hich the eigen.unction
|
,

+
,

can 3e generated .rom three
2 2
nuclear spins 6ith s
=
#
is .or all three B2components to 3e parallel, i7e71
, , # # #
|
2

+
2
= | +
2
!#"
+
2
!2"
+
2
!,"

6here only the m
s
/alues o. the indi/idual protons ha/e 3een indicated7 To operate
on the eigen.unction .ormulated as it is on the right o. the a3o/e e0uation 6e 6rite
S

in terms o. the indi/idual spin operators, s

(a+, a
=
#, 2, ,, as1
S

= s

!#" + s

!2" + s

!,"
'ach indi/idual spin operator operates only on a particular spin so that 6e ha/e1
# # #
# # #
{
s

!#"
+
s

!2"
+
s

!,"
}| +
2
!#"
+
2
!2"
+
2
!,"
=
s

!#"
| +
2
!#"
+
2
!2"
+
2
!,"

# # #
# # #
+
s

!2"
| +
2
!#"
+
2
!2"
+
2
!,"
+
s

!,"
| +
2
!#"
+
2
!2"
+
2
!,"

# # #
# # #
= |
2
!#"
+
2
!2"
+
2
!,"
+ | +
2
!#"

2
!2"
+
2
!,"

# # #
+ | +
2
!#"
+
2
!2"

2
!,"

(2+
Comparing the right2hand sides o. e0uations # and 2 6e see that1
, #

# # #
|
2

+
2
= {
#, ,
}{|
2
!#"
+
2
!2"
+
2
!,"

# # #
# # #
+ | +
2
!#"

2
!2"
+
2
!,"
+ | +
2
!#"
+
2
!2"

2
!,"
}
3+ Continue the process to determine the eigen.unctions
|
,


#

and
|
,


,

in
terms
2 2 2 2
o. the indi/idual spin .unctions7 Alternati/ely, start 6ith
|
,


,

and use S

7
2 2
+
c+ To Lnd the t6o dou3lets 6e re0uire t6o epressions .or
|
#

+
#

6hich are nor2
2 2
malised and orthogonal to each other and to
|
,

+
#

7 Try1
2 2

{#,
?
}{
2
|
#
!#"
+
#
!2"
+
#
!,"
| +
#
!#"

#
!2"
+
#
!,"

2 2 2
# # #
2 2 2
and
| +
2
!#"
+
2
!2"

2
!,"
}

{#,
2
}{| +
#
!#"

#
!2"
+
#
!,"
| +
#
!#"
+
#
!2"

#
!,"
}
2 2 2 2 2 2
Sho6 that these t6o .unctions ha/e the re0uired properties o. normalisation and
orthogonality and Lnd the corresponding t6o .unctions |
#

#
3y applying
the
2 2
lo6ering operators to the t6o
|
#

+
#

.unctions7
2 2
Chapter 5
T$e Str;#t;re an/ Spe#tros#op0
o" t$e Atom
570 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . $?
57# The eigen/alues o. the hydrogen atom . . . . . . . . . . . . . . . . . . . . . . . . . $?
572 The 6a/e .unctions o. the hydrogen atom . . . . . . . . . . . . . . . . . . . . . . $-
5727# The radial .unction, R
nl
!r " . . . . . . . . . . . . . . . . . . . . . . . . . . $%
57272 The angular .unctions,
lm
!# " and
m
!$" . . . . . . . . . . . . . . . . $$
57, !olar diagrams o. the angular .unctions . . . . . . . . . . . . . . . . . . . . . . . . #00
57,7# The s2.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0#
57,72 The %2.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0#
57,7, The d 2.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0,
57* The complete or3ital 6a/e .unctions . . . . . . . . . . . . . . . . . . . . . . . . . . #0*
575 "ther one2electron atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0*
57? 'lectron spin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #05
57- Atoms and ions 6ith more than one electron . . . . . . . . . . . . . . . . . . . . #05
57-7# The sel.2consistent Leld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0?
57-72 'lectron correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0?
57-7, The periodic ta3le o. the elements . . . . . . . . . . . . . . . . . . . . . . #0-
57% The electronic states o. the atom . . . . . . . . . . . . . . . . . . . . . . . . . . . . #0-
57%7# The L/e 0uantum num3ers o. a single electron . . . . . . . . . . . . . #0%
57%72 &uantum num3ers .or the many2electron atom . . . . . . . . . . . . . . #0%
57%7, The assignment o. term sym3ols . . . . . . . . . . . . . . . . . . . . . . . #0%
57%7* Term energies and 9undGs rules . . . . . . . . . . . . . . . . . . . . . . . ##0
57$ Spin2or3it coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ###
57$7# :ussell I Saunders or LS coupling . . . . . . . . . . . . . . . . . . . . . . ###
57$72 && coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##2
57$7, Antermediate coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##,
57$7* Anter2electronic spin2or3it coupling . . . . . . . . . . . . . . . . . . . . . ##5
57#0 Selection rules in atomic spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . ##5
57#07# Angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##5
57#07#7# 'lectric 0uadrupole transitions . . . . . . . . . . . . . . . . . ##?
57#07#72 Cagnetic dipole transitions . . . . . . . . . . . . . . . . . . . . ##?
57#072 !arity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##?
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
$? The Structure and Spectroscopy o. the Atom
57## The Neeman e..ect . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ##-
57##7# The normal Neeman e..ect . . . . . . . . . . . . . . . . . . . . . . . . . . . ##%
57##72 The anomalous Neeman e..ect . . . . . . . . . . . . . . . . . . . . . . . . #20
57#2 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2#
!ro3lems .or Chapter 5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #2$
)1. INTR23UCTI2N
An #$2?, the structure o. the hydrogen atom, and an interpretation o. the 6a/elengths o.
the /isi3le spectral lines o. the atom, 6as pro3a3ly the most immediate pro3lem .acing the
ne6 0uantum mechanics7 An his paper o. #$2?, in 6hich he inaugurated that .ormulation
o. 0uantum mechanics 6hich 6e no6 call 6a/e mechanics, SchroM dinger proposed
the correct .orm o. the 9amiltonian operator .or the pro3lem, deri/ed the re0uired
eigen/alues and eigen.unctions and sho6ed that the .ormer corresponded to the energy
le/els o. the Bohr model o. the hydrogen atom and 6ere there.ore in agreement 6ith the
eperimental data7 These results play a central role in our understanding o. the structure
o. all atoms7 The solution o. the SchroM dinger e0uation .or the hydrogen atom is a
straight.or6ard 3ut time2consuming tas4 and 6e shall not enter into it here7 Dull
details can 3e .ound in many tets7
#2
We shall 3e much more concerned, in this chapter
and in others, 6ith the .ollo6ing aspects o. the pro3lem and their implications .or our
understanding o. atomic structure, atomic spectroscopy, the periodic ta3le and the nature
o. the chemical 3ond7
What are the eigen/alues and ho6 are they determined 3y the 0uantum num3ersJ
What are the .orms o. the corresponding eigen.unctions and 6hat do they tell us a3out
the distri3ution o. the electron in space around the nucleus o. the atomJ
9o6 are the eigen/alues and eigen.unctions o. the hydrogen atom, a one2electron atom,
modiLed 3y inter2electronic repulsion in atoms 6hich ha/e more than one electronJ
What are the magnetic properties o. electrons and ho6 do they mani.est themsel/es in
the structures and spectra o. atomsJ
)1% THE EIENVA5UES 26 THE HY3R2EN AT2M
A. 6e assume that the nucleus has an inLnite mass (see Section 575 .or .urther details+,
then the eigen/alues o. the hydrogen atom are gi/en 3y a simple .ormula 6hich depends
upon @ust one 0uantum num3er (n+ 6hich is 4no6n as the %rinci%al 0uantum num3er7 At
can ta4e any positi/e integer /alue .rom # to 1
E
n
= m
e
e
*
,%h
2
?
0
2
n
2
in J or m
e
e
*
,%ch
,
?
0
2
n
2
in cm

#
(57#7#+
m
e
is the mass o. the electron, e its charge, c the /elocity o. light (in cm s

#
+, h !lanc4Gs
constant and ?
0
the permitti/ity o. a /acuum7 ;ote that the energy is a negati/e 0uantity7
This deri/es .rom the .act that our energy Kero is deLned to 3e the state in 6hich the proton
and electron are inLnitely .ar apart and motionless so that they ha/e neither potential nor
4inetic energy7 As the t6o particles approach each other, the energy o. the .orming atom
The Wa/e Dunctions o. the 9ydrogen Atom $-
decreases 3ecause o. the negati/e coulom3ic energy o. the opposite chargesP so much is
0uite o3/ious7 What is not so o3/ious is the .act that the t6o particles can only 3e 4ept
apart i. they are in motion and this motion gi/es rise to a 4inetic energy 6hich must
3e positi/e and increases as the a/erage distance 3et6een the electron and the nucleus
decreases7 9o6e/er, it is a .undamental conse0uence o. the la6s o. classical and 0uantum
mechanics that the 4inetic (- + and potential (V + energies are al6ays in eactly the same
ratio 6hich, .or a system 6here the potential energy results .rom electrostatic attraction,
is V = 2 - 7 There.ore, .or any eigen/alue, n, o. the hydrogen atom the total energy
may 3e epressed as1
E
n
= -
n
+ V
n
= -
n
2-
n
= -
n
= V
n
,2
This relationship 3et6een - and V is 4no6n as the virial theorem7 Because o. it, 6e
can 3e sure that the negati/e potential energy o. the .orming hydrogen atom 6ill al6ays
eceed the positi/e 4inetic energy7
The epression .or the energy, '0uation (57#7#+, 6as Lrst deduced 3y SchroM dinger
and it pro/ided an eact, 0uantitati/e interpretation o. the Balmer .ormula7 ;aturally, all
the other lines in the hydrogen atom spectrum can also 3e Ltted to this .ormula (Bo
57#+7 As n increases n
2
increases /ery rapidly so that /alues o. E
n
3ecome closer and
closer together as they con/erge upon the /alue o. Kero7 We see the eperimental
e/idence .or this in the positions o. the lines in the spectra o. the hydrogen atom,
Digure B57#7# and Digure 27%7 Consider the Lyman series (Bo 57#+7 The energy re0uired
to raise the electron
.rom the energy le/el, n = #, to successi/ely higher le/els, n = 2 , * . . . increases, 3ut
3y a smaller amount, .or each increase in the higher 0uantum num3er7 Dinally, 6hen
n = the electron lea/es the atom 6hich is then said to ha/e 3een ionised7 Dor the
Lyman series this ionisation limit is .ound at #0$ ?--7? cm

#
6hich corresponds to a
6a/elength o. $#72 nm7 Since the Balmer series starts .rom the le/el n = 2 its ionisation
limit is correspondingly smaller at 2- *#$7* cm

#
or ,?*7- nm7
)1& THE 4AVE 6UNCTI2NS 26 THE HY3R2EN AT2M
The 6a/e.unctions o. the hydrogen atom are not easy to descri3e in a Cartesian co2
ordinate system o. three, mutually perpendicular aes7 The polar co2ordinate system 6ith
the nucleus at the origin is much more suita3le7 The polar system is descri3ed and the
t6o systems compared in Appendi -7
Though at Lrst sight the SchroM dinger e0uation .or the hydrogen atom loo4s
more .ormida3le in polar than in Cartesian co2ordinates, the apparent compleity
conceals the .act that a most important simpliLcation is possi3le7 The SchroM dinger
e0uation in the three /aria3les (r , # and $+ can 3e se%arated into three e0uations in each
o. 6hich only one o. the /aria3les occurs7 This ma4es the solution o. the e0uation and,
more importantly .rom our point o. /ie6, the interpretation o. the results much
simpler7 Because the e0uation can 3e separated, the total 6a/e.unction can 3e 6ritten
as a product o. three .unctions, each containing only one co2ordinate /aria3le, i7e71

nlm
!r # $" = R
nl
!r "
lm
!# "
m
!$"
!5.2.#" Where the su3scripts, n, l and m, indicate the 0uantum num3ers upon 6hich
that particular part o. the 6a/e .unction is .ound to depend7 'ach o. the .unctions R!r ",
!# "
$% The Structure and Spectroscopy o. the Atom
and !$" can 3e 6ritten in a /ery general .orm and these epressions, especially those
.or R!r " and !# ", are rather complicated7 9o6e/er, since 6e are interested only in a
comparati/ely small num3er o. them, 6e shall 6rite those out eplicitly (Appendi 5+
and re.er readers 6ho re0uire the general .ormulae to more ad/anced tets7
#2
A complete 6a/e .unction may 3e thought o. as an eact description o. a region
mapped out in space 6hich can 3e occupied 3y one electron, or 3y t6o electrons 6ith
opposite spins7 The pro3a3ility o. Lnding an electron at any point in that space is .ound
3y e/aluating the 6a/e.unction at that point and multiplying the result 3y its comple
con@ugate, i7e7

7 A. the product

is integrated Zsummed up\ o/er all the space

then the result is one 3ecause the 6a/e.unctions are normalised (Section ,75+7 Since 6e
no6 4no6 that 6e cannot thin4 o. the motion o. an electron in @ust the same 6ay as 6e
thin4 o. the motion o. a planet around the sun, the epression Qor3itG is not appropriate7
To ma4e the di..erence clear, 6hile at the same time reOecting the historical origins o.
the concept, the term or*ital has 3een coined and is no6 uni/ersally used to descri3e the
.unction 7
)1&1% T$e ra/ial ";n#tion< +
n<l
!r"
The .unction R
nl
!r " is 4no6n as the radial .unction 3ecause it contains only r , the
radial co2ordinate o. the polar co2ordinate system7 '0uation (5727#+ sho6s that it is
the only part o. the 6a/e .unction in 6hich the principal 0uantum num3er, n, occurs7
When 6e study the radial .unctions (Appendi 5+ 6e see that, apart .rom a normalising
.actor, they
consist o. an eponential .unction, ep!

Or ,na
0
"

ep!

=,2", and a polynomial in

r 7 Because its argument is negati/e, the eponential .actor ensures that the /alue o. the
6a/e .unction al6ays goes to Kero at large distances .rom the nucleus7 This means that
the s0uare o. the 6a/e .unction, and there.ore the pro3a3ility o. Lnding the electron, .alls
to Kero as 6e mo/e .urther .rom the centre o. the atom7 Dor the hydrogen atom O = #,
3ut i. the /alue o. O is larger, as it is .or eample in the helium (9e
+
+ ion, then the
eponential part o. the radial .unction .alls o.. much .aster than 6hen O = # reOecting
the 6ay in 6hich a larger nuclear charge holds the electron closer to the nucleus7 The
polynomial .actor causes the radial .unction to change sign as the /alue o. r changes
as sho6n in Digure 57#7 Those /alues o. r .or 6hich any particular radial .unction is
Kero are 4no6n as the radial nodes and 6e must note that such a node has the .orm o.
a sphere, en/eloping the 6hole atom and 6ith the nucleus at its centre7 ;ot all radial
.unctions ha/e nodes7 ". those listed in Appendi 5, R
20
!r " has one node at = = 2.0
(r = 2.0a
0
P a
0
= Bohr radius+, R
,#
!r " has one node at = = *.0 (r = ?.0a
0
+ and R
,0
!r "
has t6o nodes at = = #.2?% (r = #.$0a
0
+ and *7-,2 (r = -.#0a
0
+7 The num3er o. nodes
in an eigen.unction is intimately connected 6ith the corresponding eigen/alue and 6e
shall consider the su3@ect o. nodes again 6hen 6e ha/e descri3ed the ang1lar .unctions

lm
!# " and
m
!$"7
Apart .rom plots o. R!r " itsel., t6o other representations o. the radial .unction are
.re0uently used to illustrate the 6ay in 6hich the pro3a3ility o. Lnding an electron,
i7e7 the electron density, 3eha/es as the distance .rom the nucleus increases7 Since this
pro3a3ility is proportional to the s0uare o. the 6a/e .unction, graphs o. R
2
!r " against r are
.re0uently used .or this purpose7 Another .orm o. diagram is o3tained in the .ollo6ing
manner7 Since the sur.ace area o. a sphere o. radius r is *(r
2
, the /olume element
:
n
,
l
(
r
+

#
0
2
:
n
,
l
(
r
+
*
p
r
2
:
2
:
n
,
l
(
r
+
The Wa/e Dunctions o. the 9ydrogen Atom $$
570
275
070
072
07#
d2or3ital1 l = 2
n = ,
p2or3itals1 l = #
n = 2, ,
270
#75
#70
075
s2or3itals1 l = 0
n = #, 2, ,
070
07#
0 5 #0 #5 20
r (atomic units+
6ig;re )1% 9ydrogen2atom radial .unctions
070
0 5 #0 #5 20
r (atomic units+
%
-
2s
?
5
2p
#s
*
,
2
,d
,p
#
0
275
270
#75
#70
075
070
#70
,s
075
070
0 # 2 , * 0 5 #0 #5 20 25
r (atomic units+
6ig;re )1& 9ydrogen2atom radial density .unctions
enclosed 3et6een t6o spheres o. radii r and r + )r is *(r
2
)r 7 There.ore, the proportion
o. the hydrogen2atom electron 6hich lies 3et6een t6o such spheres, i7e7 at distance r
.rom the nucleus, is *(r
2
R
2
!r ")r 7 So a graph o. *(r
2
R
2
!r " against r is a
measure
o. the pro3a3ility o. Lnding an electron at a distance r .rom the nucleus (Digure 572+ 3ut
it can easily 3e misleading7 Because the .unction r
2
increases so rapidly 6ith increasing
r , the .unction *(r
2

R
2
!r " has one or more maima 6hich must 3e interpreted
6ith
care7 Dor eample, i. 6e 6ere a3le to stand at the hydrogen nucleus and eperience the
electron density o. the #s or3ital there in the 6ay in 6hich 6e eperience a .og 6e 6ould
Lnd that the .og 6as /ery dense at the nucleus7 As 6e 6al4ed a6ay .rom the nucleus the
thic4ness o. the .og 6ould decrease eponentially and 6e 6ould not see any increase in
the region o. r = a
0
6here the graph o. *(r
2
R
2
!r " against r sho6s a maimum7 The
maimum is a conse0uence o. the .actor r
2
7 ". course, 6here there are radial nodes
the
electron density must .all to Kero at these /alues o. r and increase again at greater r 7
)1&1& T$e ang;lar ";n#tions<
l<&
!# " an/
&
!$"
We might 6ell ha/e epected that an electron circulating around a nucleus 6ould ha/e
some or3ital angular momentum associated 6ith it, and this is indeed the case7 Durther, 6e
Ta?le )1% The possi3le 0uantum num3er com3inations .or the lo6er /alues o. n
n
#
l
0
m
0
n
2
l
0
m
0
#
# 0 +#
, 0 0 * 0 0
#
# 0 +#
#
# 0 +#
2 2 # 0 +# +2 2 2 # 0 +# +2
,
, 2 # 0 +# +2 +,
4no6 .rom Chapter * that 6e can al6ays characterise t6o aspects o. angular momentum,
the s0uare o. its total /alue and its B2component7 The 0uantum num3ers l and m do
@ust that and there.ore the 0uantum num3er .or the s0uare o. total angular momentum,
l, and the 0uantum num3er .or its B2component, m, are related 3y the epressionP m =
0

2 . . .

l7
]
But the detailed solution o. SchroM dingerGs e0uation .or the hydrogen
atom re/eals that the /alue o. l is itsel. restricted to integer /alues lying 3et6een 0
and (n #+7 An summary, the three spatial 0uantum num3ers can ta4e the .ollo6ing,
interrelated /alues1
n, the principal 0uantum num3er = # 2 , . . .
l, the or3ital angular momentum 0uantum num3er = 0 # 2 . . . !n #"
m, the 0uantum num3er .or the B2component o. the or3ital a7 m7 = 0 # 2 . . . l
The possi3le 0uantum num3er com3inations .or the lo6er /alues o. n, 6hich are the
only ones o. interest to us, are as sho6n in Ta3le 57#7
We Lnd it easier to remem3er the 0uantum num3ers and their signiLcance i. 6e use
a letter instead o. a num3er .or l, and .or reasons 6hich stretch 3ac4 into the history o.
atomic spectroscopy 6e use the letters s (sharp+, p (principal+, d (di..use+ and . (.undamen2
tal+ .or l = 0 # 2 and , respecti/ely7 There.ore, there are one s2or3ital, three p2or3itals,
L/e d2or3itals and se/en .2or3itals7
The .unctions
lm
!# "


m
!$" occur in many pro3lems 6hich, li4e the atom, ha/e
spherical symmetry7 They are 4no6n as the s%herical harmonics (Appendi 5+ and they
are .re0uently 6ritten as a single .unction, S
lm
!# $"7 The .orms o. these angular
.unctions are /ery important, especially so since the distri3ution o. electrons in space
around an atomic nucleus is a ma@or .actor 6hich a..ects the strength o. chemical 3onds
and the geometry o. molecules7 Allustrations o. the angular .unctions are there.ore /ery
important in the study o. chemical 3onding7
)1' !25AR 3IARAMS 26 THE ANU5AR 6UNCTI2NS
The most use.ul illustrations o. the angular parts o. the 6a/e.unctions o. the hydrogen
atom are o3tained 3y plotting them in polar co2ordinates as descri3ed in detail 3elo67
]
"ur notation here is not 0uite consistent7 A. 6e 6ere to .ollo6 the con/ention on angular momentum 0uantum num3ers
esta3lished in Chapter *, then i. l is the 0uantum num3er characterising total angular momentum, m
l
6ould 3e the .orm o. the
0uantum num3er .or the B2component o. that angular momentum7 The su3script is omitted to con.orm 6ith the usual notation
.or the atomic 0uantum num3ers since no con.usion can result .rom this and compleity in the notation is also reduced7
!olar <iagrams o. the Angular Dunctions #0#
2
Since the 0uantum num3ers m and l are related 3y l m +l, 6e must 3e care.ul to
com3ine only those .unctions
lm
!# " and
m
!$" .or 6hich this condition is
satisLed7
)1'1% T$e s9";n#tions
We start 6ith the s2.unctions o. 6hich there is only oneP
00
!# "
0
!$" =
#

!#,(
"7 Clearly, this .unction has no dependence upon either o. the t6o angular co2ordinates7 At
is
a .unction 6hich is eactly the same in all directions around the atom, i7e7 it is spherically
symmetrical7 We can represent it 3y dra6ing a spherical 3oundary sur.ace centred at the
nucleus and o. a radius such that a gi/en proportion o. the electron is enclosed 6ithin it,
$5 Y say7 All s2or3itals are represented 3y a sphere, 3ut the radius 6ill depend upon the
radial .unction 6ith 6hich the s2type angular .unction is com3ined in any particular case7
At the ris4 o. stating the o3/ious, it is emphasised that, a.ter the last radial node, the
electron density .alls o.. eponentially 6ith r so the 3oundary sur.ace is chosen ar3itrarily
and has no physical reality7
)1'1& T$e p9";n#tions
The %2.unctions,
#m
!# "
m
!$" S
#m
!# $", are o. three .orms depending upon
the /alue o. m, i7e7 m = #, 0 or +#7 Dor purposes o. illustration it is 3est to a/oid
using the comple .unctions 6hich contain ep!mi$" and to use the alternati/e
.unctions o.
cos!m$" and sin!m$"7 The di..erence 3et6een the t6o sets o. .unctions is that the comple
.unctions are eigen.unctions o. l

B
, the operator .or the B2component o. the or3ital angular
momentum, 6hereas the sine and cosine .unctions are not (see Chapters , and *+7 But,
i. 6e are not speciLcally interested in the or3ital angular momentum o. the electron 6e
loose nothing 3y this7 The simplest %2.unction is1
S
#0
=
#0
!# "
0
!$" =

!,,*(" cos!#
"
and to plot it 6e proceed as .ollo6s (Digure 57,+7
We dra6 the B2ais 6ith the nucleus, ;, at B = 0 and a radial co2ordinate .rom the
nucleus in a direction 6hich ma4es an angle # 6ith that ais7 :ecalling that # is the angle
3et6een the B2ais and the radial co2ordinate (r +, 6e mar4 o.. a length ;p e0ual to cos!#
" on the radial co2ordinate7 We repeat this process .or a num3er o. /alues o. # and 6e
note that, 3ecause o. the 6ay # is deLned, all angles in 6hich p has a positi/e B co2
ordinate
are in the range 0 # (,2 and cos!# " is there.ore positi/e7 All /alues o. # .or 6hich
p has a negati/e B co2ordinate (e7g7 pG in Digure 57,+ lie in the range (,2 # ( and
p
p
0
0
N

;
+
6ig;re )1' !lotting the angular .unction .or a p
B
2or3ital
# ,
#02 The Structure and Spectroscopy o. the Atom
cos!# " is there.ore negati/e7 When 6e ha/e mar4ed out su.Lcient points, on 3oth sides
o. the B2ais, 6e Lnd that p and pG descri3e t6o per.ect circles 6hich touch at N 7 This is
a %olar graph o. cos!# "7 Since the .unction S
#0
has no dependence upon the angle $, an
identical result 6ould 3e o3tained .or any plane 6hich contains the B2ais7 There.ore, in
three dimensions this representation o. S
#0
consists o. t6o spheres in contact and could
3e o3tained 3y rotating the t6o circles o. Digure 57, a3out the B2ais, i7e7 through all
possi3le /alues o. $7
The angular 6a/e.unction has a /alue o. Kero at #
=
$0

, i7e7 in the xy2plane, 6here

it changes phase7 This is an ang1lar node in the 6a/e .unction and all %2.unctions ha/e
one such planar angular node as 6e shall see 6hen 6e consider the other t6o .unctions1

, #

S
#c
=
2

sin!# "

(

cos!$" and S
#s
=
2

sin!# "

(

sin!$"
To plot these .unctions is slightly more complicated7 Dirst 6e L a /alue .or # and a
con/enient choice is $0

since sin!$0

" = #7 This choice o. # means that 6e are /arying

$ in the xy2plane and 6e plot it in eactly the same 6ay as 6e plotted # a3o/e7 At is
clear that .or S
#c
6e must o3tain the t6o circles in contact since 6e are again plotting a
cosine .unction7 That the result .or the sine .unction should also 3e the same, 3ut rotated
through $0

, may not 3e immediately o3/ious, 3ut it can 3e readily demonstrated 3y a

.e6 minutes o. plotting7
An Digure 57*, the point p
x
traces out cos!$" and the .unction S
#c
and p
y
traces out
sin!$" and the .unction S
#s
7 As 6ith the .unction S
#0
, the signs o. the t6o lo3es o.
the .unction are determined 3y the sign o. sin!$" or cos!$" in the appropriate 0uadrant7
:emem3er that $ is al6ays the angle 3et6een the x2ais and the radius /ector, N

p!p

"7
To o3tain the complete angular .unctions 6e must no6 consider the result o. /arying
#
o/er its range o. 0 to ( 7 The .unction in 0uestion is sin!# " 6hich .or any constant $ gi/es
t6o circles in contact in the plane deLned 3y the B2ais and the radius /ector N p!p

"7
The diameter o. each circle is N p!p

"7 Thus, i. 6e L a /alue o. $ at say, Kero, 6e
o3tain the polar plot o. S
#c
as t6o circles in contact in the xB2plane7 The t6o .unctions
R
p
y
+
.
p

.
F

;
+

Dor p

1 ;2p

= sin0 cos. Dor p
y
1 ;2p
y
= sin0 sin.
6ig;re )1( !lotting the angular .unctions .or p
x
2 and p
y
2or3itals
S
#c
and S
#s
turn out to 3e eactly li4e S
#0
consisting o. t6o spheres in contact 3ut
aligned along the x2 and y2aes respecti/ely7
Accordingly, these three angular .unctions are 4no6n as the p
x
, p
y
and p
B
.unctions7
At is important to note that a sum o. the s0uares o. the x2, y2 and B2.unctions has no
dependence upon # or $ and is there.ore spherically symmetrical7 Conse0uently, i. each %2
.unction is occupied 3y one or 3y t6o electrons the total electron distri3ution is spherically
symmetrical7 This is clearly the case .or the single s2.unction and it is also true o. the
L/e d 2.unctions, the se/en .2.unctions and so on7
A .urther point should 3e made 6ith regard to the .orms o. the s0uared .unctions7 A.
6e ma4e a polar plot o. S
2
#0
S
2
#c
or S
2
#s
6e o3tain results similar to those
o3tained a3o/e 3ut 6ith an important di..erenceP the t6o spheres 3ecome t6o pear2
shaped lo3es7 But the directional properties o. the .unctions remain 0uite unchanged and
either .orm o. plotting is suita3le .or a discussion o. the spatial characteristics o. %2
.unctions7
)1'1' T$e d9";n#tions
!olar diagrams o. the L/e d 2.unctions can 3e o3tained in the manner descri3ed a3o/e7
They are sho6n in Digure 5757 Again, .or purposes o. illustration the real sine and cosine
.unctions ha/e 3een chosen7 :eOecting their orientation 6ith respect to the Cartesian aes,
the d 2.unctions are named, d
xy
, d
xB
and d
yB
.or the three .unctions 6hich are directed
3et6een the aes indicated, and d
x
2

y
2 .or the .unction 6ith its lo3es lying along the

and y aes7 The .unction d

B
2

S
20
, is clearly di..erent and the reason .or this can 3e a
source o. di.Lculty7 An actual .act, it is not as di..erent .rom its companions as it appears
since it can 3e 6ritten as a com3ination o. t6o .unctions, d
B
2

x
2 and d
B
2

y
2 , 6hich
ha/e eactly the same .orm as the other .our d 2or3itals, i7e7 .our lo3es 6ith their aes at
right angles and lying in a plane7 We ha/e to 6rite the d
B
2
.unction in the .orm gi/en
3ecause
R N
+ +
N
F
+
+
d
y
F
+
d
K

N R
+
R
+
d
yK
+
d
K
2

+ +
F

2
y
2
6ig;re )1) d 2or3ital angular .unctions
i. 6e used the .unctions d
B
2

x
2 and d
B
2

y
2 6e 6ould ha/e si d 2.unctions 6hich 6ere
not mutually orthogonal and there.ore not independent o. each other7 To use such a
set o.
.unctions 6ould 3e li4e trying to plot a graph on a normal piece o. graph paper on 6hich
three, rather than t6o, aes had 3een dra6n7
The phases o. the d 2.unctions sho6 that they each ha/e t6o angular nodes 6hich, .or
all ecept the d
B
2
, consist o. t6o mutually perpendicular planes7 The angular nodes o. the
d
B
2
.unction ta4e the .orm o. t6o cones 6ith their apees at the nucleus7
The se/en .2.unctions are important in the chemistry o. the lanthanides and actinides,
3ut it 6ould ta4e us too .ar .rom the main theme o. this chapter to discuss them here7
<etails may 3e .ound in re.erence
,
7
)1( THE C2M!5ETE 2R8ITA5 4AVE 6UNCTI2NS
A complete 6a/e .unction,
nlm
!r # $", 6hich .orms a solution o. SchroM
dingerGs e0uation .or the hydrogen atom, is there.ore a product o. the three .unctions
R
nl
!r "

lm
!# "


m
!$" in 6hich 6e must recognise that the three 0uantum num3ers, n, l and
m
are not entirely independent o. each other7
The num3er o. nodes in the complete 6a/e .unction is the sum o. the radial and
angular nodes and rises 6ith increasing or3ital energy7 The total num3er o. nodes is
n # (Ta3le 572+7 But the actual .orm o. the angular .unctions does not change as the
0uantum num3er n increases, they simply reach out .urther .rom the nucleus, 3ecause o.
the increasing etension o. the radial .unction, and are intersected 3y an increasing num3er
o. radial nodes7 The occupation o. the energy le/els and the .orm o. the associated 6a/e
.unctions pro/ides the 4ey to understanding the chemical 3ond and molecular geometry7
These su3@ects are discussed in much more detail in Chapter ?7
)1) 2THER 2NE9E5ECTR2N AT2MS
Though hydrogen and its isotopes,
2
9 and
,
9, are the only elements 6hich ha/e
one electron in the neutral state, many positi/e ions 6hich ha/e @ust one electron are
4no6n and their spectra are .re0uently o3ser/ed in high2energy discharges 6here
electrons are
Ta?le )1& The nodes o. the hydrogen atom 6a/e .unctions
;um3er o. nodes ;um3er o. nodes
"r3ital "r3ital
n l radial angular total n l radial angular total
#s 0 0 0 *s , 0 ,
*p 2 # ,
2s # 0 # *d # 2 ,
2p 0 # # *. 0 , ,
,s 2 0 2 5s * 0 *
,p # # 2 5p , # *
,d 0 2 2 5d 2 2 *
5. # , *
5g 0 * *
# #0$ -#-7,5 9e
+
2 #0$ -2272?
, #0$ -2%7-2 Be
+++
* #0$ -,07?2
=
Atoms and Aons 6ith more than "ne 'lectron #05
Ta?le )1' 8alues o. the :yd3erg constant (R+ .or hydrogen and some
one2electron ions
AtomHion O R(cm

#
+ AtomHion O R(cm

#
+
9 # #0$ ?--75$
2
9 # #0$ -0-7*2
,
9
Li
++
stripped a6ay .rom atoms to .orm multiply charged ions7 The energy le/els and 6a/e
.unctions o. these one2electron ions are gi/en 3y the .ormulae .or the hydrogen atom
6ith the appropriate modiLcation o. the /alue o. the nuclear charge, O7 Ta3le 57, gi/es
the /alues o. the :yd3erg constant, R (see Bo 57#+, determined .rom the spectra o. 9,
9e
+
, Li
++
and Be
+++
7 The small change in the /alue o. R as 6e go .rom 9 to Be
+++
is due to the change in the mass o. the nucleus 6hich enters the .ormula .or the energy
le/els 6hen it is 6ritten in the strictly correct .orm1
E
n
= O
2
Te
*
,%h
2
?
0
2
n
2
in J or O
2
Te
*
,%ch
,
?
0
2
n
2
in cm

#
6here T = m
e
m
N
,!m
e
+ m
N
" is the reduced mass o. the electron, m
e
, and the nucleus,
m
N
7 Dor .urther discussion o. the reduced mass see Chapter #0 and Bo #07#7
This /ariation o. R 6ith nuclear mass is not simply an arcane theoretical point7 An #$,2,
the o3ser/ation o. a /ery 6ea4 line on the higher2energy side o. each o. the Balmer lines
6as important proo. o. the eistence o. a hydrogen isotope 6ith an atomic mass o. 27
)1* E5ECTR2N S!IN
Thus .ar, this account o. the structure o. the atom has 3een .ocused on the energy o.
the electron and its distri3ution in the space surrounding the atomic nucleus7 The angular
momenta in/ol/ed are or3ital angular momenta7 But immediately prior to SchroM
dingerGs pu3lication o. the ne6 6a/e mechanics, Goudsmit and =hlen3ec4 had proposed
that the nuances o. atomic spectral data, especially the Neeman e..ect (see Section
57##+, could 3est 3e interpreted on the assumption that the electron had an intrinsic
QspinG angular
momentum 6ith s
=
#
and m
s
#
7 At almost eactly the same time, !auli proposed his
2 2
eclusion rule (Section 57-72+ according to 6hich electrons 6ith opposed m
s
/alues 6ere
paired in the spatial or3itals descri3ed in the earlier part o. this chapter7 Thus, although
he did not eamine the electron spin .unctions, SchroM dinger 6as undou3tedly 6ell
a6are that spin 6as a property 6hich 6ould ha/e to .orm a part o. any comprehensi/e
theory o. atomic structure7 We also 4no6 that, in #$2%, the 6hole concept o. electron spin
6as placed on a much Lrmer .ooting 3y <iracGs relati/istic treatment o. the hydrogen
atom7 But 6e need only note that the property o. spin adds t6o more 0uantum num3ers,
s and m
s
, to those re0uired to .ully speci.y an electron in an atom7 The .urther
conse0uences o. electron spin 6ill 3e ta4en up in Section 57% on6ards7
)1+ AT2MS AN3 I2NS 4ITH M2RE THAN 2NE E5ECTR2N
The 9amiltonian operator .or a many2electron atom contains many terms7 'ach 4inetic2
energy term and the electron2nucleus attraction term in/ol/es only one electron7 These
#0? The Structure and Spectroscopy o. the Atom
one2electron terms present little di.Lculty to the 6ould23e calculator o. atomic structure7
But the terms descri3ing the mutual repulsion o. the electrons each in/ol/e t6o electrons
and though they are simple to 6rite do6n they are /ery di.Lcult to deal 6ith computation2
ally7 The pro3lem is this7 An the helium atom .or eample, ho6 can 6e 4no6 the energy
o. electron # 6hen 6e do not 4no6 ho6 electron 2 is distri3uted around the atomJ We
need to 4no6 the distri3ution o. electron 2 in order to calculate the energy o. the # I
2 inter2electronic repulsion7 There is no closed alge3raic solution o. this three+*ody
%ro*lem
(2 electrons + # nucleus+, neither in classical nor in 0uantum mechanics7 9o6e/er, there
is a 6ay .or6ard i. 6e are prepared to carry out a long cyclic calculation7 The procedure
is as .ollo6s, 6here 6e ta4e the lithium (Li+ atom as an eample7
)1+1% T$e sel"9#onsistent Bel/
We ha/e to determine a 6a/e .unction .or each o. the three lithium electrons7 Because
e/ery atom is spherically symmetrical, 6e 4no6 that the angular .unctions 6ill 3e the same
as those o. the hydrogen atom or3itals and that 6e shall there.ore ha/e 6a/e.unctions
6hich 6e may descri3e as #s and 2s, the Lrst containing t6o electrons and the second
one7 The pro3lem is to determine the appropriate radial .unctions 6hich are strongly
inOuenced 3y the presence o. the inter2electronic repulsion7 We start 3y guessing 6a/e
.unctions .or electrons 2 and , 3asing our guess upon 6hate/er in.ormation 6e ha/e .rom
eperiment or theory7 9a/ing done this 6e sol/e the SchroM dinger e0uation .or
electron
# mo/ing in the a/eraged electrostatic Leld o. the nucleus and electrons 2 and ,7 ;et
6e sol/e the SchroM dinger e0uation .or electron 2 using the guessed 6a/e .unction
.or electron , and the calculated 6a/e .unction .or electron #7 We no6 sol/e the e0uation
.or electron , using the 6a/e .unctions calculated .or electrons # and 27 The resulting three
6a/e.unctions and total electronic energy are not the Lnal ans6er since they are 3ased
upon the original guesses7 But they do pro/ide 3etter approimations to the true ans6ers
and i. 6e repeat the cycle o. calculations 6e can ma4e a .urther impro/ement in our
6a/e .unctions and energy7 A. the cyclic calculation is continued the changes in the 6a/e
.unctions and energy 3ecome smaller 6ith e/ery cycle until, 6ithin the limits o. accuracy
re0uired .or that particular calculation, there is no .urther change in them7 When this point
is reached the electronic 6a/e .unctions are said to 3e consistent 6ith the electrostatic
Leld .rom 6hich they 6ere calculated and 6hich the electrons themsel/es produce7 The
process is 4no6n as a self+consistent Celd (SCD+ calculation7 ;o6adays, computers ma4e
this tas4 rather easy, 3ut the Lrst calculations o. the type 6ere done the hard 6ay 3y the
9artrees, .ather and son, in the #$,0s7
]
;ota3le contri3utions to the su3@ect 6ere also
made 3y 8ladimir A7 Doc4 (#%$% I #$-*+ and 6a/e .unctions calculated 3y this
method are o.ten called 9artree I Doc4 .unctions7
)1+1& Ele#tron #orrelation
9o6e/er, e/en an SCD calculation does not pro/ide an eact radial 6a/e.unction7 Because
the electrons repel each other their motions are correlated, i7e7 they 4eep out o. each otherGs
]
The .ather (W9+ 6as a retired school teacher 6ith time to spare7 9is son, the physicist and mathematician <ouglas
:ayner 9artree (#%$- I #$5%+, set him to 6or4 on the long, demanding SCD calculations 6ith 6hich the .amily name
is no6 synonymous7
The 'lectronic States o. the Atom #0-
6ay, and this e..ect is not .ully allo6ed .or in the 9artree2Doc4 method 6hich assumes
that the electrons produce a static, spherical Leld and .ails to allo6 .or the dynamic e..ects
o. the inter2electronic repulsion 6hich is 4no6n as electron correlation7 This su3@ect 6ill
3e discussed .urther in Section ?7%7
)1+1' T$e perio/i# ta?le o" t$e elements
Today, SCD 6a/e .unctions are readily a/aila3le7 The angular .unctions are eactly the
same as those o. the hydrogen atom, 3ut the radial .unctions are not7 ;or can they
3e epressed as alge3raic .unctions o. r 3ut are gi/en as ta3les o. /alues7 Apart .rom
the increase o. energy 6hich the inter2electronic repulsion engenders, it also has the
conse0uence that the electrons can no longer 3e considered as indi/idual, independent
entities since their motions depend upon those o. their .ello6s, and /ice /ersa7 There.ore,
the 6a/e .unction and energy o. any one electron must depend upon the distri3utions and
hence the 6a/e .unctions o. all the other electrons in the atom, and one cannot truly spea4
o. the 6a/e .unction o. a single electronP the 6a/e .unction .or an atom is a .unction o.
the co2ordinates o. all the electrons7
;e/ertheless, chemists ha/e .ound it possi3le, and etremely use.ul, to thin4 in terms
o. indi/idual electrons occupying indi/idual or3itals in many2electron atoms and in terms
o. 3uilding up the atom (the a1f*a1 %rinci%le + 3y Llling the or3itals in order o. increasing
energy 6ith t6o spin2paired electrons (the Pa1li %rinci%le or excl1sion r1le+7 Thus 6e
ascri3e many o. the particular properties o. the transition metals and their ions to electrons
occupying ,d (Ti2Nn+, *d (Nr2Cd+ and 5d (9.29g+ or3itals and the electron 6hich is so
readily lost 3y the al4ali metal atoms is a 2s (lithium+, ,s (sodium+, *s (potassium+ . . .
electron7 The empty or partially Llled or3itals play a similarly use.ul role7 We en/isage
that the ,s electron lost 3y sodium enters the singly occupied ,p or3ital o. chlorine 6hen
the sodium and chlorine atoms com3ine to .orm sodium chloride7
An e/ery case these are electrons or or3itals in the outer reaches o. the particular atom,
i7e7 they are valence or3itals or valence electrons and ha/e the highest, or nearly the
highest, energy and /alue o. n7 Thus, a 0uantum2mechanical /ie6 o. the periodic ta3le
is an arrangement o. the elements in 6hich those ha/ing the same electronic structure
in their outermost, normally incomplete, shell are placed in columns7 The .act that the
structure o. the incomplete outer shell o. an element controls its reacti/ity, the num3er
o. chemical 3onds 6hich it .orms (/alency+ and the geometry o. the molecules o. 6hich
it .orms a part (see Chapter ?+ eplains the /ery similar chemical properties 6hich 6ere
the Lrst stimulus to the construction o. the ta3le7
)1, THE E5ECTR2NIC STATES 26 THE AT2M
Though indi/idual or3itals are /ery use.ul .or a 0ualitati/e or semi20uantitati/e description
o. the 6ay in 6hich a many2electron atom .orms chemical 3onds to other atoms, a more
eact description is re0uired i. 6e 6ish to account 0uantitati/ely .or the energetics o.
3ond .ormation or atomic spectroscopy7 Dor these purposes 6e re0uire a description in
6hich all the electrons in the atom are includedP i7e7 the electronic state o. a many2
electron atom must 3e characterised 3y means o. 0uantum num3ers that descri3e the total
2
#0% The Structure and Spectroscopy o. the Atom
angular momentum o. the atom7 The eact .orm in 6hich these 0uantum num3ers are
gi/en depends upon the atom in 0uestion .or reasons 6hich 6e shall disco/er 3elo67 We
start out 3y descri3ing a hydrogen2li4e or one2electron atom7
)1,1% T$e BAe @;ant;m n;m?ers o" a single ele#tron
These are the1
principal 0uantum num3er n
or3ital angular momentum 0uantum num3er l
0uantum num3er .or the B2component o. or3ital angular momentum m
l
spin angular momentum 0uantum num3er s
0uantum num3er .or the B2component o. the spin angular momentum m
s
At is clear that, 6ith the eception o. the Lrst, all these 0uantum num3ers characterise an
aspect o. the angular momentum o. the electron7 (The su3script l has 3een re2introduced
in m
l
in order to distinguish it .rom m
s
+7
)1,1& Q;ant;m n;m?ers "or t$e man09ele#tron atom
As noted a3o/e, the proper description o. a many2electron atom must 3e a description
6hich includes all the electrons7 Since the spherical symmetry o. the atom is maintained
as more electrons are added, the angular momentum 0uantum num3ers remain /alid and
are central to this description7 An analogy 6ith those 6hich re.er to indi/idual electrons,
6e introduce .our ne6 0uantum num3ers, L, 5
L
, S and 5
S
, 6hich descri3e the or3ital
and spin angular momenta o. all the electrons, collecti/ely7 'tending the notation, lo6er
case letters .or one electron, upper case letters .or t6o or more electrons, 6e say that
atoms 6ith /alues o. L = 0 # 2 , . . . are in S P E 9 . . .
states7
The /alue o. S (total spin 0uantum num3er+ is important 3ecause it characterises the
multiplicity o. the spin state, i7e7 the num3er o. 5
S
/alues, 6hich is 2S + # (Section *7*+,
and the multiplicity is normally added to the sym3ol .or the state as a le.t superscript, e7g7
.or S =
#
and L = 2 6e ha/e a
2
< state (spo4en dou3let <+, .or S = 2 and L = # 6e
ha/e a
5
! state (0uintet !+7 The /alues o. 5
S
and 5
L
are not usually speciLed7 Sym3ols
such as
2
< and
5
! used to descri3e the states o. atoms are 4no6n as term sym*ols and
in the net section a method o. Lnding the possi3le L and S /alues .or a particular
arrangement o. electrons in or3itals, i7e7 a conCg1ration, is descri3ed7
]
)1,1' T$e assignment o" term s0m?ols
Gi/en a particular atomic conLguration, i7e7 an assignment o. electrons to hydrogen2li4e
atomic or3itals, the determination o. the possi3le states or terms o. the atom is 0uite
]
At is most un.ortunate that in this notation, 6hich is almost #00 years old and there.ore 0uite impossi3le to change, the
sym3ol S stands .or t6o completely di..erent angular momentum properties7 Dortunately, the possi3ilities o. error due to a
con.usion 3et6een the t6o 0uantities represented 3y S are /ery .e67
2
straight.or6ard7 Dirstly 6e recognise that i. e/ery one o. the n
2
or3itals corresponding to
a particular principal 0uantum num3er, n, is dou3ly occupied, all components o. spin and
or3ital angular momenta cancel to gi/e a total angular momentum o. Kero7 There.ore, all
such closed shells can 3e ignored in the determination o. term sym3ols7 The treatment
o. the partially Llled shells is 3est carried out 3y constructing a ta3le as illustrated in
the .ollo6ing eample in 6hich the conLguration p
2
is analysed7 We concentrate our
attention upon the possi3le B2components o. or3ital and spin angular momenta, since
these can 3e simply added 3ecause they are all aligned along B, and .or the p
2
pro3lem
the maimum 5
L
= m
l#
+ m
l2
/alue is # + # = 27 Similarly, the maimum /alue o.
5
S
is
#
+
#
=
#7 Since 6e 4no6 (Section *7*+ that the B2components, 5
U
, o. angular
2 2
momentum, U, al6ays ta4e all /alues 3et6een
+
U and

U in unit steps, our 5

L
/alues
must run .rom
+
2 to

27 Similarly, our 5
S
/alues must 3e
+
#, 0 and

#, and 6e
arrange these data as sho6n in Ta3le 57*7 The sym3ol in 3rac4ets gi/es the m
l
and m
s
o. electron # and electron 2, i7e7 (m
l#
m
s#
P m
l2
m
s2
+, 6hich add to gi/e the 5
L
and 5
S
/alues at the side and head o. the ta3le7 There is no entry in the position 5
L
= +2
and 5
S
= +# 3ecause this could only 3e achie/ed i. 3oth electrons occupied the same p
or3ital (m
l
= +#+ and had the same spin (m
s
= +
#
+ 6hich is .or3idden 3y the !auli
principle7 The 3rac4eted sym3ols are the possi3le microstates o. the system and 6e can
readily chec4 that 6e ha/e .ound the correct num3er o. them1 #57 A p electron can ha/e
si com3inations o. the 0uantum num3ers m
l
and m
s
7 There.ore, 6e ha/e a choice o. si
possi3ilities .or our Lrst electron7 Since no t6o electrons can ha/e the same com3ination
o. the L/e 0uantum num3ers, 6e ha/e only L/e possi3ilities .or the second electron
ma4ing ? 5 = ,0 possi3ilities in total7 But electrons are indistinguisha3le so that, .or
eample, !+# +
#
P 0
#
" !0
#
P +# +
#
" and there are there.ore ?
5
= #5 possi3le
2 2 2 2 2
microstates o. the system7
To Lnd the terms o. p
2
6e Lrst .ocus our attention upon the entry in the ta3le 6hich
has the highest 5
L
/alue and, i. there are more than one o. these, upon that 6hich has
3oth the highest 5
L
and the highest 5
S
/alue7 An Ta3le 57* the entry 6ith the highest 5
L
/alue is (
+
#
+
#
P
+
#

#
+7 The .act that there is a microstate 6ith an 5
L
/alue o.
+
2
2 2
tells us immediately that it must 3e accompanied .our other microstates 6ith 5
L
/alues
o. +#, 0, # and 2 and that the L/e together .orm a state 6ith L = 2, i7e7 a < state7
The same reasoning tells us that since 5
S
= 0 there are no other spin components o. this
state 6hich has S = 0 and 2S + # = #, i7e7 6e ha/e .ound a
#
< term7 We there.ore tic4
o.. one micro state in each 3o ha/ing 5
S
= 0 and 5
L
= +2 . . . 27 We do not need
Ta?le )1( The microstates o. the electron conLguration p
2
5
S
+# 0 #
+
2 (
+
#
+
#
P
+
#

#
+
2 2
+
# (
+
#
+
#
P 0
+
#
+ (
+
#
+
#
P 0

#
+ (
+
#

#
P 0
+
#
+ (
+
#

#
P 0

#
+
2 2 2 2 2 2 2 2
5
L
0 (
+
#
+
#
P

#
+
#
+ (
+
#
+
#
P

#

#
+ (
+
#

#
P

#
+
#
+ (
+
#

#
P

#

#
+
2 2 2 2 2 2 2 2
(0
+
#
P 0

#
+
2 2

# (

#
+
#
P 0
+
#
+ (

#
+
#
P 0

#
+ (

#

#
P 0
+
#
+ (

#

#
P 0

#
+
2 2 2 2 2 2 2 2

2 (

#
+
#
P

#

#
+
2 2
,
!
0
,
!
#
,
!
2
to identi.y 6hich o. the microstates, in a group 6ith more than one, 3elongs to
#
<, the
tic4ing process is merely one o. Q4eeping accountG7
We no6 identi.y the microstate among those remaining 6hich has the highest 5
L
and
5
S
/aluesP it is (
+
#
+
#
P 0
+
#
+7 Since it has 5
L = +
# and 5
S = +
# this microstate
2 2
must 3e one o. the nine 6hich .orm a
,
! term and 6e tic4 o.. microstates in Ta3le 57*
accordingly7 A single microstate 6ith 5
S
= 0 and 5
L
= 0 remains and this must 3e the
single component o. a
#
S term7 So our result is that the conLguration p
2
gi/es rise to three
termsP
#
< (5 components+,
,
! ($ components+ and
#
S !# component" = #5 components
in total = num3er o. microstates in Ta3le 57*7
At should 3e admitted here that the a3o/e method o. determining the terms o. a particular
conLguration is more /alua3le as an illustration o. the meaning o. a term sym3ol and o.
the su3tle 6ay in 6hich the spin and or3ital angular momenta o. t6o electrons com3ine
than it is as a practical research tool7 A conLguration 6ith se/eral . electrons, such as 6e
Lnd in the rare earths, is e..ecti/ely impossi3le to analyse 6ith this method (e7g7 .
*
has
#00# microstatesU+ and some etremely sophisticated mathematical techni0ues ha/e 3een
de/eloped to deal 6ith this type o. pro3lem7 'ach term in a conLguration has a di..erent
energy 3ecause o. the di..erent contri3utions .rom inter2electronic repulsion in each one7
But the !2S + #"!2L + #" components 6ithin each term ha/e almost eactly the same
energy7 An .act they 6ould 3e degenerate 6ere it not .or an e..ect 4no6n as s%in+or*it
co1%ling 6hich splits each term into a num3er o. le/els o. di..erent energy, as sho6n in
Section 57$7
)1,1( Term energies an/ H;n/s r;les
As 6e ha/e seen, a single electron conLguration can gi/e rise to se/eral terms and, in
general, all o. these ha/e di..erent energies 3ecause o. the di..erent contri3utions .rom
the inter2electronic repulsion in each one7 Ta3le 575 gi/es the energies o. some eamples
o. the conLguration np
2
7 (The energy o. the
,
!
0
state has 3een ar3itrarily set to Kero7+ The
energies o. the
,
! states are not all e0ual 3ecause o. spin2or3it coupling (see Section 57$+,
so a 6eighted mean energy is gi/en in the .ourth column o. the ta3le7
The electron spin plays an important role in determining the inter2electronic repulsion
and it does so in a rather su3tle 6ay, the details o. 6hich depend upon the connection
3et6een the electron spin and spatial 6a/e .unctions and the !auli principle7 This is
eplored in detail in Chapter ##7 9ere it 6ill 3e su.Lcient to recognise that, in order to
con.orm 6ith the !auli principle, di..erent electron spin .unctions must 3e com3ined 6ith
di..erent electron spatial .unctions7 Thus, since the inter2electronic repulsion is directly
determined 3y the spatial distri3ution o. the electrons, the energies o. the /arious terms
are di..erent7 This .act 6as noted in #$2- 3y Driederich 9und (#%$? I +, largely as a
result
Ta?le )1) The energies (in e8+ o. the terms arising .rom the conLguration np
2
,
!(mean+
#
<
2
#
S
0
Ge *p
2
070 070?$# 07#-*% 07#20# 07%%,* 2702$,
Sn 5p
2
070 0720$% 07*250 07,0?0 #70?-$ 27#2-$
!3 ?p
2
070 07$?$5 #7,205 #705?% 27??05 ,70$55
Spin2"r3it Coupling ###
o. eperimental studies o. atomic spectra7 "n the 3asis o. his o3ser/ations 9und proposed
t6o rules .or e0ui/alent electrons1
#7 The terms o. highest multiplicity lie lo6est in energy7
27 A. t6o terms ha/e the same multiplicity the lo6est is that 6ith the greatest /alue o. L7
The data in Ta3le 575 illustrate 9undGs rules7 The
,
! states are the lo6est and one o.
them,
,
!
0
, is the ground state7 Also,
#
< is lo6er than
#
S7
)1- S!IN92R8IT C2U!5IN
The origin o. spin2or3it coupling is easy to understand7 To an electron or3iting an atomic
nucleus the nucleus appears to 3e an or3iting positi/e charge7 This or3iting charge gen2
erates an electric current 6hich, in turn, produces a magnetic Leld at the electron7 This
magnetic Leld interacts 6ith the magnetic Leld due to the spin o. the electron and the
energy o. interaction is 4no6n as the spin2or3it coupling energy7 Theory sho6s that the
e..ect is proportional to O
*
, 6here N is the nuclear charge, and it there.ore increases
/ery steeply 6ith increase in atomic num3er7 The coupling o. the spin and or3ital angu2
lar momenta o. an electron, 6hich results .rom this interaction, mies those 0uantities
together so that, especially .or hea/y atoms, it is possi3le to spea4 o. L and S only as
approimate 0uantum num3ersP the only eact angular momentum 0uantum num3er 3eing
Q , 6hich is a com3ination o. the t6o7 There are t6o 6ays o. determining Q , one o. 6hich
is appropriate .or light atoms and one .or hea/y7
)1-1% R;ssell I Sa;n/ers or L' #o;pling
Dor light atoms the /alues o. Q can 3e o3tained 3y adding together the /alues o. L
and S .or the total or3ital and spin angular momenta o. the electrons determined as in
Section 57%7,7 We add the angular momenta using the .ormula (Section *7?+1
Q = L + S L + S # L + S 2 . . . |L S|
The /alues o. Q are 6ritten as a right su3script on the term sym3ol, e7g7 .or p
2
1
#
< !S = 0 L = 2" ===
#
<
2
,
! !S = # L = #" ===
,
!
2

,
!
#
and
,
!
0
#
S !S = 0 L = 0" ===
#
S
0
'ach state ha/ing a particular /alue o. Q has 2Q + # components 6ith 5
Q
/alues run2
ning .rom +Q to Q and in the a3sence o. a magnetic Leld, vide infra, all are degenerate7
Thus, as a result o. spin2or3it coupling, a
,
! term 6hich 6as nine2.old degenerate, is split
into a L/e2.old degenerate
,
!
2
, a three2.old degenerate
,
!
#
and a singly degenerate
,
!
0
term7 The L/e2.old degeneracy o. the
#
< term is not remo/ed and the
#
S
0
term has
only one component7
When 6e .ormulate spin2or3it coupling in this 6ay 6e call it LS coupling 3ecause 6e
com3ine /alues o. L and S to gi/e Q 7 At is also 4no6n as :ussell2Saunders coupling a.ter
##2 The Structure and Spectroscopy o. the Atom
t6o astronomers 6ho Lrst used it to interpret the atomic spectra o. stars in #$25, 3e.ore
the ad/ent o. 0uantum mechanics as 6e 4no6 it7
Thus, in order to o3tain a model o. the electronic structure o. a light, many2electron
atom, 6e 3uild up our description in three stages7
#7 We Lrst thin4 o. a many2electron atom as 3eing composed o. a num3er o. electrons
each mo/ing in an or3ital characterised 3y 0uantum num3ers n l m
l
s and m
s
7 We
recognise that the radial parts o. these or3itals 6ill depend upon the charge on the
nucleus and that the electrons 6ith lo6 /alues o. n 6ill there.ore 3e /ery close to
the nucleus 6hile electrons in or3itals 6ith higher /alues o. n 6ill reach out much
.urther into the space surrounding the atom7 Those 6ith the highest /alue o. n are the
/alence electrons 6hich are the most important in the .ormation o. chemical 3onds
and in atomic spectroscopy7
27 ;et 6e ta4e account o. the .act that, although the indi/idual n /alues are unchanged,
the detailed .orms o. the radial .unctions 6ill 3e changed 3y the inter2electronic repul2
sion7 Durthermore, 3ecause the electronic motions are correlated and 3ecause 6e cannot
distinguish 3et6een indi/idual electrons in a many2electron system, the indi/idual /al2
ues o. l and s are no longer meaning.ul and must 3e replaced 3y L and S 6hich
descri3e the or3ital and spin angular momenta o. the electrons as a 6hole7
,7 Dinally, 6e recognise that the e..ect o. spin2or3it coupling re0uires that 6e com3ine
L and S to gi/e a total angular momentum 0uantum num3er Q 7
At should 3e noted that the three steps a3o/e are associated 6ith three physical e..ects
o. diminishing energy7 An step # 6e ha/e the 4inetic and potential energies o. the electrons
mo/ing in the Leld o. the charged nucleus7 An the second step, 6e add the smaller energy
due to the inter2electronic repulsion7 An step , 6e add the spin2or3it coupling energy
6hich, .or atoms 6ith atomic num3ers less than 20, is e/en smaller7 When carried out
6ith proper mathematical precision, this process o. eamining the largest contri3ution to
the energy Lrst and then adding in the e..ects o. .urther, smaller energy terms in order o.
decreasing energy is called %ert1r*ation theory (Appendi *+7 At has 3een 4no6n since the
time o. Lord :ayleigh (#%*2 I #$#$+ and has etensi/e uses in 3oth classical and
0uantum mechanics7 At is important that the energy contri3utions are ta4en in order o.
decreasing magnitude and in the case o. /ery hea/y atoms the spin or3it coupling,
6hich goes as O
*
, eceeds the inter2electronic repulsion and must there.ore 3e
considered Lrst7
)1-1& ,, #o;pling
Since 6e re0uire to consider spin2or3it coupling 3e.ore inter2electronic repulsion .or atoms
in the later ro6s o. the periodic ta3le, in step 2 6e Lrst com3ine the /alues o. l and s,
adding the angular momentum 0uantum num3ers as descri3ed in Section *7?, to ma4e a
& /alue .or each indi/idual electron, i7e7 in the case o. p
2
1
.or each p electron l
=
# and s
=
#
===
&
p
=
,
and
#
2 2 2
;o6, in step ,, 6e must add the & /alues together to gi/e Q .or the 6hole atom7 Where
6e ha/e t6o ine0ui/alent electrons, e7g7 p
#
d
#
, then 6e simply com3ine all the
possi2 3le m
&
/alues .or the d2electron 6ith all those .or the p2electron, in pairs7 But
in the
, # # , # #
2 2

2

2 2

2

2 # 0 2 #

0
#
# 0
2
0
#
# 2
0

p
p
&
2
&
Spin2"r3it Coupling ##,
Ta?le )1* The 5
Q
/alues o. the microstates o. np
2
in && coupling
p
,
p
#
2 2
,
2
#
, 2
2
#

2
,

2
#
# 2
2
#

2
case o. t6o e0ui/alent electrons, e7g7 p
2
.or 6hich 6e determined the term sym3ols in
Section 57%7,, 6e eperience again the pro3lem that 6e had in constructing Ta3le 57*,
i7e7 6e must 3e a6are o. the !auli principle7 Dor the conLguration np
2
6e ha/e possi2
3le & /alues o. #
+
#
=
,
and #

#
=
#
and *
+
2
=
? possi3le m
&
/alues7 A s0uare,
2 2 2 2
? ? array o. all possi3le com3inations o. t6o m
&
/alues (Ta3le 57?+, 6ould gi/e ,?
microstates7 But there can only 3e ?

5
=
#5 states .or t6o p2electrons and the .ol2
lo6ing states must 3e re@ected1 all si states on the diagonal o. the array, 3ecause i.
t6o electrons in the same shell ha/e the same & /alue and the same m
&
/alue
then they are identical and must 3e occupying the same atomic 6a/e .unction 6ith the
same spin7 This is contrary to !auliGs principle7 Durther, since electrons are
indistinguisha3le, an o..2diagonal array element o. the .orm Z& m
&
(#+P &

m

(2+\
cannot 3e distinguished .rom its Qmirror2imageG across the diagonal Z&

m

(#+P & m
&
(2+\7 These t6o microstates
together
{
Z& m
&
!#"P &

m

!2"\

Z&

m

!#"P & m
&
!2"\
}
,

2 descri3e a state o. the system so

& &
that #5 o. the ,0 o..2diagonal microstates must 3e neglected in the state2counting process7
We ar3itrarily choose the #5 microstates 3elo6 the diagonal lea/ing ,? ? #5 = #5
microstates (Ta3le 57?+7 Dollo6ing our usual method, 6e no6 start 6ith the largest 5
Q
/alue, remo/e the remaining 2Q 5
Q
/alues associated 6ith it and repeat the process until
all 5
Q
/alues ha/e 3een accounted .or7 The p

,
p
,
triangle gi/es Q = 2 and 0, the p

,
p
# 2 2 2 2
rectangle gi/es Q = 2 and # and the p

#
p
#
triangle gi/es Q = 07 The total num3er o. states
2 2
calculated .rom these Q /alues is 5 + # + 5 + , + # = #5 conLrming the correctness o.
our 6or4ing7
)1-1' Interme/iate #o;pling
We ha/e noted a3o/e that LS or :ussell2Saunders coupling applies /ery 6ell to light
atoms and && coupling to hea/y atoms7 But 6hat a3out atoms o. intermediate mass, or N
/alueP there is no sudden change .rom LS to && couplingJ This is a pro3lem typical o.
the physical sciences and especially so o. 0uantum mechanics7 We ha/e solutions .or the
etremes o. our pro3lem 3ut not .or the intermediate region .or 6hich, in .act, no simple
solution is possi3le7 The root o. our di.Lculty lies in the application o. the steps o. the
pertur3ation theory outlined in Section 57$7#7 At is important to ta4e the larger terms 3e.ore
'
n
e
r
g
y

(
a
r
3
i
t
r
a
r
y

u
n
i
t
s
+
'
n
e
r
g
y

(
a
r
3
i
t
r
a
r
y

u
n
i
t
s
+
the smaller ones and .or light atoms this means ta4ing inter2electronic repulsion 3e.ore
spin2or3it coupling7 Dor hea/y atoms the order must 3e re/ersed7 Dor the intermediate
case the only correct approach is to ta4e inter2electronic repulsion and spin2or3it coupling
together at the same time, since they are o. compara3le magnitudes7 This cannot 3e done
in as simple a manner as in the eamples descri3ed a3o/e, e/en .or t6o electrons7 A
more complicated calculation is re0uired (see Bo 572+7 But 6ith the help o. the digital
computer the calculation o. the terms or electronic energy states o. atoms presents little
di.Lculty today7
Dor systems 6ith a small num3er o. electrons such as np
2
a correlation diagram sho62
ing the transition .rom LS, through the intermediate region, to && coupling is use.ul in the
assignment o. atomic spectra7 Digure 57?, calculated 6ith data .rom Condon and Shortley,
*
sho6s the np
2
correlation diagram7 H is proportional to the ratio o. the spin2or3it cou2
pling to inter2electronic repulsion so that the Kero on the le.t2hand end o. the a3scissa
represents pure LS coupling 6hile the Kero on the right represents pure &&7 The assign2
ment o. the n%
2
electronic states o. germanium (n
=
*+, tin (n
=
5+ and lead (n
=
?+ is
also included and the mo/e .rom LS to && coupling 6ith increase o. nuclear charge is
/ery clear7 The energy scales at the t6o ends o. the diagram are not e0ual, they ha/e
3een modiLed so that the total spread o. the states is the sameP #5 energy units7 The
details o. this modiLcation
*
need not concern us here7 9o6e/er, 6e should not lea/e
this su3@ect 6ithout remar4ing upon the /alue o. the correlation diagram in chemistry7
Because, as chemists, 6e are o.ten interested in groups o. similar species, e7g7 the aro2
matic hydrocar3ons or the atoms in a particular ro6 or column o. the periodic ta3le,
6e 6ish to understand ho6 the properties o. a particular group o. atoms or molecules
/ary as their .undamental physical properties /ary across the group7 This in.ormation
can sometimes 3e displayed in diagrammatic .orm, the most 6ell24no6n eample o. this
3eing the periodic ta3le itsel.7 But there are many other important eamples in physics
and chemistry7
LS
#0
#
S
0
& &
& & Q
#0
,H2 ,H2 0
5 Ge *p
2
Sn 5p
2
!3 ?p
2
#
<
2
0
,
!
2
5 #
0
5
,H2 ,H2 2
0
,H2 #H2 2
,H2 #H2 #
5
#0
070 075
c
#70 075
#Hc
#H2 #H2 0
070
#0
:eprinted 6ith permission, '787Condon and G797 Shortley, a-he -heory of Atomic S%ectraa,
#$,5, Cam3ridge =ni/ersity !ress7
6ig;re )1* Spin2or3it coupling in np
2
Selection :ules in Atomic Spectroscopy ##5
)1-1( Inter9ele#troni# spin9or?it #o;pling
The or3ital magnetic moment o. an electron can also interact 6ith the spin magnetic
moment o. another electron, and /ice /ersa7 9o6e/er, the energies concerned are /ery
small compared 6ith those due to the intra2electronic e..ects 6hich 6e ha/e descri3ed
a3o/e and they are usually neglected7
)1%. SE5ECTI2N RU5ES IN AT2MIC S!ECTR2SC2!Y
(<)<*
An many places in this chapter re.erence has 3een made to the in.ormation 6hich atomic
spectroscopy pro/ides a3out atomic structure7 But 6e must not thin4 that e/ery energy
state o. the atom can 3e reached .rom e/ery other state 3y the emission or a3sorption o.
radiation7 The process is su3@ect to restrictions, 4no6n as selection rules, 6hich result .rom
the re0uirements that energy and angular momentum must 3e conser/ed7 At is precisely
3ecause these restrictions eist that so much detailed in.ormation has 3een o3tained7 The
conser/ation o. energy is em3odied in the Bohr2'instein selection rule1
E = h>
The change in energy o. the atom must 3e eactly e0ual to the energy o. the photon
a3sor3ed or emitted7
)1%.1% Ang;lar moment;m
The photon o. electric dipole radiation has an angular momentum characterised 3y the
angular momentum 0uantum num3er #, 3ut 6ith only t6o B2components, +# and #,
parallel and antiparallel to the direction o. propagation7 (This su3@ect is discussed in more
detail in Section %7* and the treatment here 6ill there.ore 3e 3rie.7+ Thus, since angular
momentum is conser/ed, in one2electron atoms atomic transitions 3et6een atomic or3itals
6ith angular momentum 0uantum num3ers l and l

must 3e such that l

=
l
+
#, l or l

#,
and the B2component o. the angular momentum must also 3e conser/ed7 The electron spin
does not interact 6ith the oscillating electric Leld o. the radiation so it is not changed7
(;ote ho6e/er, that the spin does interact 6ith the radiationGs magnetic Leld and this
interaction is /ery important in magnetic resonance spectroscopy and in magnetic dipole
transitions, Section 57#07#727+
An summary, the selection rules .or dipolar radiation in one2electron atoms are1
#7 s = 0
27 l = 0, #, 3ut l = 0 is .or3idden 3y parity (see Section 57#072+
,7 m
l
=
#
There is no restriction on the change in the /alue o. the principal 0uantum num3er,
n, 6hich accounts .or series o. lines such as the Balmer series7
When 6e consider many2electron atoms the position 3ecomes more complicated and,
in general, the interaction o. spin and or3ital angular momenta must 3e considered7 An the
limit o. pure LS coupling 6e ha/e .or electric dipole radiation1
#7 S = 0
27 L
=
0,

#, 3ut L
=
L

=
0 is .or3idden
##? The Structure and Spectroscopy o. the Atom
,7 5
L
= #
*7 Q
=
0,

#, 3ut Q
=
Q

=
0 is .or3idden
As 6e mo/e a6ay .rom LS coupling, into the intermediate region and to6ards &&
coupling the 0uantum num3ers S and L 3ecome increasingly poorly deLned and the
selection rules progressi/ely less deLniti/e7 Selection rules epressed in terms o. changes
o. state 0uantum num3ers are the results o. application o. angular2momentum theory to the
coupling 3et6een atom and radiation7
*5
They apply only to idealised situations, e7g7 %1re
LS coupling7 A. eact in.ormation on a particular transition is re0uired the detailed 6a/e
.unctions .or the states in 0uestion must 3e determined and the transition moment integral
e/aluated7 This su3@ect is discussed in much more detail in Bo 5727 Sections %7- and ##7-
and Appendi $ also contain rele/ant in.ormation7
-./0././ Electric 1uadrupole transitions
An some atoms and ions, e7g7 "
2
+
, /ery 6ea4 transitions 6hich are .or3idden 3y the selec2
tion rules descri3ed a3o/e, 3ut not induced 3y spin2or3it coupling, ha/e 3een o3ser/ed7
These transitions satis.y selection rules in 6hich the photon in/ol/ed appears to carry
t6o units o. angular and they are ascri3ed to 0uadrupolar photons7
*5
9o6e/er, photons
in a 3eam o. light ha/e not, to this authorGs 4no6ledge, 3een sho6n to carry t6o 0uanta
o. angular momentumP in contrast to the case o. a 3eam o. circularly polarised light, the
photons o. 6hich ha/e 3een sho6n 3y Beth
-
to carry hH2( units o. angular momentum
each7 At 6ould appear that a deLniti/e analysis o. the conser/ation o. angular momentum
in 0uadrupolar transitions is not yet a/aila3le7
-./0./.2 "agnetic dipole transitions
The magnetic Lelds arising .rom the or3ital and spin angular momentum o. the electron
can also interact 6ith the magnetic Leld o. an impinging photon7 The transitions 6hich
result are 4no6n as magnetic dipole transitions7 They are o. the order o. #0

-
times
6ea4er than electric dipole transitions7
)1%.1& !arit0
An order to understand the concept o. parity it is 3est i. 6e Lrst consider a 6a/e.unction o.
an atom, !x y B", and per.orm upon it the operation o. multiplying the three Cartesian
co2ordinates 3y #7 We call this operation the parity operation and it can 3e represented
3y the e0uation1
6here

!x y B"
===
!

B"
is the parity operator7
A. 6e per.orm this operation on the hydrogen #s or3ital (Appendi 5+ then1
#


#s
=

(
,
O

2
a
0
#

ep!

=,2"
=
(
,
O

2
a
0
ep!=,2"
#

l
B l B
and the .unction is unchanged 3ecause = is proportional to the positi/e s0uare root o.
(x
2
+
y
2
+
B
2
+7 Conse0uently,
#s
does not change sign 6hen the signs o. the Cartesian
co2ordinates are changed and is there.ore said to 3e even7 All s or3itals are e/en7 But i.
6e apply the parity operator to the 2p
B
6a/e .unction then1


2pB
=


2
5
#

O

2
2(
a
B ep!

=,2"
=

5
O

2
a
B ep!=,2"

0 2 2( 0
and 6e Lnd that the .unction changes its sign (3ecause

B = B+7 At is odd as are all
p .unctions7 But note that the 6a/e .unction is still an eigen.unction o. the 9amiltonian
operator 6ith the same energy eigen/alue as 3e.ore7
All atomic 6a/e .unctions can 3e classiLed into t6o groups7 Those 6hich are unchanged
under the parity operation, the s, d, g, . . . .unctions, are said to 3e e/en and they are
sometimes denoted 3y g (.rom the German QgeradeG = e/en+7 Dunctions 6hich change sign
under the parity operation, the p, ., h, . . . .unctions, are said to 3e odd and denoted 3y u
(.rom the German QungeradeG+7 The rules .or com3ining parities are @ust the same as those
.or multiplying the num3ers +# and #7 Thus, i. t6o .unctions o. the same parity, e/en
or odd, are com3ined the result is a .unction o. e/en parity, 6hereas i. t6o .unctions o.
di..erent parities are com3ined the resulting .unction is o. odd parity7
'lectric 0uadrupole and magnetic dipole photons, Sections 57#07#7# and 57#07#72, are
o. e/en parity7 But the great ma@ority o. eperimental o3ser/ations in atomic spectroscopy
in/ol/e dipolar photons 6hich are o. odd (u+ parity7 This means that the initial and Lnal
states o. a transition must 3e o. opposite parity so that, (parity o. initial state+ u = (parity
o. Lnal state", and parity is conser/ed7 Alternati/ely 6e may argue (Appendi $+ that,
since the dipolar photon is o. u symmetry, the product o. the parities o. the initial and
Lnal states must also 3e u so that the transition dipole moment integral (Appendi $+ as a
6hole is g7 By 3oth arguments the parity selection rule is .ound to 3eP u g and g u
transitions allo6ed, u u and g g .or3idden7 This is 4no6n as the Laporte rule7
)1%% THE :EEMAN E66ECT
Apart .rom interacting 6ith each other, the magnetic Lelds due to the spin and or3ital
motion o. an electron can also interact 6ith an eternally applied magnetic Leld7 The
e..ect o. the interaction is to li.t degeneracy and split spectral lines, as 6as Lrst o3ser/ed
3y !ieter Neeman (#%?5 I #$*,+ in #%$?7 The 0uantum num3ers 6hich determine
the angular momenta o. the electron, l, m
l
, s and m
s
determine the associated
magnetic moments according to the .ollo6ing relationships7 A. 6e choose, as 6e
in/aria3ly do, the B2ais as that along 6hich the angular momentum is 0uantised, the
or3ital motion o. an electron gi/es rise to a magnetic moment in the B2direction7 The
relationship 3et6een the 0uantum num3er .or the B2component o. the or3ital angular
momentum (m
l
+ and the magnetic moment (T
B
+ is deri/ed .rom the classical e0uations
.or the magnetic Leld due
to a circulating electron o. charge

e and mass m
e
in Section #2727*P it is1
T
l
eh`
m
T m
6here T
eh`
=
B
=
2m
e
2m
e
T
B
is the Bohr magneton and the negati/e sign sho6s that the magnetic moment is
antiparallel to the or3ital angular momentum7
T
S
Such a simple analysis is not possi3le .or the magnetic moment due to the spin angular
momentum7 But using the relati/istic <irac e0uation it is .ound that1
B
= g
e
T
B
m
S
= 2.002,T
B
m
S
2 T
B
m
S
g
e
is 4no6n as the electron g2.actor and the approimation, g
e
= 2, is 0uite ade0uate .or
all 3ut the most eacting eperiments or calculations7
A. 6e no6 impose an eternal magnetic Leld 3B4 upon the electron there 6ill 3e an
energy change ( E+ gi/en (Bo #272+ 3y1
E
=
!T
l
+
T
S
"

/
=
!m
l
+
2m
S
"T
B
/
B

gT
B
/
B
(57##7#+
B B
6here /
B
is the component o. the Leld in the B2direction7 An this epression a use.ul eper2
imental parameter, g, has 3een introduced7 The g2/alue deduced .rom the eperimentally
o3ser/ed splitting o. spectral lines pro/ides an immediate num3er .or comparison 6ith
theoretical estimates o. m
l
+
2m
s
7 Where the true atomic electronic states are comple
mitures o. the simple microstates as, due to e..ects li4e spin2or3it coupling they normally
are, the /alue o. g 6ill not 3e the simple integer or hal.2integer 6hich '0uation (57##7#+
might lead us to epect7 Since T
B
= $.2-, #0

2*
J T

#
the energy change, or Neeman
splitting, is /ery small7 Con/erting to 6a/e num3ers, 6e Lnd that T
B
= 0.*?- cm

#
T

#
so that a Leld o. the order o. t6o Tesla is re0uired to produce a splitting o. # cm

#
7 This
eplains 6hy Daraday searched, 6ithout success, .or the e..ect o. a magnetic Leld upon
spectral lines some ,0 years 3e.ore Neeman .ound it7
)1%%1% T$e normal :eeman e""e#t
An #%$? 6hen Neeman Lrst o3ser/ed his eponymous e..ect there 6as no concept o.
electron spin7 But or3ital angular momentum and the associated magnetic e..ects 6ere
readily understanda3le 6ith classical electrodynamics and early studies o. the Neeman
e..ect there.ore ga/e a mied picture7 Some results 6ere easy to interpret and these cases
3ecame 4no6n as eamples o. the normal Neeman e..ect7 The remaining results 6ere
only understood 6hen electron spin and its magnetic e..ects 6ere postulated 3y Goudsmit
and =hlen3ec4 in #$25P prior to that they 6ere said to 3e eamples o. the anomalo1s
Neeman e..ect7 There is also an important relationship 3et6een the Neeman e..ect and the
polarisation o. light 6hich is 3est eplained diagrammatically (Digure 57-+7 The properties
o. polarised light are discussed in detail in Section %72 and that discussion 6ill not 3e pre2
empted here7 An discussing Digure 57- 6e shall simply ma4e a num3er o. 3ald statements
6hich 6ill 3e elucidated in Chapter %7
A
#
S
0
to
#
!
#
transition in the a3sence o. a magnetic Leld is illustrated in Digure
57-(a+7 An eample 6ould 3e the Fe?s
2
to Fe?s
#
?p
#
transition o. 3arium 6hich is .ound
at < = 55,.-0 nm and is responsi3le .or the 3right green colour o. the Oame test .or
3arium7 The spectrum appears as a single line since, although there are three upper states
(5
Q
= +
# 0

#+, they are all o. e0ual energy7 An Digure 57-(3+ our atom sample has
3een placed at the centre o. a solenoid so that it is su3@ect to a magnetic Leld (/ +, 6hich
is parallel to the light 3eam7 The magnetic Leld li.ts the degeneracy o. the
#
!
#
state
as re0uired 3y '0uation (57##7#+ so that it is no6 possi3le, in principle, to o3ser/e three
transitions .rom the ground to the ecited state7 Durthermore, the upper state energy le/els
ha/e angular momentum characterised 3y the 0uantum num3ers Q = # and 5
Q
= 0 #7
; S
; S
hn
;
hn
S
hn
; S
#
!
#
#
S
0
B = 0 B HH to light
B to light
+1
0
1
rcp lcp
s p s
(a+ (3+ (c+
6ig;re )1+ The normal Neeman e..ect in the
#
S
0
to
#
!
#
transition o. 3arium
There.ore, in order to conser/e angular momentum, the photon must pro/ide the angular
momentum re0uired .or transitions .rom ground state to the 5
Q
le/els o. the ecited state,
since the lo6er state has no angular momentum7 Circularly polarised light has eactly
the properties 6e re0uireP an angular momentum o. # and .or right circularly polarised
(rcp+ photons a B2component o. # and .or lcp photons +#7 Thus, i. 6e use circularly
polarised light in the Neeman eperiment 6e shall 3e a3le to see the transitions to the

# states 3ut the transition to 5

Q
=
0 6ill not 3e o3ser/ed since the B2component o. the
angular momentum cannot 3e conser/ed7
But i. 6e 3ore a hole in our solenoid and illuminate the atom sample 6ith a light 3eam
perpendicular to the direction o. the magnetic Leld (Digure 57-(c++, a ne6 polarisation
possi3ility emerges7 The oscillating electric and magnetic Lelds, 6hich are the .undamental
carriers o. the polarisation property, can only oscillate in the plane perpendicular to the
direction o. propagation o. the light7 With the eperimental arrangement o. Digure 57-(c+
the light can 3e polarised in the direction o. the Leld and i. 6e use plane polarised light
transitions to all three ecited sates can 3e seen7 The transition to 5
Q
=
0 is energised 3y
light polarised parallel to / and is denoted 3y ( (Gree4 p .or parallel+7 The transitions to
5
Q
= # are energised 3y light polarised perpendicular to / and are denoted 3y ' (Gree4 s
.or German sen4recht = perpendicular+7 The total pro3a3ility o. the transitions in each
o. the three Lgures is the same7 A. 6e set it to .our ar3itrary units in Digure 57-(a+, then
6e ha/e t6o .or each o. the transitions in Digure 57-(3+ and one .or each ' and 2 .or ( in
Digure 57-(c+7 8ery important practical use o. the Neeman e..ect is made in 0uantitati/e
analytical atomic spectroscopy 6here the a3ility to mo/e an a3sorption line 3y applying a
2
magnetic Leld ena3les the 3ac4ground o. the line to 3e measured and su3tracted7 Dinally,
6e note that the eperimentally o3ser/ed separation 3et6een the outer lines gi/es a /alue
o. g o. #702 6hich is 2 Y larger than the theoretical /alue o. #707 This pro3a3ly arises
3ecause o. miing, 3rought a3out 3y spin2or3it coupling, 6ith states ha/ing S = 0, 6hich
3rings us to the anomalous Neeman e..ect7
)1%%1& T$e anomalo;s :eeman e""e#t
When Goudsmit and =hlen3ec4 proposed that electrons had an intrinsic spin angular
momentum characterised 3y the angular momentum 0uantum num3er o.
#
3ut 6ith a
g2/alue o. 270, t6ice as large as the g2/alue .or or3ital angular momentum, the puKKling
splitting patterns o3ser/ed in many spectra 6ere rapidly elucidated and a .ormula epress2
ing the g2/alue in terms o. the 0uantum num3ers L S and Q 6as deri/ed 3y Al.red Lande
b (#%%% I #$-5+, see Section #2721
Q !Q + #" + S!S + #" L!L + #"
g = # +
2Q !Q
!5.##.2"
+ #"
This .ormula gi/es the g2/alues o. 07500, #7#?- and #7,,, .or
,
<
#
,
,
<
2
and
,
<
,
respec2 ti/ely7 These Lgures may 3e compared 6ith the eperimental data .or
corresponding states o. calcium 6hich are 0750#, #7#?2 and #7,2$7 The sodium <2lines
pro/ide a good illus2
tration o. the anomalous Neeman e..ect (Digure 57%+7 The /alues o. 5
Q

g in Digure 57%
are simply the product o. the 5
Q
/alue o. the state and the its g2/alue as determined 3y
'0uation (57##72+ and they are directly related to the spacing o. the spectral linesP e7g7
.or
2
P
,
S =
#
L = # Q =
,
gi/ing g =
*
6hence 5
Q
g = 2 and
2
7
2 2 , ,
2
2
!
#H2
2
S
#H2
C
J
_g
+1/3
1/3
+1
1
2
!
,H2
2
S
#H2
C
J
_g
+6/3
+2/3
2/3
6/3
+1
1
(a+
(3+
6ig;re )1, The anomalous Neeman e..ect on the sodium < lines
Boes .or Chapter 5 #2#
0
)1%& 8I85I2RA!HY AN3 6URTHER REA3IN
#7 L7 !auling and '7B7 Wilson, :ntrod1ction to 31ant1m 5echanics, CcGra629ill, ;e6 Ror4,
#$,5, and <o/er7
27 97 'yring, J7 Walter and G7'7 >im3all, 31ant1m Chemistry, Wiley, ;e6 Ror4, #$**7
,7 Shapes and polar plots o. .2or3itals7 97G7 Driedman, Jr7, G7:7 Choppin and <7G7 Deuer3acher,
Q. Chem. Ed1cation, (%, ,5* I ,5%, #$?*7 C7 Bec4er, Q. Chem. Ed1cation, (%, ,5% I ,?0,
#$?*7
*7 '7=7 Condon and G797 Shortley, -he -heory of Atomic S%ectra, Cam3ridge =ni/ersity !ress,
#$,57
57 :7<7 Co6an, -he -heory of Atomic Str1ct1re and S%ectra, Cali.ornia =ni/ersity !ress, Ber4eley,
#$%#7
?7 J7C7 Slater, 31ant1m -heory of Atomic Str1ct1re, 8ols7 A and AA, CcGra629ill, ;e6 Ror4, #$?07
-7 :7A7 Beth, Phys. Rev., (,, *-# (#$,5+P )., ##5 (#$,?+7
82D )1% T$e spe#tral series o" t$e $0/rogen atom
An #%$0 Johannes :o3ert :yd3erg (#%5* I #$#$+ 6rote the Balmer .ormula .or the
lines in the emission spectrum o. the hydrogen atom in the .orm 6hich is most
common today1

# #

> = R
r
2

s
2
9ere, > is the /alue in 6a/e num3ers (cm

#
+ o. the spectral line, R the
:yd3erg constant (#0$ ?--75-% cm

#
+ and r and s the principal 0uantum num3ers o.
the lo6er
and upper states connected 3y the transition respecti/ely7 =sing this .ormula the L/e
3est24no6n series o. hydrogen lines may 3e characterised as in the .ollo6ing ta3le7
Series r s Lrst line last line
>
(cm

#
+
<
(nm+
>
(cm

#
+
<
(nm+
Lyman (#$0?+ # 2, ,, . . . %2 25%72 #2#7? #0$ ?--7? $#72
Balmer (#%%5+ 2 ,, *, . . . #5 2,27$ ?5?75 2- *#$7* ,?*7-
!aschen (#$0%+ , *, 5, . . . 5 ,,#7? # %-57? #2 #%?7* %207#
Brac4ett (#$22+ * 5, ?, . . . 2 *?-7% * 05272 ? %5*7$ # *5%7%
!.und (#$2*+ 5 ?, -, . . . # ,*075 - *5$7$ * ,%-7# 2 2-$7*
The last line in each series corresponds to a transition in 6hich the upper state has
the principal 0uantum num3er o. inLnity in each case (Digure B57#7#+7 An this state the
electron has the highest energy it can ha/e and still 3e 3ound to the nucleus7 At higher
energies the electron lea/es the atom, i7e7 ionisation ta4es place7 There.ore, all series
ha/e a common upper le/el .or their transition o. highest energyP the ionisation limit7
But the energy re0uired to reach it diminishes since each series starts .rom a higher
le/el7 SchroM dingerGs result .or the eigen/alues o. the hydrogen atom ('0uation
(57#7#++
sho6s that, in cm

#
1
me
*
R
=
%ch
,
?
2
'lectron 3inding energy (#0
,
cm
#
+
#20 #00 %0 ?0 *0 20 0
l = #2#7? nm
l = #027? nm
?5?75 nm
l = $-7, nm
*%?7# nm
l = $570 nm
*,*70 nm
l = $,7% nm
*#072 nm
AoniKation
l = $#72 nm
,?*7- nm
# 2 , * n
Lyman
6ig;re 8)1%1% The Lyman and Balmer series o. the hydrogen atom
Balmer
82D )1& Inter9ele#troni# rep;lsion< spin9or?it #o;pling FS2CG an/ t$eir e""e#t
;pon transition pro?a?ilit0 an/ sele#tion r;les
The purpose o. this Bo is to pro/ide a .airly detailed eample o. the 6ay in 6hich
the relati/e magnitudes o. inter2electronic repulsion and S"C a..ects not only state
energies, as illustrated in Digure 57?, 3ut also 6a/e.unctions and hence transition
pro3a3ilities7 This 6ill also o..er an opportunity to illustrate ho6 transition pro3a2
3ilities are calculated .rom atomic 6a/e.unctions7 The eample 6ill 3e 3ased on the
conLguration p
2
and a transition to that conLguration .rom s
#
p
#
7 We 3egin 6ith
a discussion o. p
2
7
T$e energies o" t$e p
&
#onBg;ration
We ha/e .ound the terms o. p
2
in the LS and && limits in Section 57$, 3ut the methods
used there do not re/eal the com3inations o. microstates, i7e7 the 6a/e.unctions, 6hich
are associated 6ith each term7 These can 3e o3tained .or the limiting cases 3y use o.
the raising and lo6ering operators in the 6ay illustrated .or d
2
in Appendi #0, 3ut .or
the intermediate case 6hich concerns us here 6e re0uire to diagonalise (Appendi ,+
simultaneously the matrices o. the operators .or S"C, V l

s, and inter2electronic
repul2
sion, e
2
,r
#2
7
The 3asis states or microstates may 3e 6ritten in the .orm (m
l#
m
s#
m
l2
m
s2
+
6ith the m
s
/alues represented 3y a superscript plus or minus sign, e7g7 (+#
+

0

+, it
3eing al6ays understood that the microstate is actually a Slater determinant (Appendi
?+, i7e71

!
+
#
+
0

"
=
!#, 2"{|+#
+
!#"0

!2" |0

!#" + #
+
!2" }
ZA. the t6o electrons are not 3oth p2electrons it 6ould usually 3e necessary to
include the 0uantum num3er l in the notation7\ Dor p
2
there are #5 microstates and in
the matrices 6hich .ollo6 6e shall consider #0 o. them, those ha/ing 5
Q
/alues o.
+
2,
+
# and 07 The matri elements .or 5
Q
=
2 and

# are, o. course, /ery similar

to those .or 5
Q
= +
2 and
+
#7 We shall not go into the details o. the calculation o.
the electron2repulsion matri elements7 Dull treatments o. this su3@ect can 3e .ound in
numerous sources7
#I,
The re0uired integrals can 3e epressed as a sum o. products o.
angular and radial parts the Lrst o. 6hich can 3e o3tained in closed .orm and ta3ulated
.or any com3ination o. spherical harmonics (Appendi 5+, i7e7 .or all atoms7 The radial
integration, on the other hand, depends upon the radial .unctions 6hich di..er .rom
atom to atom and they must 3e determined indi/idually, either theoretically or 3y
comparison 6ith eperiment, .or each atom7 9o6e/er, the results can 3e epressed
in terms o. a small num3er o. integrals, D
0
and D
2
in the present case, 6here1

D
;
!n
a
l
a
n
*
l
*
"
=
e
2
!r
;
,r
;+#
":
#
2
!n
a
l
a
":
2
2
!n
*
l
*
"r
2
r
2
dr
#
dr
2 P R # 2
0 0
:(nl + is the radial part o. an atomic 6a/e.unction .unction, r
P
is the smaller and r
R
the larger o. r
#
and r
2
, and the electron repulsion is o3tained as a sum o. t6o terms,
A
0
D
0
+ A
2
D
2
, 6here A
0
and A
2
are the results o. the angular integrations7
The inter2electronic repulsion matri .or the microstates o. p
2
ha/ing 5
Q
= +2
and +# is1
(+#
+
+#

+
(+#
+
+#

+
D
0
+ D
2
,25
(+#
+
0
+
+
0
(+#

0
+
+
0
(+#
+
0

+
0
(+#
+
#
+
+
0
(
+
#
+
0
+
+ 0 D
0

D
2
,5 0 0 0
(
+
#

0
+
+ 0 0 D
0

2D
2
,25

,D
2
,25 0
(
+
#
+
0

+ 0 0

,D
2
,25 D
0

2D
2
,25 0
(
+
#
+

#
+
+ 0 0 0 0 D
0

D
2
,5
The eigen/alues o. this part o. the matri are D
0
D
2
,5 (,+ and D
0
+ D
2
,25
(2+7
The inter2electronic repulsion matri .or the microstates o. p
2
ha/ing 5
Q
=
0 is1
(+#
+
#

+
(+#
+
#

+
D
0
+ D
2
,25
(+#

+
0
(+#

#
+
+
?D
2
,25
(0
+
0

+
+,D
2
,25
(#
+
0
+
+
0
(
+
#

+ 0 D
0

D
2
,5 0 0 0
(
+
#

#
+
+

?D
2
,25 0 D
0
+
D
2
,25

,D
2
,25 0
(0
+
0

+
+
,D
2
,25 0

,D
2
,25 D
0
+
*D
2
,25 0
(

#
+
0
+
+ 0 0 0 0 D
0

D
2
,5
The eigen/alues o. this part o. the matri are D
0
D
2
,5 !,", D
0
+ D
2
,25 !#"
and D
0
+
2D
2
,5 !#

"7
#

#

0 #

0 #

# #
i
2
#
2
The remaining L/e states o. the electron2repulsion matri gi/e eigen/alues o.
D
0
+ D
2
,25 !2" and D
0
D
2
,5 !," so that in total 6e ha/e1 D
0
D
2
,5 !$", D
0
+
D
2
,25 !5" and D
0
+ 2D
2
,5 !#"7 Since D
0
appears on each diagonal element and
no6here else it simply sets the a3solute energy scale and can usually 3e set to Kero7
Thus, these are the states
,
!,
#
< and
#
S 6hich, 6ith D
0
= 0 and D
2
= 25 ar3itrary
units, correspond in energy and degeneracy to the etreme le.t o. Digure 57?7 The
corresponding 6a/e.unctions can 3e o3tained as com3inations o. microstates 3y diag2
onalising the 3loc4ed out matrices7 The energy matri .or p
2
in the a3sence o. S"C
is seen to 3e a .unction only o. D
2
6hich can 3e treated as a parameter and its /alue
o3tained 3y comparison o. calculated and eperimental energy le/els7
The matri elements o. the S"C are more readily o3tained than those o. electron
repulsion7 We epress the operator in the .orm o. a sum o/er (in this case t6o+
electrons1
V

l

i
s
i
= V

#
2
!l

i
+s

i

+
l

i
s

i
+"
+
l

iB
s

iB
i i
At is use.ul to dra6 up the .ollo6ing ta3le1
|+#
+
|0
+
|#
+
|+#

|0

|#

+
s

0

2|+#

2|0
+
0 0 0 l

s
+
0 0
0

2|0
+

2|#
+
0
l

B
s

B
#
|+
#
+

0

#
|
#
+

#
|+
#

0
#
|
#

2 2 2 2
l


s

#
+
#

#

#
+
#
+
#

#
+
#

|+ |+ | | | |+ | |
2 2 2 2 2 2 2 2
Drom 6hich, .or eample1
V

l

i
s
i
|+#
+
0
+
= V
#
2
|+
#
+
0
+
+
V

|+#
+
+ #

gi/ing rise to an on2diagonal matri element o.
#
V and an o..2diagonal element o.

#
2
2
2
V 6ith
+
#
+
+
#

|
7 The S"C matri .or the microstates o. p
and +# is1
ha/ing 5
Q
= +
2
(+#
+
+#

+ (+#
+
0
+
+ (+#

0
+
+ (+#
+
0

+ (+#
+
#
+
+ (+#
+

+#

+ 0 V ,

2 0 0 0 (
+
#
+
0
+
+ V ,

2 V ,2 0 0 0
(+#

0
+
+ 0 0 V ,2 0 0
(+#
+
0

+ 0 0 0 V ,2 V ,

2
(+#
+
#
+
+ 0 0 0 V ,

2 0
The eigen/alues o. this part o. the matri are +V !2" and
#
V !,"7
2
2
The S"C matri .or the microstates o. p
2
ha/ing 5
Q
= 0 is1
(
+
#
+

+ (
+
#

+ (
+
#

#
+
+ (0
+
0

+ (

#
+
0
+
+
(+#
+
#

+ V 0 0 0 0
(+#

+ 0 V ,2 V ,

2 V ,

2 0
(0
+
0

+ 0 V ,

2 0 0 V ,

2
(#
+
0
+
+ 0 0 V ,

2 V ,

2 V ,2
The eigen/alues o. this part o. the matri are +V !2 ",
#
V !2 " and 2V !# "7
When the results .or 5
Q
= # and 2 are included the #5 eigen/alues o. the spin2
or3it matri are .ound to 3e 2V !# ",
#
V !% " and +V !? " 6hich corresponds
to the etreme right o. Digure 57? 6ith V = 5 ar3itrary units7
Anspection o. the matrices o. V l


s

and e
2
,r
#2
sho6s that they are 3loc4ed out,
though not in eactly the same 6ay .or 3oth operators7 The inter2electronic repulsion
connects, i7e7 has an o..2diagonal matri element 3et6een, microstates 6hich ha/e the
same /alue o. 5
L
and the same /alue o. 5
S
6hereas the S"C lin4s microstates 6ith
the same /alue o. 5
Q
!
=
5
L
+
5
S
"7 9o6e/er, not all pairs o. states 6hich satis.y
these re0uirements are connected 3y an operator7
An cases o. intermediate coupling, 6here the S"C and inter2electronic repulsion
are o. compara3le magnitudes, 6e must sum the t6o matrices and diagonalise the
result7
A similar analysis o. the energetics o. the s
#
p
#
conLguration might 3e made, 3ut
this is not necessary .or our present purposes and it su.Lces to say that the .ollo6ing
terms are possi3leP
#
! and
,
! in the a3sence o. S"C and
#
!
#
,
,
!
2
,
,
!
#
and
,
!
0
6hen it is present7
Atomi# transition pro?a?ilities
Dirst, some preliminary o3ser/ations7 Apart .rom the Bohr2'instein condition, the
selection rules o. atomic spectroscopy are couched in terms o. the 0uantum num3ers
6hich descri3e particular aspects o. the angular momentum o. the atom7 We shall
assume that the Bohr2'instein condition is satisLed and concentrate on the condi2
tions on the 0uantum num3ers7 8ery general deri/ations o. the selection rules 6hich
rely on ad/anced angular momentum theory can 3e .ound in the specialist tets on
atomic spectroscopy7
#I,
9ere 6e shall conLne our attention to speciLc eamples
6hich illustrate the general results7
The intensity o. an electronic transition .rom an initial or3ital, $
i
, to a Lnal or3ital,
$
.
, in a one2electron atom is proportional to the s0uare modulus o. the transition
moment integral (Appendi $ and Section %7-+, i7e7 : | $
.
|er|$
i
|
2
6here e is the
electronic charge and r the /ector distance 3et6een the electron and the nucleus7 Dor
a many2electron atom : | G
.
|
;
er
;
|G
i
|
2
6here the sum o/er ; runs o/er all the
electrons and G
.
and G
i
represent electronic states7 The transition moment operator
is a one+electron operator 6hich means that .or a non2Kero TC integral the states
,

represented 3y G
i
and G
.
can only di..er 3y one or3ital 3ecause, .or eample, o. the
n terms in the .ollo6ing sum1
G
.
|
4
er
;
|G
i
= $
a
!#"$
*
!2"$
c
!," . . . $
n
!n"|
;
er
;
|$
a
!#"$
*
!2"$
x
!," . . . $
n
!n"
only1
$
c
!,"|er
,
|$
x
!," $
a
!#"|$
a
!2" $
*
!2"|$
*
!2" . . . $
n
!n"|$
n
!n"
may ha/e a /alue, all the others 3eing Kero 3ecause o. the orthogonality o. the atomic
or3itals $
c
and $
x
7
T6o approaches are open to us 6hen 6e see4 to e/aluate a TC integral such as

$
c
!,"
|
er
,
|
$
x
!,"

, one emphasises angular momentum and the other geometrical .ac2
tors7 Atomic or3itals can 3e .ormulated in a manner such that they are eigen.unctions
o. the angular momentum operators l

and l

B
7 An order to eploit this property 6e
6rite the operator er in a .orm appropriate .or le.t2 or right2circularly polarised light
(Section %7?+, using the common notation m

and m
+
respecti/ely1

lcp

m

=
!e, 2"!x iy" = !e

2"!r sin # cos $ ir sin # sin $"

= !er sin #,

2" ep!i$"

rcp

m
+
=
!e, 2"!x + iy" = !e,

2"!r sin # cos $ + ir sin # sin $"

= !er sin #,
2" ep!+i$"
Since the radial part o. an atomic or3ital is di..erent .or e/ery or3ital and e/ery
atom, only angular integration is appropriate at this point7 :adial integration can
only 3e carried out 6hen the radial .unctions o. the or3itals concerned are speciLed7
We Lnd that the only non2Kero matri elements 3et6een s and p or3itals in this
.ormulation are1

p
|
m

|
s
=
er,
, and p +

|
m
+
|
s
=
er, ,
This .orm o. TC integral is use.ul 6hen 6e 6ish to interpret spectra measured in
magnetic Lelds, as in the Neeman e..ect and magnetic circular dichroism, 6here the
le/els are split according to their m
l
/alues (Section 57## and Digures 57- and 57%+7
A. 6e epress the p2or3itals as p
x
, p
y
and p
B
and 6rite er as1
m
x
= er sin # cos $ m
y
= er sin # sin $ and m
B
= er cos #
6e Lnd that the only non2Kero TC integrals are1

p
x
|
m
x
|
s
=
p
y
|
m
y
|
s
=
p
B
|
m
B
|
s
=
er, ,
This .ormulation is appropriate .or spectra in 6hich the atom is in a non2spherical
en/ironment, e7g7 6hen su3@ected to an electric Leld7
We can no6 return to the 0uestion o. transitions 3et6een states o. the conLgura2
tions s
#
p
#
and p
2
7 Since the microstates (+#
+
+#

+ and (+#
+
0
+
+ appear at the top
and to the le.t o. Ta3le 57*, they must .orm components o. the states
#
E and
,
P o. p
2
respecti/ely7 Also, the matri o. inter2electronic repulsion sho6s that in the a3sence
o. S"C there is no miing 3et6een these states, nor do they interact 6ith any others7
2
Thus 6hen V = 0, the .ollo6ing 6a/e .unctions are true descriptions o. components
o. the
#
< and
,
! states o. p
2
1
#
< !p
2
" = !#,

2"{|+#
+
!#" + #

!2" |+#

!#" + #
+
!2" }
,
! !p
2
" = !#,

2"{|+#
+
!#"0
+
!2" |0
+
!#" + #
+
!2" }
;ote that the a3o/e 6a/e .unctions are o3tained 3y the epansion o. the Slater
determinants (Appendi ?+ represented 3y the microstates (+#
+
+#

+ and (+#
+
0
+
+7
Similar considerations sho6 that .or the conLguration s
#
p
#
6e can 6rite1
#
! !s
#
p
#
" = !#,2"{|s
+
!#" + #

!2" |+#

!#"s
+
!2"
|s

!#" + #
+
!2" + |+#
+
!#"s

!2" }
,
! !s
#
p
#
" = !#,2"{|s
+
!#" + #

!2" |+#

!#"s
+
!2"
+ |s

!#" + #
+
!2" |+#
+
!#"s

!2" }
We no6 calculate some transition moment integrals 3et6een the a3o/e states, using
the notation M = m
#
+ m
2
= er
#
+ er
2
7
# 2 # # # #

+ +

<!% "
|
M
|
P !s % "
=
!
2
2"{ +# !#" + # !2"| +# !#" + # !2"||M|
|s
+
!#" + #

!2" |+#

!#"s
+
!2" |s

!#" + #
+
!2" + |+#
+
!#"s

!2" }
= !
#

2"{ +#
+
!#" + #

!2"|M|s
+
!#" + #

!2"
+ +#
+
!#" + #

!2"|M|+#
+
!#"s

!2" + +#

!#" + #
+
!2"|M| + #

!#"s
+
!2"
+ +#

!#" + #
+
!2"|M|s

!#" + #
+
!2" }
The a3o/e reduction .rom eight integrals to .our is possi3le 3ecause those terms
in 6hich the m
s
/alue o. the electron is di..erent on either side o. the operator, e7g7
+
#
+
!#"
+
#

!2"
|
M
|+
#

!#"s
+
!2"

, are Kero 3ecause o. the integration o/er the spin
co2ordinates7 As an eample o. a non2Kero contri3ution to the transition moment 6e
can e/aluate1
+#
+
!#" + #

!2"|M|s
+
!#"+#

!2" = +#
+
!#" + #

!2"|m
#
+ m
2
|s
+
!#" + #

!2"
= +#
+
!#" + #

!2"|m
#
|s
+
!#" + #

!2" + +#
+
!#" + #

!2"|m
2
|s
+
!#" + #

!2"
= +#
+
!#"|m
#
|s
+
!#" +#

!2"|+#

!2" + +#
+
!#"|s
+
!#" +#

!2"|m
2
|+#

!2"
= +#
+
!#"|m
#
|s
+
!#"
3ecause o. the orthonormality o. the atomic or3ital 6a/e .unctions7 All .our integrals
# 2 # # #


gi/e the same contri3ution so that E!% "|M| P !s % " = 2 +#
|m|s
7 ;ote
that this is a transition in 6hich S
=
0, L
=
0 and 5
L
= +
#P although 6e ha/e
a t6o2electron atom 6e Lnd that the selection rules .or one2electron atoms apply
3ecause electron repulsion does not mi states 6ith di..erent S, L or 5
L
/alues7
ZThe reader may 6ish to conLrm, simply 3y changing a .e6 signs in the a3o/e
e0uations, that1
# 2 , # #
<!% "|M| P !s % " = 0 as epected since S = #\
But, as the a3o/e S"C matri sho6s, S"C mies states 6hich ha/e di..erent S, L
or 5
L
/alues7 We can illustrate the e..ect o. this 3y considering the t6o states in the
top le.t2hand corner o. the electron2repulsion and S"C matrices 6hich no6 interact
6ith each other 3ut 6ith no other states7 Adding the t6o matrices 6e ha/e the matri
on the le.t1
(+#
+
+#

+ (+#
+
0
+
+ (+#
+
+#

+ (+#
+
0
+
+ (+#
+

+#

+ D
0
+ D
2
,25 V ,

2 === 0 V ,

2 (+#
+
0
+
+
V ,

2 D
0
D
2
,5 + V ,2 V ,

2 V ,2 *D
2
,5
Since only the di..erence 3et6een the t6o diagonal matri elements is important here,
6e may su3tract D
0
+ D
2
,25 .rom each diagonal element and o3tain the right2hand
matri a3o/e7
A. 6e no6 suppose that V ,2
=
*D
2
,5, 6hich corresponds closely to the position
o. lead in Digure 57?, the diagonal elements are e0ual and there is an e0ual miing
o. (+#
+
+#

+ and (+#
+
0
+
+7 We can no6 no longer spea4 o. pure
#
E!%
2
" and ,
P !%
2
" statesP the eigenstates o. the atom are e0ual mitures o. the t6o7 There.ore,
transitions .rom
#
P !s
#
%
#
" to the states Lrst descri3ed as
#
E!%
2
" or
,
P !%
2
" 6ill
3e e0ually allo6ed 3ecause o. their component o.
#
E!%
2
"7 We see that the
apparent .ailure o. the selection rules is 3etter descri3ed as a .ailure in the correct
designation o. the states in/ol/ed7 The selection rules on one2electron matri elements
are al6ays rigorously o3eyed, in the a3sence o. pertur3ations, and the pro3lem lies
6ith our 4no6ledge o. the eact 6a/e.unctions o. the states in/ol/ed in the
transition7 At
should also 3e pointed out that the large S"C 6ill also cause the
#
P !s
#
%
#
" state
to
mi 6ith the
,
P !s
#
%
#
" 6hich may .urther complicate matters7 ". course, it
might 3e argued that in this case o. a high degree o. miing the situation 6ould 3e
clearP 3ut i. 6e mo/e across Digure 57? to the position o. tin, .or eample, 6e
Lnd that
D
2
=
2.%*- e8, V
=
0.2?0 e8 and H
=
5V ,D
2
=
0.*?7 The energy matri is then1
(+#
+
+#

+ (+#
+
0
+
+
(
+
#
+

+
#

+ 0 072?0
(
+
#
+
0
+
+ 072?0
27#*%
.or 6hich the mied 6a/e .unctions
#
E

!%
2
" or
,
P

!%
2
" are1
#
<

!%
2
" = 0.$$,
#
E!%
2
" + 0.##$
,
P !%
2
"
and
,
P

!%
2
" = 0.##$
#
E!%
2
" 0.$$,
,
P !%
2
"
Dor the tin atom, there.ore, it seems 0uite reasona3le to descri3e the states as
#
E!%
2
" and
,
P !%
2
", though 6e ha/e to recognise that the selection rules 6ill not
3e strictly o3eyed 3ecause o. the miing induced 3y S"C7 Dor germanium, .or
6hich
D
2
=
,.#52 e8, V
=
0.#0$ e8 and H
=
0.#- the miing is negligi3le and the limiting
LS selection rules should hold7
!ro3lems .or Chapter 5 #2$
At is 6orth noting that, although it is the S"C 6hich causes the miing o. states
o. di..erent multiplicity, the degree o. miing depends upon the energy2separation
3et6een the miing states and there.ore upon the inter2electronic repulsion7 An ger2
manium, though the miing o. states is /ery small, the S"C ma4es a measura3le
impact on the state energies through the diagonal matri element 6ith (
+
#
+
0
+
+7
Where only diagonal elements o. S"C are signiLcant in the comparison o. theory
and eperiment 6e spea4 o. Crst+order S"C7
RE6ERENCES
#7 '7=7 Condon and G797 Shortley, -he -heory of Atomic S%ectra, Cam3ridge =ni/ersity !ress,
#$,57
27 J7C7 Slater, 31ant1m -heory of Atomic Str1ct1re, 8ols7 A and AA, CcGra629ill, ;e6 Ror4,
#$?07
,7 :7<7 Co6an, -he -heory of Atomic Str1ct1re and S%ectra, Cali.ornia =ni/ersity !ress,
Ber4eley, #$%#7
!R285EMS 62R CHA!TER )
#7 !redict the .re0uencies and 6a/elengths o. a .urther series in the electronic spectrum
o. the hydrogen atom7
27 Calculate the 6a/elength o. the Lrst QBalmerG line in the spectra o. the deuterium atom
and the Be
,
+
cation7
,7 Sho6 that the num3er o. states, N
states
, in a conLguration l
%
, 6here l is the or3ital
angular momentum 0uantum num3er and % is the num3er o. electrons, is1
N
states
= 2lU,{%U !2l %"U}
9ence, conLrm the .act that there are #00# states o. f
*
ZnU = n!n #"!n 2" . . . #\
*7 <ra6 up a ta3le analogous to Ta3le 57* .or the conLguration sd and determine the
states o. the system7
57 <ra6 up a ta3le analogous to Ta3le 57? .or the conLguration sd 6ith && coupling and
determine the states o. the system7
?7 The normalised radial 6a/e .unctions .or the hydrogen atom are gi/en in Appendi 57
Sho6, using the .unctions .or n = ,, that although they are di..erent all those ha/ing
the same /alue o. n gi/e the same result .or the integral1


Oe
2
2

R
,l
!r "
*(? r
R
,l
!r "r
O
2
e
2
n
2
dr =
,2*(? a
.
0 0 0 0
This result tells us that the potential energy o. the electron is the same in all three
types o. d or3ital, despite the di..erences in their radial .unctions7 Because o. the /irial
theorem, this means that the 4inetic and total energies 6ill also 3e the same7 <etermine
the 4inetic and total energy o. a hydrogen ,d electron and compare your ans6er 6ith
'0uation (57#7#+7
-7 =se the in.ormation on s p transition pro3a3ilities in Bo 572 to conLrm the relati/e
intensities o. the spectral lines o. 3arium 0uoted in Section 57##7# and illustrated in
Digure 57-7
Chapter ?
T$e CoAalent C$emi#al 8on/
?70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #,2
?7# The 3inding energy o. the hydrogen molecule . . . . . . . . . . . . . . . . . . . . #,,
?72 The 9amiltonian operator .or the hydrogen molecule . . . . . . . . . . . . . . . #,*
?7, The Born I "ppenheimer approimation . . . . . . . . . . . . . . . . . . . . . . . . #,?
?7* 9eitler and London1 The /alence 3ond (8B+ model . . . . . . . . . . . . . . . . #,-
?75 9und and Culli4en1 the molecular or3ital (C"+ model . . . . . . . . . . . . . . #,$
?7? Ampro/ing the 6a/e .unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*0
?7?7# The /alue o. N . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*0
?7?72 !olarisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*0
?7- =niLcation1 Aonic structures and conLguration interaction . . . . . . . . . . . . #*#
?7% 'lectron correlation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*,
?7$ Bonding and anti3onding C"s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*5
?7#0 Why is there no 9eI9e BondJ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*?
?7## Atomic or3ital o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*?
?7##7# ' (sigma+ o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*-
?7##72 ( (pi+ o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*-
?7##7, ) (delta+ o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*%
?7##7* ;on23onding o/erlap . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #*%
?7#2 The homonuclear diatomic molecules .rom lithium to Ouorine . . . . . . . . . #*$
?7#, 9eteronuclear diatomic molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . #5#
?7#* Charge distri3ution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #5,
?7#5 9y3ridisation and resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #5,
?7#57# 9y3ridisation1 !auling #$,# . . . . . . . . . . . . . . . . . . . . . . . . . . #5,
?7#572 9y3ridisation and the /alence 3ond theory . . . . . . . . . . . . . . . . #5?
?7#57, 9y3ridisation o. car3on A"s . . . . . . . . . . . . . . . . . . . . . . . . . #5?
?7#57* The choice o. hy3rid or3itals . . . . . . . . . . . . . . . . . . . . . . . . . #?#
?7#575 The properties o. hy3rid2or3ital 3onds . . . . . . . . . . . . . . . . . . . #?2
?7#? :esonance and the /alence 3ond theory . . . . . . . . . . . . . . . . . . . . . . . . #?,
?7#- Colecular geometry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #?,
?7#-7# The /alence2shell electron2pair repulsion (8S'!:+ model . . . . . . #?*
?7#-72 The 8S'!: model and multiple 3onds . . . . . . . . . . . . . . . . . . . #?5
?7#% Computational de/elopments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #?-
?7#$ Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . #?%
!ro3lems .or Chapter ? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #-?
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
#,2 The Co/alent Chemical Bond
*1. INTR23UCTI2N
There can 3e no dou3t that the most important contri3ution o. 0uantum mechanics to the
science o. chemistry is the 6ay in 6hich it has ena3led us to understand the nature o. the
chemical 3ond, especially the co/alent 3ond7 The long and comple story o. the theory
o. /alency and the chemical 3ond 3e.ore the ad/ent o. 0uantum mechanics has 3een 6ell
told 3y !almer
#
and 3y :ussell
2
and 6ill not 3e repeated here7 We set the o3@ecti/es o.
this chapter 3y dra6ing .rom the Lrst .e6 pages o. a 3oo4 3y one o. the pioneers in the
application o. 0uantum mechanics to chemistry, Charles Al.red Coulson (#$#0 I #$-*+7
An his 3est2selling undergraduate tet, Q8alenceG,
,
Coulson discussed the ma@or
eperimental phenomena 6hich any /alid theory o. chemical 3onding must eplain7 9e
raised, in particular, the .ollo6ing 0uestions1
Why do molecules .orm at allJ Why is it that t6o hydrogen atoms .orm the /ery sta3le
diatomic molecule 9
2
6hile t6o helium atoms do not .orm 9e
2
J
Why is there saturation o. /alency, i7e7 i. 9
2
is sta3le, 6hy not 9
,
or 9
*
and so onJ
Similarly, 6hy do 6e ha/e C9
*
3ut not C9
5
or C9
?
J
What are the reasons .or the shapes o. moleculesJ Why, .or eample, is the car3on
dioide molecule (C"
2
+ linear 3ut sul.ur dioide (S"
2
+ 3ent, 6ith an " I S I "
3ond
angle o. ##$

J
Durther, the theory must lin4 the interpretations o. the a3o/e eperimental .acts together,
/ie6ing them as aspects o. a comprehensi/e theory o. chemical structure as a 6hole 6hich
(and here A add to CoulsonGs re0uirements+ should em3race not only co/alent compounds
3ut also ionic solids and metals7
An #$#$, Ca Born (#%%2 I #$-0+ and DritK 9a3er (#%?% I #$,*+ independently pu32
lished the energetic cycle, no6 4no6n as the Born I 9a3er cycle, 3y means o. 6hich
the energy o. an ionic lattice can 3e epressed in terms o. the properties o. the
elements .orming the lattice and the coulom3ic .orces 3et6een the ions in/ol/ed7 With
that 6or4 the essential .eatures o. the ionic 3ond 6ere 0uantitati/ely understood, though
it must 3e said that the ecellent agreement o. theory and eperiment is a little .ortuitous
due to the sel.compensating nature o. the ionic model, i7e7 the mutual cancellation o.
errors7
*
But the energetic 3asis o. the co/alent 3ond remained a complete mystery and its
eplanation 6as one o. the Lrst o3@ecti/es o. the ne6 0uantum mechanics7 At is amaKing
to note that, 6ithout the aid o. a computer or e/en an electronic calculator, 9eitler and
London produced a calculation o. the 3inding energy o. the hydrogen molecule in #$2-,
@ust one year a.ter the pu3lication o. SchroM dingerGs 6a/e e0uationU Though the
calculation 6as not 0uantitati/ely /ery accurate, 6ays in 6hich it might 3e impro/ed
6ere o3/ious and it 6as clear that 0uantum mechanics 6as on the right trac4 as .ar as
chemical 3onding 6as concerned7 By #$,,, a calculation o. the 3inding energy o. 9
2
correct to 3etter than
07? Y 6as reportedP a .ormida3le achie/ement 6hen 6e consider the compleity o. the
pro3lem, 6hich 6ill soon 3ecome apparent7 This 6or4 is descri3ed no6, gi/ing a roughly
chronological account o. the signiLcant steps in the application o. 0uantum mechanics
to the chemical 3ond in the hydrogen moleculeP this eempliLes almost all the essential
aspects o. the theory7 What it lac4s, the interpretation o. molecular geometry, i7e7 3ond
angles, is descri3ed in Section ?7#-7
The Binding 'nergy o. the 9ydrogen Colecule #,,
*1% THE 8IN3IN ENERY 26 THE HY3R2EN M25ECU5E
Be.ore em3ar4ing upon a discussion o. the calculation o. the 3ond energy o. 9I9, 6e
should 3e clear @ust 6hat is to 3e calculated and ho6 the result is to 3e compared 6ith
eperiment7 We Lrst recall (Section 57#+ that the Kero o. energy is, 3y deLnition, that state
in 6hich all particles, t6o electrons and t6o protons in this case, are inLnitely separated
and at rest so that they ha/e neither 4inetic nor potential energy7 A. 6e no6 allo6 t6o
hydrogen atoms to .orm at rest, the energy o. each atom lies #,7?05 e8 3elo6 the Kero o.
energy and 6e say that the electronic energy o. the hydrogen atom is #,7?05 e87 The
energy o. t6o 9 atoms is 2 #,.?05 = 2-.2#0 e8 (*,.5$? #0

#$
J+ (Digure ?7#P
note the t6o 3rea4s in the scale+7
A. the t6o hydrogen atoms approach su.Lciently close to each other to .orm a 3ond
then there is a .urther decrease in energy and there 6ill 3e a particular /alue o. the 9I9
internuclear distance .or 6hich the energy is a minimum, i7e7 is the most negati/e7 This
distance is 4no6n as the e0uili3rium internuclear distance, R
e
, and is .ound eperimentally
to 3e -*7# pm7 The corresponding eperimental energy is *7-*- e8 (-.?05?

#0

#$
J+
3elo6 the energy o. the t6o, non2interacting hydrogen atoms7 This is the energy 6hich 6e
shall see4 to calculate 3y determining the di..erence 3et6een the electronic energy o. t6o
independent hydrogen atoms and that o. the hydrogen (9I9+ molecule 6ith a 3ond length
o. R
e
7 The sym3ol .or this energy di..erence is E
e
7 Since 6e 4no6 the electronic energy
o. the hydrogen atom /ery accurately, .rom 3oth eperiment and theory, the pro3lem is
simply that o. calculating the electronic energy o. the molecule7
We emphasise the electronic energy 3ecause the molecule also has other .orms o.
energy that are not o. interest to us in the present contet7 At may, .or eample, 3e mo/ing
29
+
+ 2e
070 e8
2 A
9
= 2-72#0
e8
9 + 9
2-72#0 e8
<
0
= *7*-? e8
<
e
= *7-*- e8
9
2
,#7?%? e8
Kero2point energy = 072-# e8
,#7$5- e8
6ig;re *1% 'nergy le/els .or 29
+
+ 2e 29 and 9
2
#,* The Co/alent Chemical Bond
2 2 2
through space and rotating gi/ing rise to 4inetic energy contri3utions to its energy 6hich
6e do not re0uire in our current calculation7 The molecule 6ill also 3e /i3rating and
6e cannot ignore this Bero+%oint vi*rational energy (see Chapter #0 .or more details+
since it impinges upon the comparison o. theory 6ith eperiment7 'perimentally, the
energy re0uired to dissociate the hydrogen molecule into t6o hydrogen atoms is .ound
to 3e *7*-? e87 This is the energy E
0
P the energy re0uired to dissociate a real hydro2
gen molecule 6hich has Kero2point energy, as opposed to the theoretical /alue o. E
e
6hich is the dissociation energy o. an hydrogen molecule 6hich has no Kero2point energy
(Digure ?7#+7 Thus, the energy 6hich 6e see4 to calculate (E
e
+ is gi/en 3y the e0uation1
E
e
= E
0
+ Kero2point energy !?.#.#"
The Kero2point energy o. 9I9 is 4no6n .rom eperiment to 3e 072-# e8 so that,
eperimentally1
E
e
=
*.*-?
+
0.2-#
=
*.-*- e8 !?.#.2"
An the .ollo6ing 6e shall compare theoretical and eperimental /alues o. E
e
7
*1& THE HAMI5T2NIAN 2!ERAT2R
62R THE HY3R2EN M25ECU5E
Dollo6ing SchroM dingerGs method as in earlier chapters, our Lrst step must 3e to
6rite do6n an epression .or the energy o. the hydrogen molecule in classical terms7
9a/ing done that 6e then apply the rules .or con/erting the classical epressions to the
appropri2 ate operators7 A hydrogen molecule in 6hich the nuclei ha/e 3een la3elled A
and B and the electrons # and 2 is represented in Digure ?727 The .act that 6e ha/e so
la3elled the electrons and nuclei should not 3e ta4en to mean that 6e can actually
distinguish 3et6een t6o electrons or t6o nuclei7 ;othing could 3e .urther .rom the
truthP it is .undamental to 0uantum mechanics that all particles o. the same species are
totally indistinguisha3le7 The la3els are used only to ensure that 6e consider all the
possi3le terms in the 9amil2 tonianP the attraction 3et6een e/ery nucleus and e/ery
electron, .or eample7 With the aid o. Digure ?72 6e can identi.y the .ollo6ing energy
terms, their classical2mechanical epressions and the corresponding operators1
#7 The 4inetic energy o. the nuclei1
!5 V
A
"
2
!5 V
B
"
2
h ! + "
A B
25
+
27 The 4inetic energy o. the electrons1
25

(?727#+
%(
2
5
2
!mv
#
"
2
!mv
2
"
2

h
2
!

2
+
"
# 2
2m
+
2m

(?7272+
%(
2
m
,7 The potential energy due to nucleus2electron attraction1
e
2

# # # #

e
2

# # # #

(?727,+
*( ?
0 r
A#
+
r
B#
+
r
A2
+
r
B2

*( ?
0
r
A#
+
r
B#
+
r
A2
+
r
B2
*7 The potential energy due to internuclear repulsion1
e
2
#
e
2
#
!?.2.*"
*( ?
0

:
AB

*( ?
0

:
AB
The 9amiltonian "perator .or the 9ydrogen Colecule #,5
2
r
#2
#
r
A2
r
B2
r
A#
r
B#
A
:
AB
B
6ig;re *1& The 9amiltonian .or the hydrogen molecule
57 The potential energy due to interelectronic repulsion1
e
2
#
e
2
#
!?.2.5"
*( ?
0

r
#2

*( ?
0

r
#2
An these epressions e is the magnit1de o. the charge on the protons and the electrons,
m and 5 are the masses o. the electron and proton respecti/ely and ?
0
is the /acuum
permitti/ity7 The sym3ol
2
, 6hich is spo4en Qdel s0uaredG, is deLned 3y1
2 2 2
2 2 2 2
D ,D + D ,D y + D ,D K
!?.2.?"
"ur total 9amiltonian operator is there.ore the sum o. ten terms and 6e immediately
recognise that it is unli4ely that a solution o. SchroM dingerGs eigen/alue2
eigen.unction e0uation can 3e .ound, e/en .or this, the most simple o. molecules7
There.ore, i. the theory is to 3e applica3le, some 6ay, or 6ays, o. simpli.ying the pro3lem
must 3e .ound7 Such methods ha/e 3een .ound and the story o. the theory o. the
chemical 3ond since
#$2? is one o. Lnding approimate methods that ena3le us to dra6 out the essence o.
the 0uantum2mechanical description, e/en 6hen 6e are /ery .ar .rom Lnding an eact
solution o. SchroM dingerGs e0uation7 The .act 6e are una3le to sol/e SchroM dingerGs
e0uation
Qhead2onG so to spea4 is 3y no means a disaster as t6o eminent theoretical physicists,
'ugen !7 Wigner and Drederic4 SeitK, recognised in #$557 Their opening lines in a re/ie6
5
o. the theory o. the cohesion (3onding+ in metals read as .ollo6s1
QA. one had a great calculating machine, one might apply it to the pro3lem o. sol/ing the SchroM
dinger e0uation .or each metal and o3tain there3y the interesting physical 0uantities, such as the
cohesi/e energy, the lattice constant and similar parameters7 At is not clear, ho6e/er, that a great
deal 6ould 3e gained 3y this7 !resuma3ly the results 6ould agree 6ith the eperimentally determined
0uantities and nothing /astly ne6 6ould 3e learned .rom the calculation7 At 6ould 3e pre.era3le
instead to ha/e a /i/id picture o. the 3eha/iour o. the 6a/e .unctions, a simple description o. the
essence o. the .actors 6hich determine cohesion and an understanding o. the origins o. /ariation in
properties .rom metal to metal7G
A. 6e replace the 6ords metal, cohesi/e energy and lattice constant 3y molecule,
3inding energy and 3ond length respecti/ely, then this statement applies e0ually 6ell to
#,? The Co/alent Chemical Bond
'
n
e
r
g
y

(
e
8
+
(
W
i
t
h

r
e
s
p
e
c
t

t
o

i
n
.
i
n
i
t
e
l
y

s
e
p
a
r
a
t
e
d
,

s
t
a
t
i
o
n
a
r
y

p
r
o
t
o
n
s

a
n
d

e
l
e
c
t
r
o
n
s
+
'
n
e
r
g
y

#
0
#
$

(
J
+
(
W
i
t
h

r
e
s
p
e
c
t

t
o

l
o
6
e
s
t

e
l
e
c
t
r
o
n
i
c

e
n
e
r
g
y

o
.


9
2
+
the 0uantum2mechanical study o. molecules7 We no6 ha/e Qgreat calculating machinesG
6hich gi/e us much assistance in the application o. 0uantum mechanics, 3ut 6e are still
una3le to sol/e SchroM dingerGs e0uation in most cases o. chemical interest7 Wigner
and SeitKGs criteria remain as /alid today as they 6ere in #$55, and 6e shall 3ear them
/ery much in mind in this chapter7 And so to our Lrst simpli.ying approimation7
*1' THE 82RN I 2!!ENHEIMER A!!R2DIMATI2N
Ca Born and J7 :o3ert "ppenheimer (#$0* I #$?-+ 6ere among the Lrst to consider
the pro3lem o. applying SchroM dingerGs ne6 e0uation to molecules7 They recognised
that the mass o. the proton is #%,? times that o. the electron and that the nuclei there.ore
mo/e /ery much more slo6ly than the electrons7 Because o. this it should not 3e
necessary to treat 3oth types o. particle in eactly the same manner as the terms in our
9amiltonian operator a3o/e re0uire (compare '0uation (?727#+ 6ith '0uation (?7272+ and
'0uation (?727*+ 6ith '0uation (?7275++7 An #$2- they sho6ed 6ith a rigorous
mathematical analysis that only a /ery small error is introduced into the calculation
o. the electronic energy .or any particular internuclear distance (3ond length+ i. the
nuclei are held stationary at the 3ond length in 0uestion7 This remo/es the t6o nuclear
4inetic energy terms ('0uation (?727#++ .rom the 9amiltonian and the internuclear
repulsion 3ecomes a simple constant 6hich can 3e added in at the end7 The calculation
can then 3e repeated .or a num3er o. 3ond lengths and a graph o. 3ond length against
energy plotted in order to Lnd the minimum in the cur/e and the associated e0uili3rium
3ond length (R
e
+7
The type o. graph 6e epect to o3tain 3y this process is sho6n in Digure ?7,7 "n the
right o. the Lgure, 6here R is large, the cur/e o. energy against R is horiKontal7 This is
the region o. t6o non23onded hydrogen atoms 6here a change o. the internuclear distance
20 #2
#5
#%
#0
9
2 9 + 9
2*
5 E
e
E
0
,0
0
Nero2point energy
R
e
,?
50 #00 #50 200 250 ,00
Anternuclear distance (pm+
6ig;re *1' The hydrogen molecule1 energy vers1s internuclear distance
9eitler and London1 the 8alence Bond (8B+ Codel #,-
ma4es no di..erence to the electronic energy, 6hich is simply that o. the t6o hydrogen
atoms7 The energy at this point is 2-72#0 e8, as eplained in Section ?7#7
A. a sta3le molecule is to 3e .ormed, there must 3e a decrease in energy as 6e mo/e
to6ards smaller /alues o. R and this process 6ill continue until the mutual repulsion o.
the nuclei and o. the electrons 3egins to ma4e itsel. .elt and the energy 3egins to rise
againP normally 0uite steeply7 The energy di..erence 3et6een the minimum at R
e
and the
horiKontal cur/e at large R is E
e
and the 6hole cur/e can 3e constructed 3y calculating
the electronic energy o. t6o hydrogen atoms at a series o. /alues o. R7 The .act that 6e
are a3le to proceed in this 6ay, i7e7 the .act that the Born I "ppenheimer approimation
is such an ecellent one, has a signiLcance 6hich etends .ar 3eyond our present tas4 and
touches e/ery aspect o. chemistry7 "ne o. the most signiLcant ad/ances in chemistry in
the 20th century 6as the 6ay in 6hich 6e no6 thin4 o. molecules as three2dimensional
spatial entities7 The concept o. molecular shape and structure is no6 .undamental to our
understanding o. the 6ay in 6hich molecules interact and react chemically, and these
properties are also recognised to 3e /ital to ad/ances in su3@ects such as materials science
and molecular 3iology7 But i. the Born I "ppenheimer approimation could not 3e
made and the nuclei and electrons in a molecule had to 3e treated e/en2handedly,
then the motions o. the t6o sorts o. particles 6ould 3e inetrica3ly ent6ined7 And
there 6ould then 3e no 6ay in 6hich 6e could dra6 the comple structural .ormulae
upon 6hich 6e so much rely and 6hich are nothing more than representations o. the
e0uili3rium positions o. the nuclei o. the molecule7 A. the Born I "ppenheimer
approimation 6as not possi3le, then there 6ould also 3e no such thing as structural
chemistry as 6e 4no6 itU
8itally important though it is, the Born I "ppenheimer approimation still lea/es
us 6ith a lot o. 6or4 to do7 The 9amiltonian still contains se/en terms1
2 2 2
2

# # # # # #
h !
#
+
2
" e
9

=
(?7,7#+
%(
2
m

*( ?
0
r
A#
+
r
B#
+
r
A2
+
r
B2

r
#2

:
AB
and a direct solution o. the SchroM dinger e0uation is still impossi3le7
At this @uncture 6e recall the discussion, in Section *7$, o. the pro3lem o. calculating
an o3ser/a3le 0uantity .or a system 6hich is not in an eigenstate o. the appropriate
operator7 According to '0uation (,7$72+, a mean or epectation /alue o. the energy 6hich
6e re0uire can 3e .ound .or a normalised trial 6a/e .unction ( + using the e0uation1

E =

9

dv
#
dv
2
!?.,.2"
;ote that, since 6e no6 ha/e t6o electrons to consider, 6e ha/e to integrate o/er the
three spatial coordinates o. 3othP a total o. si integrations7 This is not a tri/ial calculationU
But, although 6e ha/e the 9amiltonian operator, 6e ha/e no 6a/e .unction7 9o6 can
6e proceedJ
*1( HEIT5ER AN3 52N32N: THE VA5ENCE 82N3 FV8G M23E5
An the Lrst success.ul calculation o. the energy o. a co/alent 3ond, Walter 9eitler
(#$0* I #$%#+ and DritK London (#$00 I #$5*+ proposed that an approimate 6a/e
.unction could 3e o3tained .rom our 4no6ledge o. the 6a/e .unctions o. the hydrogen
atom in the .ollo6ing manner7 We Lrst suppose that our t6o hydrogen atoms are .ar apart
6ith electron # in $
A
, the normalised #s atomic or3ital around nucleus A, and electron 2
in $
B
,
#,% The Co/alent Chemical Bond
James and CoolidgeP #,2term .unction *7-2 -75? -*70
>olos and :oothaanP 502term .unction *7-*?- -7?0*- -*7#
d
'perimental /alues *7-*?% -7?0*% -*7#
07000- 0700#
R
the #s or3ital around nucleus B7 The 6a/e .unction, G , .or this system o. t6o separated
hydrogen atoms 6ill 3e1
G
=
$
A
!#"

$
B
!2" !?.*.#"
;ote that the t6o #s .unctions are com3ined as a product 3ecause each is a pro3a3ility
.unction and the pro3a3ility o. t6o e/ents ta4ing place is the %rod1ct o. the pro3a3ilities
o. each o. the indi/idual e/ents ta4ing place7
;o6 imagine that the t6o atoms mo/e close enough together to .orm a 3ond7 Then 6e
might assume, to a Lrst approimation, that the a3o/e 6a/e .unction remains /alid7 This
is 6hat 9eitler and London suggestedP 3ut 6ith one important addition7 When the t6o
atoms .orm a 3ond the electrons occupy a common region o. space and can no longer
3e thought o. as conLned to one particular nucleus7 Durthermore, it is .undamental to the
0uantum theory that electrons are indistinguisha3le7 Thus, the alternati/e 6a/e .unction1
G = $
B
!#" $
A
!2" !?.*.2"
is e0ually suita3le, and .or a correct description o. the molecule 3oth are re0uired1

/3
= ;{$
A
!#" $
B
!2" + $
B
!#" $
A
!2"} !?.*.,"
We should also note that 6hen the t6o hydrogen atoms are 3rought together so that
the electrons occupy a common region o. space, then the !auli principle re0uires that the
spins o. the electrons must 3e paired and the a3o/e 6a/e .unction represents the interac2
tion o. t6o hydrogen atoms 6ith opposite electron spins7 The inter2relationship 3et6een
the spin and the spatial distri3ution o. electrons raises many etremely important 0ues2
tions 3ut, .ortunately, 6e need only the spatial parts o. the 6a/e .unctions .or our present
Ta?le *1% A summary o. some o. the calculations on the hydrogen molecule
Type o. 6a/e .unction E
e
a
*
e
He8 ,J #0

#$
Hpm
Simple /alence 3ond (N = #+ ,7#* 570, %?7$
Simple molecular or3ital (N = #+ 27?% *72$ %570
8B 6ith N = #.#?? ,7-% ?70? -*7,
C" 6ith N = #.#$- ,7*$ 575$ -,72
8B + polarisation (N = #.#-, N = 0.#2,+ *702 ?7** -*70
H!co/alent" + <H !ionic" !< 0.25" *705 ?7*$ -*7$
Best calculation 6ithout eplicit inclusion o.
electron correlation
*72- ?7%* -*70
c
a
<issociation energy per molecule
*
'0uili3rium 3ond length
c
Calculated .or this /alue o. : only7
d
An #$?%, >olos and Wolnie6icK reported a calculation using a #002term .unction7
Generally, 3ut not al6ays 3ecause o. the hea/y calculations in/ol/ed, each successi/e, impro/ed calculation
incorporates the impro/ements made in earlier 6or47 An etensi/e re/ie6 o. the early calculations on the
hydrogen molecule may 3e .ound in the paper 3y A7<7 CcLean, A7 Weiss and C7 Roshimine, Rev. 5od. Phys.,
'&, 2## (#$?0+7
9und and Culli4en1 the Colecular "r3ital (C"+ Codel #,$
purposes so, .or the moment, 6e postpone the additional complication o. spin7 "ne aspect
o. the space2spin pro3lem is eplored in Bo ?7* and the su3@ect is discussed more thor2
oughly in Section ##757 The .actor ; has 3een introduced to normalise the 6a/e .unction
'0uation (?7*7,+ (Bo ?7#+7 Anserting the 6a/e .unction
/3
into '0uation (?7,72+ ena3led
9eitler and London to calculate the epectation /alue o. the energy, E, and 3y /arying R,
to Lnd an energy minimum and a /alue .or the e0uili3rium 3ond length o. the hydrogen
molecule7 The calculated energy o. ,7#* e8 and 3ond length o. %?7$ pm do not compare
/ery 6ell 6ith the eperimental /alues o. *7-* e8 and -*7# pm (Ta3le ?7#+7 9o6e/er, the
result represented an enormous ad/ance on the pre/ious position and, moreo/er, it 6as
immediately clear ho6 the 6a/e .unction could 3e reLned, there3y impro/ing the result7
But 3e.ore 6e consider the possi3le impro/ements 6e should introduce another .orm o.
6a/e .unction, a concept 6hich 6as suggested 3y Driederich 9und (#%$? I + and
:o3ert Sanderson Culli4en (#%$? I #$%?+ among others7
*1) HUN3 AN3 MU55I=EN: THE M25ECU5AR 2R8ITA5
FM2G M23E5
9und and Culli4en approached the pro3lem o. Lnding a suita3le 6a/e .unction .or 9I9
in a rather di..erent 6ay7 The solutions o. SchroM dingerGs e0uation .or the hydrogen
atom, the atomic or3itals, may 3e regarded as regions o. space 6hich can 3e occupied
3y one or t6o, 3ut not more, electrons7 9und and Culli4en suggested that one might
en/isage similar regions o. space surrounding not one 3ut t6o (or more+ nuclei7 These they
called molecular or3itals and .or the hydrogen molecule they suggested the .ollo6ing
.orm1
G
mo
= ;

{$
A
+ $
B
} !?.5.#"
There are important points to 3e made a3out this 6a/e .unction7 The .actor ;

is again
a normalising constant (Bo ?7#+7 The atomic or3ital .unctions are the normalised #s .unc2
tions o. nuclei A and B as 3e.oreP 3ut note that there is, as yet, no mention o. the electrons7
At is .or this reason that 6e ha/e a sum o. the t6o .unctions rather than a product7 At this
stage 6e are concerned merely to esta3lish a .orm .or the molecular or3ital 6hich 6e
shall later populate 6ith t6o spin2paired electrons7 As 6ith the 9eitler I London
.unction, the 9und I Culli4en .unction ('0uation (?757#++ is an approimation7 The
@ustiLcation .or its .orm is solely that 6e 4no6 that the .unctions $
A
and $
B
are the eact
atomic or3itals an electron occupies 6hen it is in the region o. a single hydrogen
nucleus, remote .rom all other atoms7 9und and Culli4enGs .unction simply assumes that
this remains the case 6hen t6o such atoms approach to 6ithin 3onding distance7 The
calculation 6ill sho6 @ust ho6 /alid this assumption is7 We must no6 introduce the
electrons into our molecular or3ital7 Both can 3e accommodated in the one or3ital i.
they ha/e opposite spins and 6e 6rite1

mo
=
G
mo
!#"

G
mo
!2" !?.5.2"
The calculation 6ith the 9und and Culli4en .unction gi/es a 3inding energy o. 27?% e8
and a 3ond length o. %570 pm (Ta3le ?7#+7 This result is mar4edly in.erior to that o. 9eitler
and London, 3ut the molecular or3ital method o. o3taining a 6a/e .unction has pro/ed to
3e one o. the most .ruit.ul concepts in the application o. 0uantum mechanics to chemical
pro3lems, as 6e shall see7
#*0 The Co/alent Chemical Bond
*1* IM!R2VIN THE 4AVE 6UNCTI2NS
The results o. the early calculations 6ere /ery encouraging, 3ut it 6as clear that impro/e2
ments 6ere re0uired and directions 6hich these should ta4e 6ere rapidly recognised7 The
Lrst impro/ements suggested .or 3oth 6ere the same and they are important not only
3ecause they gi/e 3etter numerical results .or the calculation o. the 9I9 3inding energy,
3ut also .or the physical insight 6hich they 3ring to the pro3lem7 But 3e.ore 6e em3ar4
upon a 3rie. description o. that 6or4 6e need to address an important pro3lem1 6hat is
the criterion 3y 6hich 6e shall @udge the impro/ement, or lac4 o. itJ
The o3@ect o. the calculation is to determine the energy o. the hydrogen molecule 6hich
lies mar4edly lo6er than the simple calculations predict, i7e7 the calculated /alue o. E
e
is
smaller than the eperimental /alue7 At seems natural, there.ore, to suggest that the lo6er
our calculated energy the 3etter the 6a/e .unction7 But is there not a danger that 6e
might choose a 6a/e .unction that predicts an energy lo6er than the eperimental /alue,
and 6hat 6ould such a result implyJ Dortunately, this dilemma 6ill not trou3le us7 A
theorem 4no6n as the /ariation theorem, 6hich is pro/ed and applied to another pro3lem
in Appendi 2, sho6s that no legitimate 6a/e .unction .or any 0uantum2mechanical
pro3lem can gi/e an energy 6hich is less than the true lo6est energy eigen/alue o. the
system 6hich it descri3es7 There.ore, 6e can modi.y our C" and 8B 6a/e .unctions in
any reasona3le 6ay, conLdent that the closer 6e get to the eperimental energy the 3etter
is our calculation and the 6a/e .unction used7
*1*1% T$e Aal;e o" :
An the isolated hydrogen atom the electron mo/es under the electrostatic attraction o. a
single nucleus, 3ut in the molecule it mo/es in the Leld o. t6o nuclei7 Though it may not
.eel t6ice the attracti/e .orce 6hich it does in the atom, on account o. the screening e..ect
o. the other electron and the .act that the t6o nuclei are not coincident, it is, ne/ertheless,
to 3e epected that an electron 6ill 3e dra6n in more closely to the t6o nuclei than it is
in the atom7 9o6 can this 3e allo6ed .or in the 6a/e .unctionJ
The alge3raic epression .or the normalised #s atomic or3ital (A"+ o. the hydrogen
atom is (Appendi 5+1
#
$
=
(
,

N

2
a
0
ep

Nr

a
0
!?.?.#"
9ere, a
0
is the Bohr radius, r is the distance 3et6een the electron and the proton and N
represents the charge on the nucleus in units o. the charge on the proton7 An the isolated
hydrogen atom N = #7 At 6as suggested 3y S7C7 Wang that the increase in the attraction
to the nuclei .elt 3y electrons in the hydrogen molecule as opposed to the hydrogen atom
implied an increase in the /alue o. N, 6hich 6ould ha/e the e..ect o. dra6ing the A"s $
A
and $
B
a little closer around their respecti/e nuclei7 An #$2% detailed calculations sho6ed
that increasing N did indeed produce impro/ed /alues o. E
e
and R
e
(Ta3le ?7#+ and the
3est /alues o. N 6ere .ound to 3e #7#?? and #7#$- .or the 8B and C" 6a/e .unctions
respecti/ely7
*1*1& !olarisation
An #$,#, ;7 :osen noted that the presence o. another nucleus at the side o. each #s A"
6ould 3e epected to distort that A" .rom the pure spherical shape it 6ould ha/e in
F

(
a
0
+
=niLcation1 Aonic Structures and ConLguration Anteraction #*#
,
2
07#0
#
0720
07,0
0
0725
#
07#5
2
0705
,
, 2 # 0 # 2 ,
N (a
0
+
6ig;re *1( !olarisation o. the hydrogen #s A" 3y addition o. 2p
K
an isolated atom7 9e proposed that this e..ect could 3e allo6ed .or 3y 3uilding a 8B
or C" 6a/e .unction .rom a composite atomic 6a/e .unction centred on each nucleus7
The ma@or contri3utor to the .unction 6ould 3e the #s A" as 3e.ore, 3ut there 6ould 3e
a small addition o. a 2p A" pointing in the direction o. the other nucleus7 ;eglecting
normalising .actors and choosing the K2direction as the internuclear ais, the polarised
atomic .unction, $

, 6ould 3e o. the .orm1
$

= Z$
#s
+ N $
2p
K
\ !?.?.2"
N is simply a num3er 6hich, in accordance 6ith the /ariation theorem, is to 3e /aried
until the lo6est energy (greatest 3inding energy+ is .ound7 Because or3itals ha/e a phase,
the positi/e com3ination o. a #s and a 2p
K
or3ital produces a .unction 6hich has a larger
electron pro3a3ility in the positi/e K2direction than in the negati/e7 Thus, the electron
density is no longer spherically symmetrical 6ith respect to the nucleus 3ut is polarised
in the positi/e K2direction 6hich is @ust 6hat 6e re0uire7 The distortion is illustrated in
Digure ?7* .or N = 0.#57 The other 9 atom can 3e polarised in the negati/e K2direction
3y .orming the negati/e com3ination o. #s and 2p
K
7 :osen carried out a calculation 3ased
on the 8B 6a/e .unction plus polarisation and .ound the impro/ed /alues o. E
0
and R
e
sho6n in Ta3le ?7#7 The 3est /alue o. N 6as 07#2, (#75 Y o. $
2p
K
+ .or N
=
#.#-7
*1+ UNI6ICATI2N: I2NIC STRUCTURES
AN3 C2N6IURATI2N INTERACTI2N
The impro/ements in the 6a/e .unction suggested 3y Wang and :osen ha/e a /ery clear
physical 3asis in the mutual electrostatic attraction o. positi/e and negati/e charges7 They
sho6 us that, e/en in the realms o. 0uantum mechanics, simple electrostatic reasoning can
still 3e applied 6ith /ery 3eneLcial results7 An .act, as 9ellmann and Deynman indepen2
dently pro/ed, 6e re0uire SchroM dingerGs e0uation to determine the electron
distri3ution
#*2 The Co/alent Chemical Bond
in a 0uantum2mechanical system 3ut once 6e ha/e that distri3ution 6e can calculate the
potential energy using classical electrostatics7
9o6e/er, in spite o. the great success o. the theory thus .ar, 6e are still some 6ay .rom
the le/el o. agreement 3et6een theory and eperiment 6hich 6e re0uire to pro/e that
0uantum mechanics is the theory 6hich interprets the chemical 3ond 0uantitati/ely7 And
more importantly, 6e ha/e t6o models, the C" and the 8B7 The t6o di..erent methods
cannot 3e simultaneously correct unless they can 3e sho6n to 3e di..erent .ormulations
o. the same theory7 An #$,, S7 Wein3aum 3rought the C" and 8B approaches together
in the .ollo6ing manner 6hich, again, has a strong 3asis in simple physical2chemical
reasoning7
We Lrst 6rite out the simple 8B .unction o. 9eitler and London ('0uation (?7*7,++,
neglecting the normalising constants1

/3
= $
A
!#" $
B
!2" + $
B
!#" $
A
!2" !?.-.#"
The simple, un2normalised C" 6a/e .unction ('0uation (?7#*++ is1

mo
= Z$
A
+ $
B
\!#" ZZ$
A
+ $
B
\!2"
Z$
A
!#" + $
B
!#"\ Z$
A
!2" + $
B
!2"\ (?7-72+
At can 3e multiplied out in eactly the same 6ay as the product o. t6o 3rac4ets in
alge3ra gi/ing .our terms1

mo
= $
A
!#" $
A
!2" + $
B
!#" $
B
!2" + $
A
!#" $
B
!2" + $
B
!#" $
A
!2"
(?7-7,+ We note that the last t6o terms o. this .unction are eactly the same as those
o. the
8B .unction 6ith the electrons in di..erent A"s, 6hile the Lrst t6o terms ha/e either
3oth electrons in the A" $
A
or 3oth in $
B
7 The physical meaning o. the /arious terms
is clear7 Those contri3utors to the 6a/e .unction in 6hich 3oth A"s are occupied 6ith
one electron each distri3ute the t6o electrons o/er the molecule as one 6ould epect in
a co/alent 3ond7 The other t6o terms place 3oth electrons in the region o. one nucleus
so that the molecule is negati/ely charged at one end and positi/ely charged at the other7
This is an ionic structure, 9
+
I9

, and 6e see that the C" 6a/e .unction consists o.

ionic and co/alent structures in e0ual proportions ('0uation (?7-7*++1

mo
= H !co/alent" + H !ionic" !?.-.*"
6hereas the 8B 6a/e .unction has only co/alent structures7 Drom our 4no6ledge o.
chemistry, 6e do not epect ionic 3onding to play a /ery important role in the structure
o. 9I9, though it may 6ell do so in the case o. a molecule such as 9ID, 6here there
is a large di..erence in the electronegati/ities o. the t6o atoms in/ol/ed7 At there.ore
seems li4ely that the C" theory o/er2emphasises the importance o. ionic contri3utions
to the 3onding and it might 6ell impro/e the 6a/e .unction i. a 6ay could 3e .ound
o. reducing the importance o. these ionic terms7 An the same /ein, although 6e epect
the contri3utions o. the ionic terms to the 3onding to 3e small, it 6ould impro/e the
8B .unction i. 6e could add a small proportion o. ionic structures to the purely co/alent
description 6hich 6e currently ha/e7 Wein3aum did this 3y 6riting the 8B 6a/e .unction
as a sum o. co/alent and ionic terms in the .orm1

/3
= H !co/alent" + <H !ionic" !?.-.5"
'lectron Correlation #*,
and /arying < to Lnd the maimum E
e
7 The /alue o. < .ound 6as in the region o. 0725,
the eact Lgure 3eing determined 3y the /alues o. the other /aria3le parameters in/ol/ed,
i7e7 N and N 7 At should 3e noted that this is a /ery hea/y calculation indeed, in that the
e..ects o. screening and polarisation ha/e also to 3e considered since the /alues o3tained
.rom earlier calculations cannot 3e ta4en o/er unchanged into a di..erent 6a/e .unction7
We sa6 this earlier 6hen t6o di..erent /alues o. N 6ere .ound .or the C" and 8B 6a/e
.unctions (Section ?7?7#+7
At this point it is natural to as4 6hat change might 3e made to the C" 6a/e .unction
to impro/e it 3y reducing the contri3ution o. the ionic terms7 The ans6er lies in the
out2o.2phase com3ination o. the hydrogen #s atomic or3itals 6hich, as 6e shall see in
Section ?7$, represents a higher energy state o. the hydrogen molecule7 We place the t6o
electrons in this higher2energy C" 6ith the t6o spin2paired electrons eactly as 6e did
in '0uation (?7-72+ and 6rite the simple, un2normalised C" 6a/e .unction,

mo
, as1

mo
= Z$
A
$
B
\!#" ZZ$
A
$
B
\!2"

Z$
A
!#"

$
B
!#"\

Z$
A
!2"

$
B
!2"\ (?7-7?+
At can 3e multiplied out in the same 6ay as 3e.ore gi/ing1

mo
= $
A
!#" $
A
!2" + $
B
!#" $
B
!2" $
A
!#" $
B
!2" $
B
!#" $
A
!2"
(?7-7-+ We see immediately that the co/alent terms no6 carry a negati/e sign so
that in a
com3ined C" 6a/e .unction, , o. the .orm1
=
mo
T

mo
!?.-.%"
The /alue o. T can 3e used to decrease the contri3ution o. the ionic terms @ust as < 6as
used in the 8B 6a/e .unction ('0uation (?7-75++ to increase it7 The procedure 6here3y a
6a/e .unction is impro/ed 3y the addition o. another arrangement o. electrons in or3itals,
i7e7 another conLguration, is 4no6n as conCg1ration interaction7 The 8B 6a/e .unction
6ith the addition o. ionic terms and the C" 6a/e .unction 6ith conLguration interaction
can 3e made identical 6ith suita3ly chosen /alues o. < and T7 With Wein3aumGs 6or4
uniLcation 6as complete and the t6o approaches to the pro3lem had con/erged, as they
must do i. they are descri3ing the same truth7 But the calculated /alue o. E
e
6as still
only %5 Y o. the eperimental /alue and this 6as not good enough to pro/e that 0uantum
mechanics pro/ides a 0uantitati/e description o. the co/alent 3ond7 Something more 6as
re0uired and it 6as pro/ided 3y 97C7 James and A7S7 Coolidge 6ho recognised the
pro3lem o. electron correlation7
*1, E5ECTR2N C2RRE5ATI2N
An reLning the 6a/e .unctions used to descri3e the hydrogen molecule, :osen realised
that the presence o. nucleus A 6ould polarise (distort+ the spherically symmetrical #s
electron distri3ution around nucleus B and /ice /ersa (Digure ?7*+7 This is essentially a
static distortion, 3ut there is another, dynamic distortion process that is caused 3y the
mutual repulsion o. the t6o electrons, 6hich there.ore mo/e in such a 6ay as to reduce
this repulsion7 They a/oid each other7 This e..ect upon their motion is 4no6n as electron
correlation7 James and Coolidge sho6ed that this e..ect must 3e eplicitly allo6ed .or, not
@ust in the 9amiltonian operator as in '0uation (?7,7#+, 3ut also in the 6a/e .unction itsel.7
#** The Co/alent Chemical Bond
'
l
e
c
t
r
o
n
s

p
e
r

=
n
i
t

L
e
n
g
t
h

(
e
H
a
0
+
An a .ormida3le calculation, 6ithout the aid o. a computer and using a 6a/e .unction that
6as the sum o. #, terms, they o3tained E
e
= *.-2 e8 and R
e
= -*.0 pm7 This /alue o.
E
e
is $$7* Y o. the eperimental /alue and this impressi/e result le.t little room .or dou3t
concerning the applica3ility o. 0uantum mechanics to the pro3lem o. the chemical 3ond7
An #$?0 >olos and :oothaan repeated the James and Coolidge calculation 6ith a
502term .unction and o3tained a result that agrees 6ith eperiment to 6ithin eperimen2
tal accuracy (Ta3le ?7#+7 An .act, the result is 3etter than it should ha/e 3een 3ecause
the Born I "ppenheimer approimation, though good, is not that good7 The
eceptional agreement o. theory and eperiment is attri3uted to a .ortunate cancellation o.
the small errors due to the Born I "ppenheimer approimation in this particular
pro3lem7 An /ery recent years calculations 6hich do not in/o4e the Born I "ppenheimer
approimation at all ha/e 3een carried out7 The results completely conLrm the positi/e
conclusions a3o/e and today 6e do not dou3t that 0uantum mechanics pro/ides a
0uantitati/e theoretical model o. the chemical 3ond in all its .orms7
But as Wigner and SeitK so clearly recognised, a 6a/e .unction composed o. 50 terms is
not a /ery /isual thing and 6e need a more pictorial description o. the 3ond7 An Digure ?75
6e attempt to pro/ide this picture7 The horiKontal ais o. the Lgure runs through the t6o
hydrogen nuclei 6hich are sho6n as t6o dots at

0.-0 a
0
7 The /ertical ais gi/es the
num3er o. electrons that can 3e .ound 6ithin a disc o. inLnite radius and # a
0
thic4 at right2
angles to the internuclear ais7 The continuous lines are the graphs .or the A"s $
A
and
$
B
centred on the t6o protons as they 6ould 3e i. there 6ere no interaction 3et6een the
t6o hydrogen atoms7 The area under each graph is e0ui/alent to one electron7 The dotted
line is the graph corresponding to the most simple C" 6a/e .unction ('0uation (?7#7#*++
3ut multiplied 3y t6o so that the area 3eneath it is e0ui/alent to t6o electrons and is
there.ore directly compara3le 6ith the sum o. the areas under the t6o A" plots7 We see
that the electron density in the 3onding C" is greater in the internuclear region than the
sum o. the t6o A" densities7 This is a direct result o. the .act that the electron density is
gi/en 3y the s0uare o. the 6a/e .unction so that !$
A
+
$
B
"
2
is greater than !$
A
"
2
+
!$
B
"
2
3ecause o. the presence o. the cross2term, 2$
A
$
B
, in the .ormer7 The increased electron
density in the internuclear region dra6s the nuclei together and is the primary cause o. the
07%
07?
07*
072
070
? * 2 0 2 * ?
Anternuclear Ais (a
0
+
6ig;re *1) 'lectron distri3ution in the 3onding molecular or3ital o. the hydrogen molecule
'
l
e
c
t
r
o
n
s

p
e
r

=
n
i
t

l
e
n
g
t
h

(
e
H
a
0
+
Bonding and Anti3onding C"s #*5
9I9 3ond7 9ere again 6e see that, once 0uantum mechanics has 3een used to determine
electron distri3ution, 6e can understand the .orces acting 3et6een the /arious particles
.orming a molecule using classical electrostatics7 :ecall at this point that the data 6e
ha/e plotted are dra6n .rom the most simple C" 6a/e .unction, 6hich gi/es a rather
poor 3inding energy7 Allo6ing .or the polarisation o. the 3asic #s A"s and a reduction
in importance o. the ionic terms, as descri3ed a3o/e, increases the di..erence 3et6een the
C" electron density and the sum o. the t6o A" densities in the internuclear region and
outside it7
*1- 82N3IN AN3 ANTI82N3IN M2s
An the a3o/e interpretation o. the origin o. the co/alent hydrogen 3ond 6e noted that,
as a result o. the cross2term +2$
A
$
B
, 6hich arises .or the C" 6a/e .unction ('0ua2
tion (?757#++, there 6as a 3uild2up o. electronic charge 3et6een the t6o protons7 But i.
6e had chosen to .orm a molecular or3ital 3y ta4ing the A" com3ination $
A
$
B
, 6e
6ould ha/e .ound a negati/e cross2term, 2$
A
$
B
, and a conse0uent dimunition o. charge
in the internuclear region7 Let us call these t6o possi3ilities G
+
and G

i7e71
G
+
= ;
+
{$
A
+ $
B
} (?757#a+
G

= ;

{$
A
$
B
} (?7$7#+
But 6hy should 6e e/en consider the possi3ility o. com3ining the t6o A"s 6ith
opposite signs, i7e7 o. ta4ing the out2o.2phase com3inationJ There is more than one ans6er
to this 0uestion, 3ut one o. the most important is that such an C" is 4no6n .rom
eperiment to eist7 When the hydrogen molecule is irradiated 6ith light o. a 6a/elength
in the region o. ##0 nm ($

#0
%
cm

#
+ it a3sor3s that light and is ecited to a higher
energy state that has 3een sho6n 3y spectroscopic studies to 3e a state in 6hich the C"
G
+
contains one electron and the C" G

one electron7
A graph o. the C" G

o. the same .orm as Digure ?75 is sho6n in Digure ?7?7 We no6
ha/e a situation in 6hich the electron density in the internuclear region is much reduced
07%
07?
07*
072
070
? * 2 0 2 * ?
Anternuclear Ais (a
0
+
6ig;re *1* 'lectron distri3ution in the anti3onding C" o. the hydrogen molecule
#*? The Co/alent Chemical Bond

(3ecause o. the negati/e cross2term+ compared 6ith the sum o. the t6o A" densities7
Andeed, since the A"s are com3ined 6ith opposite phases, the electron density must 3e
eactly Kero mid26ay 3et6een the nuclei7 C"s o. this type are called anti3onding C"s
since electrons occupying them cause the atoms to separate rather than to .orm a 3ond7
This means that molecules 6ith electrons in anti3onding or3itals are unsta3le and reacti/e
and they .re0uently decompose or enter into chemical reactions7 The a3sorption o. light is
the most common cause o. electrons entering anti3onding C"s and the chemical reactions
6hich then ensue are called photochemical reactions7 The most important photochemical
reaction is the process o. photosynthesis 6hich ta4es place in green plants7 Another
important, 3ut less 3eneLcial, one is the primary reaction in the se0uence 6hich generates
photochemical smog1
;"
2
!gas" + h> ;"(gas+ + "(gas+
*1%. 4HY IS THERE N2 HEIHE 82N37
When 6e recognise that anti3onding as 6ell as 3onding C"s eist, an eplanation o. the
.act that there is no helium (9eI9e+ molecule is /ery clear7 Consider the energy le/el
scheme (Digure ?7-(3++, 6hich is 0ualitati/ely the same as that .or 9I9 (Digure ?7-(a++,
apart .rom the .act that 6e no6 ha/e .our electrons to 3e placed in the a/aila3le C"s7
Both 3onding and anti3onding C"s are no6 .ull and 3onding and anti3onding .orces are
0uite e/enly 3alanced7 An .act, more sophisticated calculations sho6 that the anti3onding
eceeds the 3onding and no sta3le helium molecule can 3e .ormed7
*1%% AT2MIC 2R8ITA5 2VER5A!
An the last section, the sign and magnitude o. the cross2term generated 6hen a C" 6a/e
.unction is s0uared 6as seen to 3e a /ery important criterion in the description o. a
co/alent 3ond7 A large positi/e term places a large electron density 3et6een the nuclei
dra6ing them to6ards it to .orm a 3ond, 6hile a large negati/e term remo/es electron
density .rom 3et6een the nuclei 6hich then ha/e nothing to pull them together7 :ather,
the mutual repulsion o. their positi/e charges, lac4ing the screening o. an intermediate
electron cloud, dri/es the nuclei apart7
The nature o. the cross2term is such that it only has a /alue in those regions o. space
6here 3oth $
A
and $
B
each ha/e a signiLcant /alue, i7e7 in the region 6here the t6o
A"s overla%7 Dor this reason 6e call $
A
$
B
an or3ital o/erlap and it plays a central role
Anti23onding s
molecular or3ital
;on2interacting 9

#s atomic or3itals

Anti23onding s
molecular or3ital
;on2interacting 9e

#s atomic or3itals

(a+
Bonding s molecular
or3ital

(3+
Bonding s molecular or3ital
6ig;re *1+ Colecular or3ital energy2le/el schemes .or 9
2
and 9e
2
Atomic "r3ital "/erlap #*-
in 0ualitati/e discussions o. 3onding in 3oth diatomic and polyatomic molecules7 Apart
.rom its sign, the o/erlap is characterised 3y its symmetry 6ith respect to rotation a3out
the internuclear ais in the .ollo6ing 6ay7
*1%%1% ' FsigmaG oAerlap
' o/erlap is cylindrically symmetrical 6ith respect to rotation a3out the internuclear ais
(Digure ?7%(a++7 That is, i. 6e /ie6 the 3ond .rom one end along the internuclear ais then
a rotation o. the molecule causes no apparent change in 6hat 6e see7 Both the positi/e and
the negati/e $
A
$
B
o/erlap in the hydrogen molecule are o. this type and 6e distinguish
them 3y using a

to indicate the anti3onding o/erlap7 We also add in.ormation a3out the
atomic or3itals in/ol/ed in the o/erlap and spea4 o. ' (#s+ and ' (#s+

o/erlap or '
(#s+
3onds and ' (#s+

anti3onds7
Cylindrically symmetrical o/erlap can also arise 6hen p2A"s o/erlap 6ith s2A"s
or 6ith other p2A"s, as illustrated in Digure ?7%(a+7 Typical descriptions o. this type
o. o/erlap are ' (#s22p+ or ' (2p+

7 Generally, since it is strongly directed along the

internuclear ais, ' o/erlap produces the strongest 3onds and the strongest anti3onds7
That is, the decrease in energy 6hen a ' 3ond is .ormed is larger than 6hen other
types o. 3onds are .ormed and the increase in energy 6hen a '

anti3ond is .ormed is
correspondingly greater7
*1%%1& ( FpiG oAerlap
When t6o A"s o/erlap in such a 6ay that rotation a3out the internuclear ais produces
a change o. sign e/ery #%0

then the o/erlap is termed ( o/erlap (Digure ?7%(3++7 A
s o/erlap
+ +
+
+
s (#s2#s+ s (#s2#s+S
s (#s22p+S

+ +
+ +
s (2p22p+ s (2p22p+S
(a+
p o/erlap
+ +
+
+ +

+ +
p (2p22p+ p (2p22p+S p (2p2,d+
(3+
6ig;re *1, ' ( ) and non23onding A" o/erlap
#*% The Co/alent Chemical Bond
y
d o/erlap
d (,d2,d+
(c+
d (,d2,d+S
non23onding o/erlap
+
+ +

+

(#s22p+ (2p22p+
(d+
;ote1 An Digure ?7%(c+ shading has 3een used to indicate phase in order to ma4e
the relati/e positions and orientations o. the t6o d

y
2
or3itals clear7
6ig;re *1, (contin1ed +
good eample is the o/erlap o. t6o 2p2A"s 6hich are orientated at right2angles to the
internuclear ais, as in the car3on2car3on ( 3ond in ethene7 The

to denote anti3onding
is also used and in ethene 6e ha/e ( (2p+ 3onding and ( (2p+

anti3onding interactions7
( (2p2,d+ is a rather special case o. o/erlap 3et6een p and d A"s 6hich is important in
organometallic chemistry and in the phosonitrilic compounds7
*1%%1' ) F/eltaG oAerlap
A. t6o nd
y
or nd

2
2
A"s 6ith their nuclei on the K ais are 3rought together, .ace2to2
.ace so to spea4, then they o/erlap in such a 6ay that rotation a3out the internuclear ais
produces a change o. sign e/ery $0

7 Such o/erlap is termed ) o/erlap (Digure ?7%(c++

and 6e can ha/e 3onding )(,d+ and anti3onding )(,d+

interactions7 This .orm o. o/erlap
plays an important role in some metal2metal 3onds, usually 6ith n R ,7
*1%%1( Non9?on/ing oAerlap
Apart .rom the eamples o. 3onding and anti3onding o/erlap 6e ha/e descri3ed a3o/e,
it is also possi3le .or A"s to o/erlap in such a 6ay that there is no interaction 3et6een
them7 An eample o. this non23onding o/erlap can 3e seen in Digure ?7%(d+ 6here the
o/erlap o. a 2s A" o. atom A 6ith a 2p A" o. atom B is illustrated7 The 2p A" is
orientated at right2angles to the internuclear ais and there are e0ual and opposite regions
o. o/erlap 3et6een the t6o A"s7 The 3onding and anti3onding interactions 3et6een them
The 9omonuclear <iatomic Colecules .rom Lithium to Dluorine #*$
Ta?le *1& Atomic #s, 2s and 2p or3ital o/erlap and 3onding
The o/erlapping
atomic or3itals
Type o. 3ond
a
Bonding or
anti3onding
#s + #s ' Bonding
#s

#s '

Anti3onding
2s + 2s ' Bonding
2s

2s '

Anti3onding
2s
+
2p
K
' Bonding
2s

2p
K
'

Anti3onding
2p
K
+
2p
K
' Bonding
2p
K

2p
K
'

Anti3onding
2p

+
2p

( Bonding
2p


2p

(

Anti3onding
2p
y
+
2p
y
( Bonding
2p
y

2p
y
(

Anti3onding
2s + 2p

non23onding
*
2s + 2p
y
non23onding
*
2p

+ 2p
y
non23onding
*
2p

+ 2p
K
non23onding
*
2p
y
+
2p
K
;on23onding
*
a
The internuclear ais is the K2ais7
*
;on23onding o/erlap does not depend upon the sign o. the or3ital
com3ination7 An2phase (++ and out2o.2phase (+ com3inations are
3oth non23onding7
cancel eactly and the total interaction 3et6een the t6o A"s is Kero7 At is important to
recognise that not all the A"s o. an atom can necessarily ta4e part in the .ormation o.
chemical 3onds or anti3onds, e/en 6hen their spatial distri3utions o/erlap7 The possi3le
o/erlaps and 3onding 3et6een #s, 2s and 2p A"s are summarised in Ta3le ?727
*1%& THE H2M2NUC5EAR 3IAT2MIC M25ECU5ES
6R2M 5ITHIUM T2 65U2RINE
At is much easier to construct simple, 0ualitati/e energy2le/el schemes .or molecules 6ith
the C" model than 6ith the 8B7 An constructing such schemes to descri3e the 3onding in
the a3o/e molecules 6e must ta4e account not only o. the relati/e magnitudes and signs
o. the o/erlap, 3ut also o. the relati/e energies o. the #s, 2s and 2p atomic or3itals o.
the elements in 0uestion7 The #s al6ays lies 6ell 3elo6 the 2s in energy and the 2s and
2p ha/e e0ual energies in the case o. hydrogen and mo/e .urther apart as 6e go to6ards
Ouorine7 The situation is .urther complicated 3y the .act that, as 6e ha/e seen a3o/e, 2s
and 2p A"s can interact i. the latter are orientated along the internuclear ais7 The most
important e..ect o. these changes in the relati/e energies o. the 2s and 2p A"s and the
2s22p ' interaction is that the order o. E!( #" and E!' ," changes (Digure ?7$+ and 6e
re0uire t6o energy2le/el diagrams, one .or the molecules lithium to nitrogen and another
.or oygen and Ouorine7 Coulson
,
and Currell, >ettle and Tedder
?
ha/e good discussions
o. these points7
But once 6e ha/e constructed suita3le energy le/el schemes, it is /ery easy to determine
the electronic conLgurations o. the molecules in 0uestion7 We simply Lll the C"s 6ith the
#50 The Co/alent Chemical Bond
s
;itrogen
s
*
"ygen
s
*
p
2
p
2
2p
s
,
2p
p
#
p
#
,
s
2
2s
s
2
s
#
2s
(a+
s
#
(3+
Lithium to nitrogen
"ygen and .luorine
6ig;re *1- Colecular or3ital energy2le/el schemes .or homonuclear diatomic molecules o. the
Lrst ro6 o. the periodic ta3le
a/aila3le electrons starting 6ith the lo6est (au.3au or 3uilding2up principle+ and placing
t6o, 3ut not more than t6o, electrons (!auli principle+ in each C"7 This is illustrated
.or nitrogen in Digure ?7$(a+ and .or oygen in Digure ?7$(3+7 The concept o. 3onding
and anti3onding o/erlap allo6s us to dra6 conclusions a3out the strength o. the 3ond
@oining the t6o atoms7 An the case o. nitrogen, .or eample, the #s2#s ' 3onding is /ery
small 3ecause the t6o #s A"s are /ery close to their respecti/e nuclei and their o/erlap
is almost Kero7 Thus, no 3onding (or anti3onding+ results .rom these .our core electrons7
The ' (2s+ 3onding o. C" '
#
, is e..ecti/ely cancelled 3y the ' (2s+

anti3onding o.
C"
'
2
, so no 3ond results .rom the .our electrons 6hich 6e place in these t6o C"s7 The
2p

22p

and 2p
y
22p
y
3onding interactions produce t6o 3onding ( C"s o. e0ual
energy
((
#
degenerate+ and they can accommodate .our electrons7 'ach dou3ly2occupied 3onding
C" constitutes one 3ond so 6e ha/e t6o 3onds7 Dinally, the last t6o electrons can 3e
placed in the 3onding ' C" .ormed 3y the 2p
K
22p
K
o/erlap, '
,
7 They pro/ide one more
3ond .or the molecule 6ith the result that 6e ha/e a /ery strong ;

; triple 3ond, in
agreement 6ith the usual description o. the molecule7 '
2
contains a little 2p
K
and '
,
a
little 2s, 3ut the sHp miing is small 3ecause o. the large E
2s
,E
2p
energy gap7
Dor the oygen molecule 6e proceed in the same 6ay until 6e come to the point 6here
only t6o electrons remain to 3e placed in C"s7 The C"s net in energy are a pair o.
degenerate (

C"s ((
2
+ and, .ollo6ing 9undGs rule, 6e must place one electron in each
o. these C"s and the spins o. the t6o electrons must 3e the same7 The result o. this
parallel orientation o. t6o electron spins is that theory predicts that the oygen molecule
9eteronuclear <iatomic Colecules #5#
is paramagnetic (Section #272+ and this is /ery unusual .or a simple, sta3le molecule7 But
the oygen molecule is indeed paramagnetic and the simple and clear 6ay in 6hich this
result is o3tained in the C" description is a /ery strong point in .a/our o. the applica3ility
that theory7 A count o. 3onding electron pairs minus anti3onding electron pairs (the t6o
electrons in the t6o (

C"s each contri3ute hal. a 3ond+ sho6s that the oygen molecule
has an ecess o. t6o 3onds o/er anti3onds in agreement 6ith the usual .ormulation o.
the molecule as "
=
"7
*1%' HETER2NUC5EAR 3IAT2MIC M25ECU5ES
When 6e see4 to apply the C" theory to heteronuclear diatomic molecules 6e ha/e
to consider a pro3lem 6hich did not arise in the homonuclear case7 There, there 6as
ne/er any 0uestion o. the proportions o. A"s in/ol/ed in an C" since, 3y symmetry,
each atom had to contri3ute e0ually7 This is not the case i. the atoms are not the same
as, .or eample, in the hydroyl radical, "9, 6hich is o3ser/ed spectroscopically 6hen
hydrogen 3urns in oygen7 At is also .ormed 3y the photolysis o. 6ater at high altitudes
and is important in the chemistry o. troposphere, i7e7 the atmosphere 3elo6 #0 4m7 The
#s A" o. the hydrogen atom is a3le to .orm a 3onding o/erlap 6ith 3oth the 2s and the
2p
K
A"s o. the oygen atom (K is the internuclear ais+ and 6e may .ormulate C" 6a/e
.unctions such as1
G
=
C
#
$
9#s
+
C
2
$
"2s
+
C
,
$
"2p
K
!?.#,.#"
But 6e do not 4no6 the relati/e magnitudes o. the three coe.Lcients, C
#
, C
2
and C
,
, i7e7 6e do not 4no6 to 6hat degree the t6o atoms contri3ute their A"s to the C"7 The
method 3y 6hich the /alues o. C
#
, C
2
and C
,
could 3e .ound 6as 4no6n e/en 3e.ore the
ad/ent o. 0uantum mechanics since similar types o. pro3lem occur in classical mechanics7
But apart .rom a .e6 small molecules and the special case o. the con@ugated hydrocar3ons
(see Section #27#+, it 6as scarcely possi3le to sol/e the necessary e0uations 3e.ore the
ad/ent o. the digital computer in the #$50s7
;o6adays, numerous computer programs .or sol/ing the pro3lem at di..erent le/els o.
approimation are a/aila3le7 The method employed is to use the /ariation method to Lnd
the 3est /alues o. the C
i
s 3y setting up the secular e0uations in the manner descri3ed in
detail in Appendi 27 An this particular case the measurea3le property, P , o. Appendi 2
is the energy, E, and the associated operator is the 9amiltonian, 9

7
An energy2le/el diagram .or "I9 calculated 6ith such a program .or the eperimen2
tally o3ser/ed "I9 3ond length o. $-70 pm is sho6n in Digure ?7#07 The positi/e lo3e
o. the oygen 2p
K
or3ital is directed to6ards the hydrogen atom7 "n the right o. the
diagram the #s A" o. hydrogen is sho6n at an energy o. #,7?0 e87 "n the le.t o. the
diagram the 2s and 2p A"s o. the oygen atom are plotted at ,27,0 e8 and #*7%0 e8
respecti/ely7 The oygen #s A" is not in/ol/ed in the 3onding and does not .eature in
the diagram7 An the centre o. the Lgure the calculated energy le/els o. "I9 are sho6n at
,,7,$ e8, #57%5 e8, #*7%0 e8 (dou3ly degenerate+ and +?7?2 e87 The dots indi2
cate the Llling o. the a/aila3le C"s 6ith electrons7 "n the .ar right o. the Lgure the
coe.Lcients o. the A"s, i7e7 C
#
, C
2
and C
,
, .or each ' C" are sho6n7 They tell us ho6
each A" contri3utes to each C" and the signs also sho6 the 3onding or anti3onding
nature o. the C"7 Ammediately 3eneath each coe.Lcient its s0uare is entered 3ecause it
is the s0uare o. the 6a/e .unction 6hich gi/es the electron density and the second ro6
#52 The Co/alent Chemical Bond
)#0
0
'nergy (e8+
"I9 :adical
s
3
"2pK "2s 9#s
07?$ 07-0 #720
07*- 07*$ #7**
I#0
I20
"2p
9#s
p
s
2
07%- 0720 072?
07-? 070* 070-
I,0
"2s
070* 07%$ 072#
s
1 0700 07-$ 070*
I*0
I + +
+
6ig;re *1%. A molecular or3ital energy2le/el scheme .or the "9 radical
o. Lgures there.ore re/eals ho6 the electrons are distri3uted in that particular C"P i. it
contains any7
Let us Lrst consider the C" o. lo6est energyP '
#
, E
=
,,.,$ e87 The ma@or con2
tri3utor 6ith a coe.Lcient o. +07%%$ is the oygen 2s A" and hydrogen #s also plays a
part 6ith a coe.Lcient o.
+
072#27 The contri3ution o. oygen 2p
K
is too small to concern
us7 ;ote that the or3ital is 3onding, 3ecause the t6o A" contri3utors o/erlap in phase,
and o. ' type7 We place t6o o. our se/en electrons in this C"7
The C" net in energy ('
2
, E
=
#5.%5 e8+ in/ol/es the same three A"s 3ut the
oygen 2p
K
no6 plays 3y .ar the most important role7 ;ote that the oygen 2s2hydrogen
#s o/erlap is anti3onding 6hile the oygen 2p
K
2hydrogen #s o/erlap is 3onding7 The last
is 3y .ar the greater and dominates so that the C" is 3onding in total7 But it is important
to o3ser/e that, 6here many A"s are in/ol/ed, 3oth 3onding and anti3onding interactions
can 3e .ound 6ithin the same C"7
The net t6o C"s, the degenerate pair o. ( symmetry at E = #*.%0 e8, are non2
3onding C"s7 The ( 2type oygen 2p

and oygen 2p
y
A"s ha/e Kero o/erlap 6ith the
' 2type hydrogen #s A" and there is no interaction 3et6een them7 Conse0uently these
t6o oygen 2p A"s are .ound in the molecule 6ith an unchanged energy o. #*7%0 e87
Their A" coe.Lcients are each #707 Since se/en electrons are a/aila3le to Lll the C"s o.
"I9 (the oygen #s electrons 3eing omitted .rom the diagram+, the last three electrons
must 3e placed in these t6o or3itals, o. 6hich one 6ill 3e only hal.2.ull7 The unpaired
electron ma4es the "I9 radical paramagnetic and /ery reacti/e7
The highest C" ('
,
+ is /ery high in energy (E
= +
?.?2 e8+ and strongly anti3onding
in all its o/erlaps7 A. electrons Lnd their 6ay into this C", 3y a3sor3ing light .or eample,
the molecule 3ecomes e/en more reacti/e7
An order to indicate, in a simple manner, the 6ay in 6hich the /arious A"s contri3ute
to the C"s lines connecting A"s and C"s are .re0uently dra6n, as in Digure ?7#07
"ccasionally lines o. di..ering thic4ness or dotted lines are used to indicate greater or
smaller A" contri3utions7
*1%( CHARE 3ISTRI8UTI2N
A .urther piece o. interesting in.ormation can 3e o3tained .rom the results o. an C"
calculation7 Drom the atomic or3ital coe.Lcients .or each occupied C" and the calcu2
lated o/erlap integrals the distri3ution o. the electrons throughout the molecule may 3e
calculated7 An the present eample o. the "I9 radical it is .ound that the se/en /alence
electrons are distri3uted such that ?7*% o. them are on the oygen atom and 0752 on the
hydrogen7
]
Thus, the hydrogen carries a partial positi/e charge o. approimately +e,2
and the oygen a partial negati/e charge o. e,2, 6here e is the charge on the proton7
This type o. analysis o. the distri3ution o. the electrons 6ithin the molecule is usually
termed Culli4en population analysis, a.ter :7S7 Culli4en 6ho Lrst introduced the idea7
*1%) HY8RI3ISATI2N AN3 RES2NANCE
The .act that a description o. the electronic structure o. a molecule is usually easier in
terms o. the C" rather than the 8B model stems .rom the .act that in the .ormer 6e
lea/e all consideration o. the electrons and their spins until the Lnal step I the Llling o.
the C"s 6ith electrons7 An the 8B model, on the other hand, 6e .orm our trial 6a/e
.unction .rom atoms complete 6ith their electrons, 6hich ha/e to 3e unpaired in
their atomic or3itals so that they can pair 6ith unpaired electrons on the other reacting
atom(s+7 An Sections ?7#5 and ?7#? 6e introduce the concepts o. hy*ridisation and
resonance, 6hich arose .rom this re0uirement .or complete atoms 6ith unpaired
electrons and .orm an important part o. the 8B model7
*1%)1% H0?ri/isation: !a;ling %-'%
Linus Carl !auling (#$0# I #$$*+ 6as the greatest chemist o. the 20th century7 <uring
a long career he made momentous contri3utions to chemistry and 6as also acti/e in 6orld
a..airs7 9e 6as a6arded the ;o3el !riKe .or Chemistry in #$5* and the ;o3el !eace !riKe
in #$?,7 The concept o. hy3ridisation, 6hich he put .or6ard in #$,#, is more important
in the 8B theory than in the C", as 6e shall see in Section ?7#5727 But 6e can readily
appreciate the need .or such an idea, e/en 6ithin the C" theory7 The construction o.
C"s .or 9I9 is /ery simple since 6e must al6ays ha/e e0ual contri3utions .rom the
t6o hydrogen atoms and there are only t6o hydrogen #s A"s to 3e considered7 When
6e see4 to .orm C"s .or molecules 6hich ha/e 2s and 2p /alence A"s many ne6
pro3lems present themsel/es, e/en 6hen @ust t6o identical atoms are to 3e com3ined, as
6e ha/e seen in Section ?7#27 A. the atoms to 3e com3ined are di..erent, and especially
]
This statement means that each electron spends ?7*%H- or $, Y o. its time in the /icinity o. the oygen atom and 0752H-
or - Y o. its time in the /icinty o. the hydrogen atom7
F

o
r

R

a

i
s

(
a
0
+
i. there are more than t6o, the pro3lem o. choosing suita3le com3inations o. A"s can
3e /ery complicated indeed7 Consider the three C"s o. "I97 T6o A"s o. oygen, the
2s and the 2p
K
, are al6ays in/ol/ed, al3eit sometimes in a rather une0ual measure7 But
they 3oth play a /ery signiLcant role in the C" o. highest energy 6ith /ery nearly
e0ual contri3utions .rom each7 This o3ser/ation leads to a potential simpliLcation in the
construction o. C"s7 :ather than consider the oygen 2s and oygen 2p
K
A"s separately,
6e Lrst ma4e com3inations o. them o. the .orms1

#
and
$
+
=
$

=
2
!$
2s
+
$
2p
K
" !?.#5.#a"

#
2
!$
2s

$
2p
K
" !?.#5.#3"
These or3itals are called hy3rid atomic or3itals and a contour diagram o. $
+
is sho6n
in Digure ?7##7 $

has eactly the same .orm 3ut the larger lo3e is directed along K7
'ach hy3rid or3ital is much enhanced in one direction and is there.ore particularly suited
to 3onding interaction 6ith the A"s o. a second atom lying in that direction7 An this /ie6,
the lo6est ' C" (
'
+ 6ill 3e the com3ination o. $
+
6ith hydrogen #s, i7e71

# #

#
'
=
2
!$
+
+
$
#s
"
=
2
!$
2s
+
$
2p
K
"
+
2
$
#s
(?7#572a+
There 6ill also 3e a strong anti3onding interaction 3et6een $
+
and 9#s corresponding
to the 6a/e .unction
'

1
# #

#
'

=
2
!$
+

$
#s
"
=
2
!$
2s
+
$
2p
K
"

2
$
#s
(?7#5723+
2
#
0720
0
07,0
0750
0720
07,0 07#0
07#0
07*0
#
0
2
"ygen sp hy3rid
# 0 # 2
N ais (a
0
+
6ig;re *1%% An sp hy3rid or3ital .or oygen
The other hy3rid !$

" points a6ay .rom the hydrogen atom and 6ill there.ore play
little part in the 3onding to that atom, i7e7 it 6ill 3e a non23onding or3ital7 Thus, 6e
ha/e simpliLed our thoughts a3out the 3onding in "I9 3y reducing the pro3lem to
one o. the interaction o. a single hy3rid or3ital ($
+
+ rather than t6o atomic or3itals,
$
2s
and $
2p

7 An energy le/el scheme .or "I9 constructed 6ith hy3rid oygen A"s is
sho6n in Digure ?7#27 This scheme is purely 0ualitati/e and no attempt has 3een made
to o3tain numerical /alues .or the energy le/els, .or reasons 6hich 6ill 3e made clear in
Section ?7#5757
The correspondence 3et6een the calculated C" scheme in Digure ?7#0 and the one
constructed 6ith hy3rid A"s is not particularly good in this case, since the assumption
that the 2s and 2p
K
A"s o. the oygen atom contri3ute e0ually to the t6o hy3rids is
a /ery poor one .or the t6o lo6er C"s7 Close inspection o. the A" coe.Lcients in
Digure ?7#0, or their s0uares, sho6s that the oygen atom contri3ution to the 3onding
C" ('
#
+ is entirely oygen 2s 6hile the contri3ution to the non23onding C" ('
2
+ is
almost eclusi/ely oygen 2p7 This illustrates a 6ea4ness o. the hy3rid or3ital approach
to chemical 3onding, 3ut it has the great ad/antage that 6e can construct an energy2
le/el scheme, 0uite literally, Qon the *ac; of an envelo%e G7 Durthermore, the use o. hy3rid
A"s leads to /ery speciLc predictions concerning molecular geometry, as 6e shall see
in more detail in Section ?7#57,7 Dor the moment 6e note that the .ormation o. a hy3rid
A" usually leads to an A" that points strongly in a particular direction in space and
is there.ore /ery 6ell suited to o/erlap 6ith the A"s o. a second atom 6hich lies in
that direction, 6hile the o/erlap 6ith the A"s o. an atom in any other position is much
diminished7
c("2s + "2p+ c9#s
"ygen hy3rid 9#s
anti3onding C"
c("2s "2p+
"ygen hy3rid
non23onding C"
"ygen hy3rid 9#s
3onding C"
c("2s + "2p+ + c9#s
"r3ital phases1 positi/e negati/e
6ig;re *1%& Colecular or3ital energy2le/el scheme .or the ' C"s o. "I9 using sp hy3rid oygen
or3itals
*1%)1& H0?ri/isation an/ t$e Aalen#e ?on/ t$eor0
:ecall the essential di..erence 3et6een the 6ays in 6hich the simplest trial 6a/e .unction
.or the hydrogen molecule 6as constructed using the C" and the 8B theories7 An the C"
theory, the .orm o. a molecular or3ital 6as Lrst determined (as the sum o. t6o hydrogen
#s A"s+ and the t6o electrons 6ere then placed in that C" 6ith their spins paired7 An the
8B theory, ho6e/er, the t6o hydrogen atoms, complete 6ith their electrons, 6ere 3rought
together in such a 6ay that their spins paired7 The hydrogen molecule is eceptional in
that a .air approimation to the molecular 6a/e .unction can 3e o3tained, 3y either the
C" or the 8B method, using only t6o A"s7 An almost all other molecules more than t6o
A"s are in/ol/ed in the 3onding o. t6o or more atoms7 At is 0uite easy to etend the C"
theory to em3race a large num3er o. A"s, 3ut this is not true o. the 8B theory 6here
6e need to Lnd a single electron in an A" on one com3ining atom 6hich can 3e paired
6ith another unpaired electron occupying an A" on another com3ining atom7 (We re0uire
a singly occupied A" 3ecause 6e must pair electrons to .orm 3onds7+ Durthermore, 6e
normally re0uire a hy3rid or3ital on at least one o. the com3ining atoms 3ecause 6e need
to direct the or3ital /ery speciLcally to6ards the other atom i. 6e are to .orm a strong
3ond7 But in atoms the electrons, .ollo6ing the au.3au (3uilding2up+ and !auli principles,
occupy the or3itals in pairs 6ith opposed spins7 Thus, the Lrst step in a 8B description
o. the chemical 3onding in a polyatomic molecule is the .ormulation o. a set o. singly
occupied hy3rid A"s .or the atoms in/ol/ed7 The classic and most important eample o.
this is the description o. the 3onding 3et6een car3on and hydrogen and 3et6een car3on
and car3on in the hydrocar3ons7
*1%)1' H0?ri/isation o" #ar?on A2s
An Section ?7#57# 6e noted 3rieOy that the .ormation o. hy3rid A"s has many implications
.or molecular geometry and it is use.ul, there.ore, to re/ie6 /ery 3rieOy the ma@or .eatures
o. the geometry o. the hydrocar3ons, 6hich any theory should reOect, 3e.ore 6e proceed
to discuss the A" hy3ridisation in these compounds7
Type #1 The car3on atom is 3onded to .our other atoms arranged at the corners o. a
tetrahedron 6ith the car3on atom at the centre7 The 3ond angles at the car3on
atom are /ery close to the tetrahedral angle o. #0$75

7 'amples are methane

and the higher saturated hydrocar3ons7
Type 21 The car3on atom is 3onded to three other atoms and all .our atoms lie in a plane
6ith 3ond angles at the car3on atom o. approimately #20

7 'amples are ethene

and the aromatic hydrocar3ons7
Type ,1 The car3on atom is 3onded to t6o other atoms and the 3ond angle at the car3on
atom is #%0

7 'thyne is the 3est eample o. this type o. 3onding7

The car3on atom in its state o. lo6est electronic energy has the conLguration
(#s+
2
(2s+
2
(2p+
2
6here, in accordance 6ith 9undGs rule, the t6o 2p electrons occupy
di..erent 2p A"s 6ith parallel spins7 The car3on atom has only t6o unpaired electrons
and 6e might there.ore epect that it 6ould .orm @ust t6o 3onds7 Durthermore, since any
t6o p A"s are orientated at right2angles to each other 6e might epect that these t6o
3onds 6ould enclose an angle at the car3on atom o. approimately $0

7 These predictions
are totally at /ariance 6ith the ma@or .eatures o. hydrocar3on structure outlined a3o/e7
A. 6e are to .orm .our 3onds 6e must, in a 8B description, Lrst generate .our unpaired
electrons7 There is one o3/ious 6ay o. doing this and that is to promote one o. the 2s
electrons to the /acant 2p A"7 This promotion re0uires energy7 But i. it leads to more and
stronger 3onds then the energy o. the molecule Lnally .ormed 6ill 3e that much lo6er,
i7e7 the molecule 6ill 3e more sta3le, and the in/estment o. energy 6ill ha/e 3een 6orth
6hile7 The eperimental o3ser/ation o. compounds o. Type #, and theoretical calculations
pro/e that the o/erall energetics o. the process are .a/oura3le7
But the promotion o. a 2s electron to a 2p A" is not o. itsel. su.Lcient to eplain the
tetrahedral geometry o. Type # compounds7 An .act, in the case o. methane .or eample,
the car3on atom conLguration (#s+
2
(2s+
#
(2p

+
#
(2p
y
+
#
(2p
K
+
#
might 3e epected to
produce three identical CI9 3onds directed along the , y and K aes and one di..erent
3ond 6ith no particular directional characteristics7 But, eperiment sho6s that
methane has .our
identical CI9 3onds 6ith 9ICI9 angles o. #0$75

7 Clearly, something more is re0uired7

Since the geometry o. methane is tetrahedral, it is clear that the strongest CI9 3onds
are .ormed .rom hy3rids 6ith enhanced electron densities along .our tetrahedral directions7
Digure ?7#, sho6s a cu3e in 6hich the three cartesian aes pass through the centre point
o. the .aces and 6e place a car3on atom at the centre o. the cu3e, 6hich is also the origin
o. the coordinate system7 A. 6e no6 place .our hydrogen atoms at alternate corners o.
the cu3e 6e ha/e a model o. the methane molecule7 The hydrogen atom # (9
#
+ at
+
x,
+y, +B, .or eample, is identically placed 6ith respect to the three car3on 2p or3itals
and a com3ination o. all three 2p A"s in e0ual proportions (2p

+
2p
y
+
2p
K
+ must, 3y
symmetry, produce a hy3rid or3ital directed along the line CI9
#
7 A hy3rid A" directed
to6ards 92 can 3e .ormed 3y the com3ination 2p

2p
y
+ 2p
K
7 And similarly .or
9, and 9*7 Since the 2s A" is spherically symmetrical it has no inOuence upon the
directional properties o. the hy3rid A"s, 3ut 6e must use it since 6e need .our hy3rid
A"s in total and these can only 3e constructed .rom an e0ual num3er o. unhy3ridised
A"s7 We there.ore ha/e to .ulLl the .ollo6ing re0uirements .or our hy3rid A"s1
The .our hy3rid A"s must QconsumeG all the .our 2s and 2p A"s o. the car3on atomP
no more and no less7
N
+ +
2
+ +
#
+
+
C R
+
,
+

F
*
(3+ (c+
(a+
6ig;re *1%' The methane molecule 6ith the .our hydrogen atoms (# *+ arranged at the corners
o. a cu3e centred at the car3on atom7
0
0705
07#0
0720
0720
07,0
07,0
07#0
0705
Car3on sp
,
hy3rid
2
2
2
2
F

o
r

R

(
a
0
+

The resulting hy3rid A"s must point to the corners o. a tetrahedron, i7e7 they must
contain the 2p A"s 6ith the appropriate signs as indicated .or 9# and 92 a3o/e7
Apart .rom their direction in space, all the hy3rid A"s must 3e eactly the same, i7e7
they must each contain the same proportions o. 2s and 2p A"s7
'ach hy3rid A" must 3e normalised to one7
The a3o/e re0uirements are satisLed 3y the hy3rids1
G
#
=
#
{$
2s
+ $
2p
G
2
=
#
{$
2s
$
2p
G
,
=
#
{$
2s
$
2p
+ $
2p
y
$
2p
y
+ $
2p
y
+ $
2pK
} (?7#57,a+
+ $
2p
K
} (?7#57,3+
$
2p
K
} (?7#57,c+
G
*
=
#
{$
2s
+ $
2p
$
2py
$
2p
K
} (?7#57,d+
9y3rid A"s o. this .orm are usually 4no6n as sp
,
hy3rids since they are composed o.
one 0uarter s and three 0uarters p A"s7 The proo. that they are orthogonal and normalised
is gi/en in Bo ?72 and a contour plot is sho6n in Digure ?7#*(a+7 The hy3rid A"s are
clearly highly directional and in a 8B calculation o. the methane molecule one electron
6ould 3e placed in each hy3rid A" and com3ined 6ith the singly occupied #s A" o.
the hydrogen atom to 6hich it is directed7 The interaction 6ith hydrogens at the other
corners o. the tetrahedron 6ould 3e neglected as a Lrst approimation7
The 3onding in hydrocar3ons o. Type 2 geometry can 3e interpreted in terms o. hy3ridi2
sation in a similar 6ay7 Consider the ethene molecule (Digure ?7#5+7 All si atoms lie in
the y2plane so the car3on 2p
K
A" plays a role di..erent .rom that o. the 2p

and 2p
y
7
,
2
#
0
#
2
6ig;re *1%(
,
2 # 0 # 2 ,
N (a
0
+
(a+
0705
0
07#0
0705
0720
07,0
0720
07,0
07#0
Car3on sp
2
hy3rid
07#0
0
0720
0705
0720
07,0
0705
07,0
07#0
Car3on sp hy3rid
F

o
r

R

(
a
0
+
F

o
r

R

(
a
0
+
,
2
#
0
#
2
,
2 # 0 # 2 ,
N (a
0
+
(3+
,
2
#
0
#
2
,
2 # 0 # 2 ,
N (a
0
+
(c+
6ig;re *1%( Car3on sp
,
, sp
2
and sp hy3rid or3itals
R
9
9
C C F
9
9
6ig;re *1%) 'thene
The car3on 2s, 2p

and 2p
y
are com3ined to .orm hy3rid A"s according to the .ollo6ing
e0uations1

G
#
=
!#,

G
2
=
!#,

?"{
?"{

2$
2s

$
2p

+

2$
2s

$
2p

,$
2p
y
}
(?7#57*a+

,$
2p
y
}
(?7#57*3+
G
,
=
!#, ,"
{
$
2s
+
2$
2p

}
(?7#57*c+
9y3rids o. this .orm are called sp
2
hy3rids 3ecause they are composed o. one third s
and t6o thirds p A"s7 They are directed to6ards the corners o. an e0uilateral triangle and
are there.ore ideally suited .or o/erlap and electron pairing 6ith atoms lying in a plane
and su3tending 3ond angles o. #20

7 They are also orthogonal and normalised7 The 2p

K
A" o. the car3on atom is not in/ol/ed in the hy3rids and there.ore remains a/aila3le .or
3onding 6ith 2p
K
A"s on ad@acent car3on atoms7 Whereas the o/erlap o. the sp
2
hy3rid
A"s gi/es rise to ' 3onding, the o/erlap o. the 2p
K
A"s on ad@acent car3on atoms results
in ( 3onding and the CIC 3ond in ethene is a dou3le 3ond 6ith ' and ( contri3utions7
The most important eample o. this type o. 3onding is .ound in the aromatic hydrocar3ons
o. 6hich 3enKene is the simplest representati/e7 An ( 3onding the electrons are not tightly
conLned in the internuclear region as they are in ' 3onding7 The nature o. ( 3onding
is such that the electrons in/ol/ed in it lie a3o/e and 3elo6 the plane o. the molecule
and are a3le to mo/e o/er all the car3on atoms .orming the molecule7 These delocalised
electrons are responsi3le .or the many properties o. the aromatic hydrocar3ons 6hich
distinguish them .rom the sp
,
23onded, saturated hydrocar3ons7 Dor eample, almost all
organic dyes are 3ased upon aromatic hydrocar3ons and the .act that they a3sor3 light in
the /isi3le region o. the spectrum, rather than at higher energy in the ultra2/iolet, is due
to the presence o. ( 2electron C"s7
'thyne (Digure ?7#?+ is a typical eample o. hydrocar3ons o. Type , in 6hich the
geometry at the car3on atom is linear7 The simple sp hy3rid A"s1

#
and
G
#
=
G
2
=
2
{
$
2s

$
2p

}
!?.#5.5a"

#
2
{
$
2s
+
$
2p

}
!?.#5.53"
produce 3onds to the hydrogen and car3on atoms 6ith an 9ICIC 3ond angle o. #%0

7
The remaining, unhy3ridised 2p
y
and 2p
K
A"s on the car3on atoms .orm t6o ( 3onds
gi/ing a total o. three 3onds in accord 6ith our usual .ormulation o. the CC triple 3ond
in ethyne7 Since they are .ormed .rom 2p A"s at $0

, the t6o ( 3onds are also at right

angles to each other7 As in the case o. Type 2 compounds, this ( 3onding pro/ides a 6ay
in 6hich the electrons in/ol/ed can 3e delocalised o/er the 6hole car3on2atom system i.
the triple 3onded car3ons are lin4ed to others as in the polyethynes7 Some /alues o. CI9
and CIC o/erlap integrals calculated 6ith Slater2type A"s (Bo ?7,+ and hy3rid A"s are
gi/en in Ta3les ?7, and ?7*7
6ig;re *1%* 'thyne
9 C C 9
'
(
Ta?le *1' Car3on I hydrogen atomic or3ital
o/er2 lap .or Slater2type car3on 2p and 2s and A"s
a
6ith
O

=
,.25 and a hydrogen #s A" 6ith O

=
#.2
r!CI9" = #0$.0 pm r!CI9" = #0$.0 pm
9#s|C2s = 0.5%5# 9#s|Csp
,
= 0.-?$?
9#s|C2p
K
= 0.550$ 9#s|Csp
2
= 0.-%-?
9#s|Csp = 0.%0,,
a
Bo ?7, ;ote ho6 the o/erlap o. the hydrogen #s 6ith
the car3on hy3rid A"s eceeds the o/erlap 6ith unhy2
3ridised car3on A"s7
Ta?le *1( Car3on I car3on atomic or3ital o/er2
lap .or Slater2type A"s
a
6ith O

= ,.25
Bond CIC C=C CC
rHpm #5*7, #,57, #207%
*
2s|2s 07,,$# 07*,0# 0750-0
2p|2p
07,2%% 07,2?? 072$,#
c
2p|2p
07#$0$ 072?*2 07,,,*
d
sp
,
|sp
,
07?*?? 07-2,? 07-5,$
sp
2
|sp
2
07?-5* 07-?5# 07%0-%
sp|sp 07?$-$ 07%0?$ 07%-0*
a
Bo ?7,7
*
The 3ond lengths correspond to typical single, dou3le
and triple car3on I car3on 3onds7
' c
The

2p
|
2p

o/erlap decreases as the 3ond length
decreases due to the o/erlap o. positi/e and negati/e
portions o. the 2p A"s7
(
d
The 2p|2p
decreases7
o/erlap increases as the 3ond length
*1%)1( T$e #$oi#e o" $0?ri/ or?itals
The reader may regard the preceding discussion o. hy3ridisation in hydrocar3ons as a
rationalisation o. the eperimentally o3ser/ed geometries, rather than a description o. a
procedure 3y means o. 6hich the eperimental energies and geometries may 3e calculated7
9o6e/er, to ta4e methane as our eample, the choice o. tetrahedral hy3rids is simply a
rational Lrst step, gi/en that a set o. singly occupied or3itals on the car3on atom is an
important simpliLcation in the application o. the 8B theory to methane7 A. 6e choose to
use the 2s and three 2p A"s o. car3on as our starting point, 6e 6ould o3tain eactly the
same result in the end, and it 6ould 3e possi3le to epress the molecular 6a/e .unction
o3tained in eactly the same .orm as that determined .rom an initial assumption o. sp
,
hy3rids, 3ut the calculation 6ould 3e considera3ly more complicated7 The Lnal results,
ground state energy and 6a/e .unction, are not determined 3y the starting point7
An interesting and detailed analysis o. this pro3lem, .rom a /ie62point 6hich appears to
ha/e 3een ta4en 3y .e6 other authors, has 3een gi/en 3y J7 W7 Linnett7
-%
Linnett eplored
the conse0uences o. the !auli elusion principle on the /alence electron distri3ution in
atoms7 An outline o. his approach is gi/en in Bo ?7*7 The .act that electrons o. the same
spin cannot occupy the same region o. space 3ecause o. the !auli principle, together 6ith
their mutual electrostatic repulsion, means that electrons o. di..erent spins tend to 4eep
together 6hile those o. the same spin 4eep apart7 Thus, .or neon, the electron distri3ution
o. highest pro3a3ility, as .ar as spin correlation e..ects are concerned, is an outer shell
consisting o. .our electron pairs at the corners o. a regular tetrahedron7
This 6ould also 3e true o. the C
*

ion, i. it eisted7 Thus, 6hen C
*

3inds to .our
protons the strongest 3onds 6ill 3e .ormed i. the protons are arranged at the corners o. a
regular tetrahedron7 The .ormation o. electron2pair 3onds rein.orces the pairing tendency
o. electrons ha/ing opposed spins7 An this /ie6, the choice o. .our tetrahedral sp
,
hy3rids
.or car3on 6ould 3e a natural choice, e/en i. 6e did not 4no6 the geometry o. methane7
These ideas do not appear to ha/e 3een 6idely eplored and this may 3e 3ecause a theory
o. molecular geometry, apparently 3ased purely upon electron repulsion, 6hich leads to
essentially the same conclusions in a manner 6hich is easier to apply, has .ound 6ider
acceptance7 This approach to molecular geometry is descri3ed in detail in Section ?7#-,
3ut it should 3e noted here that the concepts outlined immediately a3o/e pro/ide the
theoretical .oundation o. the simpler method (Bo ?7*+7
*1%)1) T$e properties o" $0?ri/9or?ital ?on/s
The .act that the o3/ious choice o. hy3rid or3itals reOects so precisely the salient .eatures
o. the molecular geometry o. hydrocar3ons and emphasises the t6o2electron nature o. each
identical CI9 3ond are the strong points o. the 8B theory and go a long 6ay to eplain
6hy concepts deri/ed .rom it, resonance (see Section ?7#?+ .or eample, are so pre/alent
in organic chemistry7 Andeed, these points are so appealing to the chemist see4ing a
0uantum2mechanically 3ased understanding o. molecular structure that the hy3rid or3itals
themsel/es can easily 3e ele/ated to a signiLcance a3o/e their true status7 This pro3lem is
especially clear 6hen 6e consider energiesP and 6e again ta4e methane as our eample7
Because all .our CI9 3onds are 4no6n eperimentally to 3e identical, and this .act
is echoed in the 8B description o. the molecule using .our sp
,
hy3rids, it is tempting to
conclude that there is a .our2.old degeneracy in the electronic energy le/els o. methane7
But i. 6e measure the energies o. the methane /alence electrons using photo2electron
spectroscopy, 6e Lnd a set o. three degenerate energy le/els at a3out #, e8 and a
single energy le/el at a3out 2, e87 Calculations sho6 that the triply degenerate le/els
arise .rom the 3onding o. the .our hydrogen #s A"s to the car3on 2p A"s and the single
le/el .rom the 3onding 3et6een the hydrogen #s or3itals and the car3on 2s A"7 That
this should 3e so is immediately conLrmed 3y a study o. Digure ?7#,, 6hich sho6s that,
3ecause o. the high cu3ic symmetry, each o. the three car3on 2p A"s has eactly the same
3onding interaction 6ith the appropriate phase com3ination o. the .our hydrogen #s A"s
6hile that o. the car3on 2s A" is clearly di..erent7 (Digures ?7#,(3+ and ?7#,(c+ sho6 the
or3ital phases .or 3onding o/erlap 3et6een the .our hydrogen #s A"s and the car3on 2s
and car3on 2p
K
A"s respecti/ely7 Dor clarity the A"s are not sho6n o/erlapping7+ The
price that 6e pay .or the simple description o. 3onds and their orientation pro/ided 3y
hy3ridisation is the loss o. in.ormation on energy 6hich use o. the unhy3ridised car3on
2s and 2p A"s ma4es o3/ious7 9y3rid or3itals, unli4e atomic and molecular or3itals,
are not eigen.unctions o. an energy operator and it is important to grasp this .act7 But
0uantum2mechanical 6a/e .unctions do not ha/e to 3e eigen.unctions o. some operator
in order to 3e o. /alue to us7
Colecular Geometry #?,
I
I
" " "
C C C
" " " " " "
I I I I
(a+
(3+
6ig;re *1%+ :esonance structures o. 3enKene (a+ and the car3onate anion (3+
*1%* RES2NANCE AN3 THE VA5ENCE 82N3 THE2RY
The 8B theory is also the origin o. and pro/ides the theoretical @ustiLcation .or the con2
cept o. resonance 6hich is /ery 6idely used in chemistryP in spite o. 3eing declared
incompati3le 6ith dialectical materialism in Stalinist :ussia7 Consider the .amiliar struc2
tural .ormulae .or 3enKene (Digure ?7#-(a++7 The three lines that ha/e di..erent positions in
the t6o structures represent the di..erent possi3le pairings o. the electrons in the car3on
2p
K
A"s7 Both o. these pairing schemes are re0uired to descri3e the 3onding in 3en2
Kene in a 8B calculation 6here the electrons, 6ith speciLed spin .unctions, are assigned
to A"s in the Lrst step o. the calculation7 The t6o structures are 4no6n as resonance
.orms o. 3enKene and 6e must 3e care.ul to recognise that they ha/e no independent
eistence7 'ach contri3utes e0ually to our 8B description (6a/e .unction+ o. the 3onding
in 3enKene7 Both are essential, 3e it in a representation o. the 3onding on paper or in
the mathematical .ormulation o. the 8B 6a/e .unction7 (The .ormulation o. 3enKene as
a ring inside a regular heagon is more a4in to an C" representation o. the electronic
structure7+ :esonance structures occur etremely .re0uently in discussions o. molecular
electronic structure7 An the case o. the car3onate anion (Digure ?7#-(3++, .or eample, three
structures are re0uired to epress the .act that all CI" 3onds are eactly the same7 This
cannot 3e sho6n 6ith one classical /alence (electron pairing+ structure7
*1%+ M25ECU5AR E2METRY
Any sel.2respecting theory o. molecular electronic structure must ha/e the a3ility to
predict molecular geometry7 A. calculations o. su.Lcient accuracy can 3e per.ormed, then
it is only necessary to repeat the calculation o. the total electronic energy o. the molecule
.or a /ariety o. geometries and to determine the geometry 6hich gi/es the lo6est (most
negati/e+ energy7 This 6ill 3e the e0uili3rium eperimental geometry o. the molecule7
But there are aspects o. this apparently straight.or6ard approach 6hich are unsatis.actory
i. 6e see4 a 6idely applica3le solution to the pro3lem7
The most important di.Lculty arises .rom the re0uired accuracy o. the calculation7 The
change in the total energy o. a molecule 6hich results .rom a small change o. 3ond angle
6ill normally 3e less than 07# Y o. the total energy7 Clearly, a /ery accurate and there.ore
tedious calculation is re0uired to achie/e this le/el o. accuracy .or a small molecule, and
it may 6ell 3e impossi3le .or a large molecule7 The practising chemist needs a theory
that can 3e applied more easily, and here 6e again recall the maim o. Wigner and SeitK
(Section ?72+7 What 6e re0uire is a pictorial /ie6 o. a molecule .rom 6hich 6e can dra6
conclusions a3out its geometry and particularly its 3ond angles7 The 8B theory 6ith its
emphasis upon the o/erlapping and interaction o. t6o singly occupied A"s, one .rom
each o. the atoms .orming the 3ond, is 3etter suited to this purpose than is the C" theory7
#?* The Co/alent Chemical Bond
Ta?le *1) Bond angles in simple hydrides
Colecule
F9
,
9IFI9 angle
(degrees+
FI9
(pm+
Colecule
F9
2
9IFI9 angle
(degrees+
FI9
(pm+
F F
; #0-7% #0#7- " #0*75 $57-
! $,7? #*#7$ S $27# #,,7?
As $#7% #5#7$ Se $# #*?
S3 $#7, #-07- Te $0 #-07-
Consider the 6ater molecule (9
2
"+7 ;eglecting the #s electrons, the electron conLguration
o. the oygen atom is1 (2s+
2
(2p

+
2
(2p
y
+
#
(2p
K
+
#
7 Dour o. the si /alence electrons
occupy the oygen 2s and one o. the oygen 2p A"s (6e ha/e ar3itrarily chosen the
2p

+ 6ith their spins paired and the remaining t6o electrons occupy the other t6o
oygen 2p A"s 6ith parallel spins and are a/aila3le to .orm 3onds7 Since the t6o singly2
occupied oygen A"s ha/e their maimum electron densities directed along the y2 and K2
aes, the greatest o/erlap and hence the strongest 3ond should 3e .ormed 6hen the t6o
hydrogen atoms
lie on those aes and .orm an 9I"I9 3ond angle o. $0

7 An .act, the eperimentally

determined 3ond angle o. the 6ater molecule is #0*75

7 A. the principal 0uantum num3er

2 is replaced 3y ,, then the argument @ust gi/en also applies to the 9ISI9 3ond angle
in hydrogen sulLde, the eperimental /alue o. 6hich is $27#

7 At should also apply to the

hydrides o. Group #5 (5A+ elements7 Ta3le ?75 gi/es some eamples7 These results are
remar4a3le .or such simple considerations7
*1%+1% T$e Aalen#e9s$ell ele#tron9pair rep;lsion FVSE!RG mo/el
An e/en simpler theory 6hich, in its application, ma4es minimal appeal to the concept
o. atomic or3itals 6as Lrst suggested 3y ;787 Sidg6ic4 and 97C7 !o6ell in #$*0 and
ela3orated 3y :7J7 Gillespie and :7S7 ;yholm in #$5-7 At is 4no6n as the Sidg6ic42!o6ell2
Gillespie2;yholm or as the 8alence Shell 'lectron2!air :epulsion (8S'!:+ model7 The
/alence shell electrons are those in the outermost shell o. the atom and they are the only
electrons that play a signiLcant role in the .ormation o. chemical 3onds7 Sidg6ic4 and
!o6ell, recognising that the /alence shell o. a chemically23onded atom contained 3ond
pairs and lone pairs o. electrons, suggested that the orientation in space o. the electron
pairs, and hence o. the 3onds around a central atom, 6ould 3e that 6hich minimises the
inter2electronic repulsion 3et6een them7 The concept 6hich the 8S'!: theory em3odies,
and 6hich 6as ne6 in #$*0, is the idea that lone pairs, i7e7 electrons in the /alence shell
3ut not in/ol/ed in 3onding, also ha/e a /ery important part to play in the determination
o. molecular geometry7
Sidg6ic4 and !o6ell assumed that the 3ond pairs and lone pairs 6ere o. e0ual impor2
tance, 3ut among many reLnements o. the theory Gillespie and ;yholm proposed that the
electrostatic repulsion 3et6een electron pairs diminishes in the se0uence1 lone pair2lone
pair R 3ond pair2lone pair R 3ond pair23ond pair7 The .ollo6ing interpretation o. the
situation is commonly gi/en7 Since a 3ond pair is dra6n a6ay .rom the central atom
to6ards the atom to 6hich it is 3onded, the region o. electron density associated 6ith
such a pair lies .urther a6ay .rom the central atom than does the corresponding region
Colecular Geometry #?5
o. a lone pair and conse0uently the repulsion eerted 3y it is less7 9o6e/er, recent the2
oretical 6or4 has thro6n dou3t upon this eplanation and it appears that the e..ect is
more su3tle7 But the order gi/en a3o/e certainly appears to apply and it pro/ides a use.ul
guide to molecular geometry7 We must hope that .urther 6or4 6ill clari.y the 3asis o.
this /alua3le idea 6hich is /ery easy to use7
We can illustrate the 8S'!: approach to molecular geometry 3y again considering
the shape o. 6ater7 We .ocus our attention upon the region o. space around the central
oygen atom7 The /alence shell o. oygen, i7e7 the shell 6ith principal 0uantum num3er
e0ual to 2, contri3utes si electrons to this region and each hydrogen contri3utes its single
/alence electron7 There.ore, there are eight electrons, i7e7 .our pairs, o. /alence electrons
surrounding the oygen atom7 A. the .our pairs o. electrons 6ere all eactly the same, their
mutual repulsion 6ould 3e at a minimum i. they 6ere located in .our regions directed
to6ards the corners o. an imaginary tetrahedron centred on the oygen atom7 The 9I"I9
3ond angle 6ould then 3e #0$75

7 But the electron pairs are not all identicalP 6e ha/e

t6o 3ond pairs and t6o lone pairs and the une0ual repulsion 3et6een these pairs 6ill
result in an increase o. the angle 3et6een the t6o lone pairs, 6hich 6e cannot measure,
and a decrease in the 9I"I9 angle in accord 6ith o3ser/ation7 Since the sul.ur atom
also has si /alence electrons (n = ,+ eactly the same reasoning can 3e applied to the
hydrogen sulLde molecule so that 3oth 6ater and hydrogen sulLde are predicted to 3e
3ent 6ith 9IFI9 angles less than the tetrahedral angle (Ta3le ?75+7 An ammonia (;9
,
+,
6ith three 3ond pairs and one lone pair, 6e predict that the lone pair23ond pair repulsions
6ill reduce the 9I;I9 3ond angle 3elo6 the tetrahedral angle, as indeed 6e o3ser/e
(9I;I9 in ammonia
=
#0-.%

+7
A num3er o. e..ects may contri3ute to the larger decrease o. the 9IFI9 angle .rom
#0$75

6hen F is a second2ro6 element7 A. 6e compare 6ater and hydrogen sulLde, the
t6o 3onding electron pairs are .urther apart in hydrogen sulLde than in 6ater 3ecause o.
the greater siKe o. the sul.ur atom and 3ecause the smaller electronegati/ity o. the sul.ur
atom allo6s the electrons to mo/e a6ay to6ards the hydrogen atomsP note the longer
SI9 3ond length in Ta3le ?757 This permits a reduction in the 9ISI9 angle relati/e to
the 9I"I9 angle7 A. 6e reLne our argument 3y introducing the concept o. the sort o.
or3itals 6hich the electron pairs might occupy then, since our starting point is a tetrahedral
arrangement, 6e naturally thin4 o. sp
,
hy3rid or3itals7 An this light 6e might then argue
that the tendency to hy3ridisation o. the s and p or3itals is less in sul.ur than in oygen
so that the SI9 3onds are .ormed 6ith sul.ur ,p A"s gi/ing 9ISI9 angles o. $0

7 This
is e0ui/alent to saying that the promotional energy re0uired to hy3ridise the ,s and ,p
A"s o. sul.ur cannot 3e reco/ered in the .ormation o. t6o SI9 3onds7
Dinally, 6e should repeat the 6arning a3o/e7 Although these eplanations o. the trends
in 3ond angle appear plausi3le 6e are dealing 6ith /ery su3tle e..ects and our /ie6s may
re0uire modiLcation in the light o. .urther research on this su3@ect7 LinnettGs ideas, 6hich
.ocus more attention on electron spin (Section ?7#57* and Bo ?7*+, may play an important
role in a .ull understanding o. the 8S'!: model7
*1%+1& T$e VSE!R mo/el an/ m;ltiple ?on/s
The 8S'!: theory treats multiple 3onds in much the same 6ay as it does single 3onds
regarding the t6o or three electron pairs o. a dou3le or triple 3ond as a single super2pair7
'lectron
pairs
Basic
shape
B!s L!s 'ampl
2 linear 2 0 t6o B!Gs at #%0

P linear BeD
2
, trigonal , 0 three B!Gs at #20

P trigonal BD
,
, d 2 # t6o B!Gs at P#20

P 3ent SnCl
2
a
* tetrahedral * 0 .our B!Gs at #0$75

P tetrahedral C9
*
* , # three B!Gs at P#0$75

P trigonal 3ipyramidal ;9
,
* d 2 2 t6o B!Gs at P#0$75

P 3ent "9
2
5 trigonal 5 0 trigonal 3ypyramid o. B!Gs !Cl
5
5 3ipyramidal * # L! in e0uatorial position SD
*
5 , 2 t6o e0uatorial L!GsP eTd2shaped ClD
,
5 2 , three e0uatorial L!GsP linear FeD
2
? octahedral ? 0 si B!Gs at $0

P octahedral SD
?
? 5 # s0uare pyramid AD
5
? d * 2 t6o aial L!GsP planar FeD
*
? d , , implies a central atom 6ith $ electrons
? d 2 * implies a central atom 6ith #0 electrons
#?? The Co/alent Chemical Bond
As an eample 6e may compare the geometries o. car3on dioide and sul.ur dioide7 An
the case o. car3on dioide (C"
2
+, the car3on atom contri3utes .our /alence electrons and
6e must assume that the oygen atoms each contri3ute t6o since oygen is in/aria3ly
di/alent7 (Spea4ing o. the 3onding in the usual 6ay, 6e 6ould say that the car3on atom
.orms one ' 3ond and one ( 3ond 6ith each oygen atom7+ Thus, the /alence electron
region surrounding the car3on atom contains eight electrons, 6hich 6e group into t6o
super2pairs7 Their mutual repulsion is minimised 3y an "ICI" angle o. #%0

and car3on
dioide is predicted to 3e linear7 An the case o. sul.ur dioide (S"
2
+, 6e ha/e ten electrons,
6hich 6e group into t6o super2pairs (S!s+ plus a lone pair7 The arrangement o. lo6est
energy .or three groups o. electron pairs is 3asically one in 6hich they are disposed at
Ta?le *1* 8S'!: predictions o. molecular shapes and eamples
e
Linear Trigonal Tetrahedral
ABA
=
#%0

ABA
=
#20

ABA
=
#0$.5

A
B A A
A
B A
B
A
A A A
Trigonal23ipyramidal "ctahedral
ABA = $0

P 'B' = #20

ABA = $0

A A
' A
A
A B B
'
A A
A A
a
An the /apor phase, not in the solid state7
Computational <e/elopments #?-
Ta?le *1+ 8S'!: interpretation o. molecular shapes
Colecule 8alence electrons Charge Total electrons ;um3er o. pairs Colecular shape
AB
n
A nB B!s S!s L!s
C9
*
* * 0 % * 0 0 tetrahedral
Z;"
2
\
+
5 * +# % 0 2 0 linear
ZACl
2
\
+
- 2 +# % 2 0 2 3ent
a
Z;"
2
\

5 * # #0 0 2 # 3ent
*
ZACl
2
\

- 2 # #0 2 0 , linear
c
"
,
? * 0 #0 0 2 # 3ent
*
!Cl
5
5 5 0 #0 5 0 0 trigonal 3ipyramidal
Z;"
,
\

5 ? # #2 0 , 0 trigonal
ZC"
,
\
2

* ? 2 #2 0 , 0 trigonal
FeD
*
% * 0 #2 * 0 2 s0uare planar
d
ZCl"
*
\

- % # #? 0 * 0 tetrahedral
ZS"
*
\
2

? % 2 #? 0 * 0 tetrahedral
Z!"
*
\
,

5 % , #? 0 * 0 tetrahedral
a
A tetrahedral disposition o. .our electron pairs 6ith t6o lone pairs7
*
A trigonal disposition o. three electron pairs 6ith one lone pair7
c
The three lone pairs occupy the aial positions o. the trigonal 3ipyramidal array o. L/e electron pairs7
d
The t6o lone pairs occupy the aial positions o. the octahedral array o. si electron pairs7
#20

to each other7 The o3ser/ed "ISI" angle o. ##$75

suggests that the 3ond pair23ond
pair and lone pair23ond pair repulsions are /ery similar in this molecule7 This might 3e
rationalised 3y o3ser/ing that the repulsion due to the 3ond pairs has increased 3ecause
they are no6 superpairs o. .our electrons each7 Be that as it may, there is a /ery positi/e
prediction o. a linear car3on dioide molecule and an angled sul.ur dioide, and this is
the ma@or .eature that 6e ha/e to eplain7 Ta3les ?7? and ?7- summarise the application
o. the 8S'!: model7
*1%, C2M!UTATI2NA5 3EVE52!MENTS
The ad/ent o. digital computers and their e/er2increasing po6er has had an enormous
impact on the calculation o. molecular properties 3y 0uantum2mechanical methods7 At
Lrst, apart .rom special pro3lems such as 9
2
, calculations on molecules o. chemical
interest could only 3e carried out i. all the electron2repulsion integrals and many others
6ere treated as parameters 6hich 6ere not calculated 3ut determined 3y comparison o.
theory and eperiment and inserted into the calculation at the outset7 ;ota3le ad/ances
6ere made 6ith these semi+em%irical C" methods and they are only no6 decreasing in
importance as the a*+initio C" methods, in 6hich all integrals are calculated .rom scratch,
are 3ecoming increasingly .easi3le7 The corresponding de/elopments in 8B theory did
not ta4e place since it pro/ed to 3e much more di.Lcult to implement the 8B theory
computationally, largely on account o. the re0uirement that the electron spins, correctly
paired, 3e introduced at the start o. the calculation rather than at the endP compare the
t6o treatments o. the hydrogen molecule (Sections ?7* to ?7-+7 But nota3le ad/ances in
the 8B theory and coding it 6ere made in the last t6o decades o. the 20th century and
a*+initio 8B calculations .or chemically interesting molecules are no6 reported on a
regular 3asis7 Concurrently 6ith the rise o. a*+initio 8B calculations a ne6 4id appeared
#?% The Co/alent Chemical Bond
on the 3loc4, density f1nctional theory (<DT+, 6hich ta4es a /ery di..erent approach to
the pro3lem o. calculating the physical properties o. molecules, 3ut appears to hold out
great promise in terms o. 0uality o. results and computational e.Lciency7
The 3i3liography, to 6hich A add some comments here, contains a .e6 leading re.2
erences to this etensi/e and still rapidly ad/ancing Leld o. chemical research7 Le/ine
$
has a long chapter 6hich pro/ides an ecellent introduction to C" methods, 3oth semi+
em%irical and a*+initio, and to <DT7 The 3oo4 3y 9inchli..e
#0
is a compact introduction
to a*+initio C" methods7 T6o /olumes in the 'lse/ier series, -heoretical and Com%1+
tational Chemistry, comprise ad/anced treatments o. modern <DT
##
and 8B
#2
6or4 3y
multiple authors7 Gerratt, a pioneer o. the modern 8B methodology, and some colleagues
ha/e 6ritten a chemistry2orientated re/ie6
#,
o. that theory7
This is also an appropriate place to note an eciting and /ery recent eperimental
ad/ance
#*
3ecause the ne6 techni0ue has pro/ided, .or the Lrst time, an image o. a
molecular or3ital 6hich can 3e directly compared 6ith theoretical results7 Colecular
or3itals are essentially a mathematical construct (Section ?75+, 3ut the .act that so many
eperimental measurements can 3e 0uantitati/ely interpreted 3y C" methods has gi/en us
reason to 3elie/e that they represent much more than that7 ;o6, eperiments using laser
pulses on the .emto2second (#0

#5
s+ time scale ha/e pro/ided an image o. the highest
occupied C" (9"C"+ o. nitrogen (;
2
+ ('
,
in Digure ?7$+ 6hich compares remar4a3ly
6ell, 0uantitati/ely, 6ith a similar image produced 3y an a*+initio C" calculation7 At
should 3e emphasised that the image is o. the C" itsel., not o. the s0uare or electron
density, and 6e see the epected pattern o. phases7 The authors 3elie/e that it 6ill 3e
possi3le to o3tain such images on a time scale 6hich 6ill allo6 us to .ollo6 the change
in electron distri3ution during a chemical reaction I an insight into the /ery essence o.
chemistry7
*1%- 8I85I2RA!HY AN3 6URTHER REA3IN
#7 W7G7 !almer, A 8istory of the Conce%t of Valency to IWXY, Cam3ridge =ni/ersity !ress, #$?57
27 C7A7 :ussell, -he 8istory of Valency, Leicester =ni/ersity !ress, #$-#7
,7 C7A7 Coulson, Valence, 2 nd edn, ".ord =ni/ersity !ress, #$?#7 : CcWeeney, Co1lson6s
Valence, , rd edn, ".ord =ni/ersity !ress, #$-$7
*7 C7S7G7 !hillips and :7J7!7 Williams, :norganic Chemistry, ".ord =ni/ersity !ress, #$?57
57 '7!7 Wigner and D7 SeitK, Solid State Physics, %, $- (#$55+7
?7 J7;7 Currell, S7D7A7 >ettle and J7C7 Tedder, Valence -heory, 2nd edn, Wiley, London, #$-07
-7 J7W7 Linnett, Wave 5echanics and Valency, Cethuen, London, #$?07
%7 J7W7 Linnett, -he Electronic Str1ct1re of 5olec1les, Cethuen, London, #$?*7
$7 A7;7 Le/ine, 31ant1m Chemistry, 5th edn, !rentice29all Anc7, ;e6 Jersey, 20007
#07 A7 9inchli..e, Com%1tational 31ant1m Chemistry, Wiley, Chichester, #$%%7
##7 J7C7 Seminario and !7 !olitKer ('ds+, 5odern Eensity 91nctional -heory, 'lse/ier, Amsterdam,
#$$57
#27 <7L7 Cooper ('d+, Valence /ond -heory, 'lse/ier, Amsterdam, 20027
#,7 J7 Gerratt, <7L7 Cooper and !7B7 >arada4o/, Chem. Soc. Revs., &*, %- (#$$-+7
#*7 J7 Atani, J7 Le/es0ue, <7 Neidler, 97 ;i4ura, 97 !ebpin, J7C7 >ie..er, !7B7 Cor4um and
<7C7
8illeneu/e, Nat1re, ('&, %?- (200*+7
The .ollo6ing three 3oo4s illustrate 6ell the application o. the 0uantum2mechanical theory o.
chemical 3onding to a /ery 6ide range o. real chemical pro3lems, in 6ays 6hich emphasise the
pictorial rather than the mathematical aspects o. the theory7
A / / A
$
2
/
Boes .or Chapter ? #?$
#57 T7A7 Al3right, J7>7 Burdett and C797 Whang3o, 4r*ital :nteractions in Chemistry, Wiley, ;e6
Ror4, #$%57
#?7 ;7W7 Alcoc4, /onding and Str1ct1re Str1ct1ral Princi%les in :norganic and 4rganic Chem+
istry, 'llis 9or6ood Ltd, Chichester, #$$07
#-7 A7 Dleming, 9rontier 4r*itals and 4rganic Chemical Reactions, Wiley, Chichester, #$-?7
82D *1% Normalisation o" t$e Aalen#e ?on/ FV8G an/ mole#;lar or?ital FM2G
waAe ";n#tions "or t$e $0/rogen mole#;le
The 8B 6a/e .unction to 3e normalised is1
= ;Z$
A
!#"$
/
!2" + $
/
!#"$
A
!2"\
A. the 6a/e .unction is normalised then the /alue o. the normalising constant ;
must 3e such that1

2
dv
#
dv
2
= ;
2
Z$
A
!#"$
/
!2" + $
/
!#"$
A
!2"\
2
dv
#
dv
2
= #.0
;
2
{Z$
A
!#"$
/
!2"\
2
+ Z$
/
!#"$
A
!2"\
2
+ 2Z$
A
!#"$
/
!2"\

Z$
/
!#"$
A
!2"\
}
dv
#
dv
2
=
#.0
N
2
$
2
!#" dv
#
$
2
!2" dv
2
+
$
2
!#" dv
#
$
2
!2" dv
2
+
2 $
A
!#"$
/
!#" dv
#
$
/
!2"$
A
!2" dv
2
= #.0
But, 3y deLnition, $
A
and $
/
are normalised #s atomic or3itals o. the hydrogen
atom, i7e71
A
!#" dv
#
= $
2
!#" dv
#
= #.0
There.ore, the Lrst t6o terms o. the epression a3o/e are each e0ual to #70 and
6e ha/e1
;
2
{2 + 2
$
A
!#"$
/
!#" dv
#
$
/
!2"$
A
!2" dv
2
} = #.0
Since all electrons are identical, the t6o integrals in the a3o/e e0uation are e0ual
and they can only ha/e a /alue in the region o. space 6here the atomic 6a/e .unctions,
$
A
and $
/
, 3oth ha/e non2Kero /alues7 A. 6e dra6 3oundary sur.aces .or the t6o A"Gs
separated 3y the 9I9 3ond length (Digure B?7#7#+ then 6e see that this condition is
only .ulLlled 6here the t6o A"s o/erlap7 Dor this reason, integrals o. this 4ind are
called overla% integrals7
The o/erlap integral is usually denoted 3y S1

S = $
A
!#"$
/
!#" dv
#
.
A
.
B
6ig;re 8*1%1% The o/erlap o. t6o #s atomic or3itals
Ta?le 8*1%1% The /alues o. S #s|#s as a .unction o. the or3ital eponent (N+ and
the inter2nuclear distance (:+ in atomic units
: (a
0
+
N 07% #70 #72 #7* #7? #7% 270
07$ 07$2# 07%%2 07%,% 07-$# 07-*2 07?$2 07?*#
#70 07$05 07%5% 07%0- 07-5, 07?$- 07?*# 075%?
#7# 07%%- 07%,, 07--5 07-#* 07?52 075$2 075,,
#72 07%?% 07%0- 07-*2 07?-5 07?0% 075** 07*%,
#7, 07%*% 07-%0 07-0% 07?,? 075?5 07*$% 07*,5
6here the triple integral sign reminds us that this is an integration o/er all three spatial
co2ordinates o. electron #7 Some /alues o. the integral are gi/en in Ta3le B?7#7#7 We
there.ore ha/e1
#
;
2
!2
+
2S
2
"
=
#.0

;
= {
2!#
+
S
2
"
}

2
The C" 6a/e .unction to 3e normalised is1
= ;

{!$
A
+ $
/
"!#"}
A. 6e call the normalisation constant ;

, then .or a normalised C" 6e must ha/e1

2
dv
#
= ;

2
{!$
A
+ $
/
"!#"}
2
dv
#
= #.0

;
2
{
$
2
!#"
+
$
2
!#"
+
2$
A
!#"$
/
!#"
}
dv
# =
#.0
A /
There.ore1
;

2
{2 + 2S} = #.0
#
;

= {
2!#
+
S"
}

2
2
2s 2p
$
2
*

82D *1& !roo" t$at t$e "o;r sp

'
$0?ri/ A2s o" E@;ation F*1%)1'G are normalise/
an/ ort$ogonal
N2RMA5ISATI2N

#
=
#
{$
2s
+ $
2p

+ $
2p
y
+ $
2p
K
}

2
dv
=
#
{
$
2s +
$
2p +
$
2p +
$
2p }
2
dv
#
*
y K
(Dor the sa4e o. simplicity 6e omit the electron in these e0uations7+
When the a3o/e 6a/e .unction is s0uared 6e Lnd terms o. t6o types1
a+ s0uared .unctions such as $
2
and $
2

3+ cross2terms such as $
2s
$
2p

and $
2p

$
2p
y
Since A"s o. the same atom, i7e7 $
2s
$
2p

$
2p
y
and $
2p
K
, are orthogonal and
nor2 malised, the .our s0uared terms each gi/e #70 and the #2 cross2terms each
contri3ute
Kero1
2s
dv = #.0 and $
2s
$
2p

= 0.0
There.ore

2 #
&'<7
#
dv
=
*

*
=
#.0
2RTH22NA5ITY


#

2
dv =
#
{Z$
2s
+ $
2p

+ $
2p
y
+ $
2p
K
\ Z$
2s
$
2p

$
2p
y
+ $
2p
K
\} dv
As 3e.ore, all the cross2terms gi/e Kero7 Dor the .our s0uared terms 6e ha/e1
#

2 2 2 2 #
&'<7
*
{
$
2s

$
2p


$
2p
y
+
$
2p
K
}
dv
=
*
{
#

#

#
+
#
} =
0
82D *1' Slater9T0pe 2r?itals FST2sG
The /ast ma@ority o. the calculations o. molecular 6a/e .unctions, 8B and C",
proceed .rom a 3asis set o. atomic or3itals7 As 6e ha/e seen (Section 57-+, the
radial .unctions o. accurate sel.2consistent2Leld or3itals .or an atom 6ith more than
one electron cannot 3e epressed in analytical .orm and 6ould there.ore 3e totally
impractica3le in general use7 Durthermore, since the electron cloud surrounding each
atom must undergo considera3le changes 6hen 3onds are .ormed, approimate atomic
or3ital .unctions may pro/ide as suita3le a starting point as more accurate ones7 "ne
o. the earliest proposals .or the construction o. suita3le analytical atomic radial .unc2
tions .or calculations on molecules 6as made 3y Slater in #$,0 (J7C7 Slater, Phys.
Rev., '*, 5- (#$,0++ and these .unctions ha/e 3een etensi/ely used, 3oth in their
original .orms and 6ith some modiLcations7 The original .orms ha/e 3een adopted
.or the calculation o. atomic or3ital o/erlap in this chapter7
Slater Lrst made a radical simpliLcation o. the radial .unction 3y proposing a
.unctional .orm 6hich had no nodes as opposed to the n # radial nodes .ound in
the eact 6a/e .unctions (see Chapter 5, Section 27# and Bo 57,+7 9e proposed the
normalised .unctions1

nlm
=

!2O

,n"
2n
+
#

#,2
!2n"U
r
n#
ep!O

r,n" R
lm
!# $"
6here N

is an effective nuclear charge .or a single electron in a central Leld resulting
.rom the nuclear charge and the repulsion o. the remaining electrons in the atom7 The
other sym3ols ha/e the meanings eplained in Chapter 57
Drom an analysis o. atomic spectral data, Slater o3tained a set o. rules .or calcu2
lating the screening, S, o. the electrons 6hich is then su3tracted .rom the true nuclear
charge, N, to gi/e N

(in units o.
+
e+7 S is calculated according to the .ollo6ing
rules1
#7 The electrons are di/ided into groups7 'ach electron in a group has the same
shielding constant 6hich di..ers .rom that o. the electrons in other groups7 The
groups are #sP 2s + 2pP ,s + ,pP ,dP *s + *pP *dP *.P 5s + 5pP etc7
27 The screening constant, S, is then gi/en as a sum o. the indi/idual contri3utions,
s, 6hich are calculated as .ollo6s1
(a+ Dor any electron outside the shell
f
under consideration s
=
0.07
(3+ Dor each other electron in the group considered s = 0.,5, ecept .or the #s
6here s = 0.,07
(c+ A. the group considered is an s + p group then s = 0.%5 .or each electron in
the net inner shell
f
and s = #.00 .or all electrons .urther in7
(d+ A. the group is a d or . group then s = #.00 .or e/ery electron inside it7
The .ollo6ing eamples illustrate the calculation o. N

.or the occupied or3itals
o. the iron atom, (#s+
2
(2s+
2
(2p+
?
(,s+
2
(,p+
?
(,d+
?
(*s+
2
7
Dirst .orm the re0uired electron groups1 Z#s\
2
P Z2s
+
2p\
%
P Z,s
+
,p\
%
P Z,d\
?
P Z*s\
2
7
N

!#s" = 2? !# 0.,0" = 25.-0
N

!2s" = 2? !- 0.,5" !2 0.%5" = 2#.%5 = N

!2p"
N

!,s" = 2? !- 0.,5" !% 0.%5" !2 #.00" = #*.-5 = N

!,p"
f
A shell is the set o. atomic or3itals ha/ing the same principal 0uantum num3er, n7
K
,
N

!,d"
=
2?

!5

0.,5"

!#%

#.00"
=
?.25
N

!*s" = 2? !# 0.,5" !#* 0.%5" !#0 #.00" = ,.-5
Because the .unctions ha/e no radial nodes, ST"s pro/ide a /ery poor description
o. the inner regions o. the atom7 9o6e/er, they are a much 3etter representation o.
the outer atomic regions, and since these are the regions o. most signiLcance .or
chemical 3inding ST"s ha/e 3een 6idely used in theoretical chemistry, though their
use is no6 in decline7 The Slater rules also re0uire that the higher principal 0uantum
num3ers, n, o. *, 5 and ? 3e replaced 3y ,7-
]
, *70 and *72
]
respecti/ely and the
0uality o. the ST"s deteriorates signiLcantly as n rises7 "ne 6ay o. impro/ing on
ST"s is to use a com3ination o. t6o o. them, each 6ith a di..erent /alue o. N

, to
represent one atomic or3ital7 "r3itals o. this type are 4no6n as dou3le2Keta .unctions7
]
The normalisation .actor in the ST" .ormula gi/en a3o/e does not apply .or non2integral /alues o. n7
82D *1( Ele#tron spin #orrelation: An example "ollowing J141 5innett
%
"ur purpose here is to demonstrate in more detail the 6ay in 6hich the !auli principle,
3y allo6ing only 6a/e .unctions 6hich are antisymmetric 6ith respect to electron
echange, eerts an important inOuence upon the energies o. states ha/ing di..erent
multiplicities and also upon the orientation o. electron distri3utions in space7 Suppose
that 6e ha/e an atom 6ith a closed #s electron shell, 6hich 6e ignore, and one
electron in each o. the 2s and 2p
K
or3itals, i7e7 conLguration #s
2
2s
#
2p
#
7 An Section
*7$ it is sho6n that i. the t6o electrons ha/e opposed spins the resulting state is a
singlet state and i. their spins are parallel 6e ha/e a triplet state and that the
spin 6a/e
.unctions o. the states 6ith S
B
=
0 are1
and

spin
!singlet"
=
!#, 2"{L!#"K !2" K!#"L!2"}

spin
!triplet" = !#

2"{L!#"K !2" + K!#"L!2"}.

When the electrons are echanged the sign o. the singlet .unction changes 6hile
that o. the triplet remains the same so that the singlet spin .unction is antisymmetric
6ith respect to electron echange 6hile the triplet is symmetric7 But the !auli prin2
ciple re0uires that the total electronic 6a/e .unction 3e antisymmetric 6ith respect
to electron echange, so to .ulLl that re0uirement the symmetric spin .unction must
3e com3ined 6ith an antisymmetric space .unction, and /ice /ersa7 This is ho6 spin
.unctions determine space .unctions and hence electron repulsion energies and the
su3@ect is eplored in more detail in Section ##757
The appropriate space .unctions are o. /ery similar .orm and 6e choose the sym2
metric .unction .or the singlet and the antisymmetric .unction .or the triplet1

space
!singlet"
=
!#, 2"
{
2s!#"2p
K
!2"
+
2p
K
!#"2s!2"
}
,
,
and

space
!triplet" = !#

2"{2s!#"2p
K
!2" 2%
K
!#"2s!2"}
We must no6 gi/e the indi/idual 2s and 2p
K
.unctions a more speciLc .orm7
The 2s is purely a .unction o. r since it is spherically symmetrical and the 2p
K
is a
.unction o. r multiplied 3y an angular part o. cos # (Appendi 5+7 There.ore, 6e 6rite
2s
=
f
s
!r " and 2p
K
=
f
%
!r "

cos # and assume that the .unctions are normalised7 At
is not necessary to ma4e the .unctions more eact, they already contain the essential
elements as 6e shall see7 Since 6e are concerned 6ith electron repulsion, 6e only
need to study the space .unctions 6hich can no6 3e 6ritten1

and

space
!singlet"
=
!#,

space
!triplet" = !#

2"
{
f
s
!r#"

f
%
!r2"

cos #
2
+
.
%
!r#"

cos #
#

f
s
!r2"
}
2"{f
s
!r#" f
%
!r2" cos #
2
f
%
!r#" cos #
#
.
s
!r2"}
When the t6o electrons are at the same radius, r

say, the epressions a3o/e
3ecome1
and

space
!singlet" = !#,

2"f
s
!r

"

f
%
!r

"
{
cos #
2
+
cos #
#
}

space
!triplet"
=
!#, 2".
s
!r

"

.
p
!r

"
{
cos #
2

cos #
#
}
The electron pro3a3ility is proportional to the s0uare o. the 6a/e .unction 6hich
is at a maimum .or the singlet .unction 6hen #
#
= #
2
= 0 or 6hen #
#
= #
2
= ( 7
Con/ersely, the maimum o. the triplet .unction occurs 6hen #
#
=
0 and #
2
=
(
or /ice /ersa7 Thus, i. the electrons in the 2s and 2p
K
or3itals ha/e a high pro3a3ility
o. 3eing at the same distance .rom the nucleus then, .or the singlet state, the spin
correlation places the electrons on the same side o. the nucleus 6hereas, .or the triplet
state, the most li4ely position .or the electrons is on opposite sides o. the nucleus7 The
hydrogen atom radial electron density .unctions illustrated in Digure 57, sho6 a /ery
mar4ed o/erlap o. the 2s and 2p .unctions so that 6e may epect spin correlation
to play an important role in the determination o. molecular geometry7 Durthermore,
it is clear that the interelectronic repulsion o. the electrons is lo6er in the triplet
state than in the singlet7 This illustrates the underlying reason .or 9undGs rule and
in/ites us to en0uire .urther into the theoretical .oundations o. the 8S'!: method
(Section ?7#-7#+7
An Section ##75 6e sho6 that the electron2repulsion energy o. the singlet and triplet
states deLned a3o/e are gi/en 3y1
E
triplet
= Q
2s2p
@
2s2p
and E
singlet
= Q
2s2p
+ @
2s2p
6here Q
2s2p
= 2s!#"2p!2"|#,r
#2
|2s!#"2p!2"
and @
2s2p
= 2s!#"2p!2"|#,r
#2
|2p!#"2s!2" .
The electron repulsion Q
2s2p
is called the Coulom3ic repulsion and represents the
classical repulsion o. t6o electrons, one in the 2s or3ital and the other in the 2p7
The repulsion @
2s2p
is called the echange repulsion and ma4es a contri3ution to
the interelectronic repulsion 6hich has no classical counterpart7 Though @
2s2p
itsel.
is a positi/e 0uantity, the .act that it appears 6ith a negati/e sign in the epression
.or E
triplet
should alert us to its non2classical nature7 At represents the repulsion o.
the t6o electrons in the o/erlap regions, i7e7 electron density 2s(#+2p(#+ repelling
density 2s(2+2p(2+7 Such a term can only arise in 0uantum mechanics 6here electron
pro3a3ility is gi/en 3y the s71are o. a .unction, not 3y the .unction itsel.7 The presence
o. such a term in the epression .or repulsion energy immediately con.ronts us 6ith
a /ery .undamental 0uestion7 Are 6e @ustiLed in tal4ing a3out electron2pair repulsion
in molecules in purely classical termsJ
Calculations 3y J7 Lennard2Jones and J7A7 !ople
2
thro6 some light upon that
0uestion7 They used Slater2type or3itals (Bo ?7,+ to calculate the /alues o. Q
2s2p
and @
2s2p
, in atomic units, .or the 3eryllium atom and .ound the /alues sho6n in
Ta3le B?7*7#7 N

is the e..ecti/e nuclear charge7
The data in the Lrst ro6 o. the ta3le sho6 that the non2classical term is a3out
22 Y o. the classical term 6hich pro/ides some @ustiLcation .or our neglect o. it 6hen
6e apply the 8S'!: theory7 The /alues in the second ro6 are also rele/ant to this
discussion, 3ut they Lrst re0uire .urther eplanation7 Drom the 2s and 2p or3itals 6e
can .orm normalised hy3rid or3itals (called e71ivalent or3itals 3y Lennard2Jones and
!ople+ o. the .orms1

h
+
=
!#, 2"{2s + 2p
K
} h

= !#,

2"
{
2s

2p
K
}
and i. 6e calculate Q and @ 6ith these hy3rids 6e o3tain the results in the second
ro6 o. the ta3le7 We Lrst note that the total electron repulsion energy, Q @ , is
constant, independent o. the change to hy3rid or3itals, 6hich is 0uite generally true
as Lennard2Jones and !ople
2
pro/e7 The .ormulation o. the electron distri3ution in
terms o. hy3rids reduces the non2classical term .rom 22 Y to 27* Y o. the classical7
Clearly, in this case, a classical /ie6 o. electron repulsion is more @ustiLed 6hen
hy3rids rather than the 2s and 2p or3itals themsel/es are used7 The same is true in
other situations, e7g7 .our sp
,
hy3rids as opposed to a 2s and three 2p or3itals, though
the di..erence is less mar4ed7 The reason .or the decrease in the magnitude o. @
6hen hy3rid or3itals are used is the reduction o. the o/erlap electron densities due
to the localised and directional character o. the hy3rids7 At is .ortunate, there.ore,
that the localised groups o. 3onding or lone2pair electrons 6hich 6e en/isage 6hen
6e apply the 8S'!: method are @ust those electron distri3utions in space 6hich 6e
also associate 6ith hy3rid or3itals7 Though it is not essential to in/o4e hy3ridisation
6hen applying the 8S'!: theory, it does appear that hy3rid or3itals ma4e a classical
approach to electron repulsion more accepta3le .rom a strictly 0uantum2mechanical
point o. /ie67
Ta?le 8*1(1% 'lectron repulsion integrals .or Be1 #s
2
2s
#
2p
#
Q
a3
,E
9
@
a3
,E
9
!Q
a3
@
a3
",E
9
a = 2s, 3 = 2p 07#%#? N

070*0# N

07#*#5 N

a
=
h+ 3
=
h 07#*50 N

0700,5 N

07#*#5 N

2
#
RE6ERENCES
#7 J7W7 Linnett, Wave 5echanics and Valency, Cethuen, London, #$?07
27 J7 Lennard2Jones and J7A7 !ople, Proc. Roy. Soc., A&.&, #?? (#$50+7
!R285EMS 62R CHA!TER *
#7 =se the .ollo6ing data to dra6 an energy2le/el diagram, similar to Digure ?7#, .or the
-
Li
2
molecule7 Calculate E
e
7
Li Li
+
+ e A' = 5.,$ e8 *,*-, cm

#
Li
2
Li + Li E
0
= #.0, e8 %,0- cm

#
Nero2point energy =
#
h> = 0.022 e8 #-5.- cm

#
27 !7 Corse proposed that, .or a diatomic molecule, the /ariation o. the energy (E+ 6ith
internuclear distance (r + could 3e 6ritten1
E = E
e
Z# ep{K!R
e
r"}\
2
Dor Li
2
R
e
, the e0uili3rium internuclear distance = 2?-., pm and K is a constant related
to the /i3rational .re0uency (>+ o. the molecule and the reduced mass (T+1
m
#
m
2
,.50$ a7m7u7 K
=
*.0?#-

#0

*

>

#
T

2
T
=
!m + m
2
"
=
E
e
(The last epression gi/es K in cm

#
6hen T is entered in a7m7u7, > in s

#
and E
e
in cm

#
7+
!lot the Corse cur/e .or Li
2
.or r
=
5 I #?0 nm using the data a3o/e7 (This is
a pro3lem 6here a spread sheet 6ith a graph2plotting .acility, e7g7 'FC'L, is /ery
use.ul7+
,7 The .unction $ is a normalised #s atomic or3ital7
#
$
=
(

O

,,2
a
0
ep!Nr,a
0
" a
0
= Bohr radius = 52.$2 pm
Allustrate the etension o. the or3ital into the space surrounding the atom 3y plotting
the .unction $ /ersus r .or N = 0.5, #70, #757 (9ere, again, a spread sheet can 3e /ery
use.ul7+
*7 Sho6 that the sp
2
hy3rid or3itals ('0uation (?7#57*++ are normalised, orthogonal and
orientated at #20

to each other7 (8ector alge3ra, regarding a normalised p2or3ital as a
unit /ector along the appropriate ais, or trigonometry can 3e used .or the orientation
pro3lem7+
57 This pro3lem is essentially a repeat o. 9eitler and LondonGs Lrst 8B calculation o. the
3inding energy o. the hydrogen molecule7 We 6or4 in atomic units 6hich are much
easier to use in calculations7 The energies 6hich 6e determine can 3e easily con/erted
to SA energy units, i. that is re0uired7
!ro3lems .or Chapter ? #--
9

An a7u7 the 9amiltonian (9

+ o. '0uation (?7,7#+ 3ecomes1
# 2 # 2
# # # # # # =
2

#

2

2

r A#

r
B#

r
A2

r
B2
+
r
#2
+
R
AB
#
Rou 6ill Lnd it use.ul to note that a pair o. terms such as

#

or

#

2
2 #
r A#
2 #
#
r B#
constitute the 9amiltonian operator .or a hydrogen atom7 There.ore, i. 6e denote
such a pair 3y 9

#s
and a hydrogen #s or3ital 3y $
A
then1
9

#s
$
A
!#" = E
#s
$
A
!#"
The 8B 6a/e .unction ('0uation (?7*7,++ is1
= ;{$
A
!#" $
B
!2" + $
B
!#" $
A
!2"}
6here the normalising constant (;+ is determined in Bo ?7#7
Sho6 that the epectation /alue o. the energy (E+ is gi/en 3y1
E
=
G |9

|G Q + @
Where1
G |G
=
# + S
2
Q

= 2E
#s
+ 23 + Q + #,R
AB
@

= 2S
2
E
#s
+ 2S3

+ @ + S
2
,R
AB
3 = $
A
!#"| #,r
B#
|$
A
!#" 3

= $
A
!#"| #,r
B#
|$
B
!#" S = $
A
!#"|$
B
!#"
Q = $
A
!#" $
B
!2"|#,r
#2
|$
A
!#" $
B
!2" and
@ = $
A
!#" $
B
!2"|#,r
#2
|$
B
!#" $
A
!2"
Sho6 that i. 6e set 2E
#s
= 0.0 then the di..erence in energy ( E+ 3et6een the
molecule and t6o hydrogen atoms is1
23
+
2S3

+
Q
+
@ #
E =
# + S
2
+
R
AB
Sho6 that the trial 6a/e .unction, G

= $
A
!#" $
B
!2", is normalised and gi/es an
epectation /alue .or the energy o.1
E

=

G
|
9
|
G

G

|G


=
Q
=sing the data in the .ollo6ing ta3le, plot graphs o. E and E

against internuclear
distance, R
AB
7 The result sho6s that the 3inding energy o3tained 6ithout allo6ing .or
electron QechangeG is a3out one2sith o. that o3tained 6ith the .ull 6a/e .unction7 But
the 6a/e .unction G

is 0uite unaccepta3le since it contradicts the .undamental theo2
retical re0uirement that 3oth terms, $
A
!#"

$
B
!2" and $
A
!2"

$
B
!#", must 3e included
3ecause electrons are indistinguisha3le7
R
AB
,a
0
0.25
S
0.$%$-,
3,E
9
0.$?-,5
3

,E
9
0.$-,50
Q ,E
9
0.?#$%?
@,E
9
0.?0$-*
0.-5 0.$#52#
0.%#2-0 0.%2??*
0.5%25$ 0.50?%*
#.25 0.-$,%?
0.?5225 0.?**?*
0.52,#, 0.,?*-$
#.50 0.-25#-
0.5%,?$ 0.55-%,
0.*$0,* 0.2$?%*
#.?5 0.?%,22
0.5*?%2 0.50%$,
0.*-0?# 0.25$*0
#.-5 0.?552-
0.52,$% 0.*--%%
0.*5-?0 0.2,?#2
2.00 0.5%?*5
0.*-25, 0.*0?0#
0.*25$- 0.#%*#?
2.50 0.*5%,#
0.,$05- 0.2%-,0
0.,?%,$ 0.#0??2
,.00 0.,*%5#
0.,,00, 0.#$$#5
0.,#$%0 0.05%5#
,.50 0.25$#$
0.2%*5* 0.#,5%$
0.2-$$* 0.0,0-?
*.00 0.#%$2?
0.2*$5% 0.0$#5%
0.2*-55 0.0#5?0
*.50 0.#,?0$
0.2220- 0.0?##0
0.22##$ 0.00-?0
5.00 0.0$?5%
0.#$$$5 0.0*0*,
0.#$$5- 0.00,#%
Dind the epectation energy, E

, .or the 6a/e .unction G

, 6hich represents an
unsta3le state o. 9
2
1
G

= ;

{$
A
!#" $
B
!2" $
A
!2" $
B
!#"}
!lot E

against R and compare the cur/e 6ith your results .or G and G

7
?7 Consider the molecule sho6n in the Lgure1
#
3
9
3
2 9
g
9
,
9ydrogen atoms 2 and , o. the 9
,
molecule are e0ually 3onded to atom # 3ut the
3ond 3et6een 9# and 92 is not necessarily o. the same strength and this is reOected
in the /alues o. the interaction elements o. the energy (9amiltonian+ matri1
$
#
|9

|$
2
= $
#
|9

|$
,
= K 3ut $
2
|9

|$
,
= N
6here $
n
is a hydrogen #s A" on atom n7 ;ote that K and N are negati/e 0uantities
3ecause they represent 3onding interactions 6hich reduce the energy o. the molecule
vis+aZ +vis the isolated atoms7 A. 6e ar3itrarily L the Kero o. the energy scale 3y
setting the on2diagonal elements o. the matri to L 6e ha/e1
9

$
#
$
2
$
,
$
#
L K K
$
2
K L N
$
,
K N L
Dind the eigen/alues o. this matri (Appendi ,+7 (A. you .orm ro6s and columns
o. $
#
!$
2
+ $
,
",

2 and !$
2
$
,
",

2 you 6ill Lnd that the matri 3loc4s out into a

# # and a 2 2 matri7+
T6o etreme .orms o. the molecule may 3e en/isagedP one (the linear molecule+
in 6hich N 0 and the other in 6hich N = K (the e0uilateral triangle+7 <etermine the
eigen/alues .or these t6o species7
=se a spread sheet to plot a correlation diagram relating the molecular or3ital
energies o/er the 6hole range o. relati/e /alues o. K and N 7 (At is con/enient to set
L = 0.0 K = #0.0 and N = 0.0 to #070 in steps o. #707+
A. the energies o. the molecular or3itals o. an 9
,
species 6ere measured and .ound
to 3e *72 e8, +07% e8 and +,7* e81
(a+ Where on the correlation diagram should the molecule 3e placedJ
(3+ What 6ould the relati/e /alues o. K and N 3eJ
(c+ What 6ould the a3solute /alues o. K and N 3eJ
ZAns6ers1 (a+ N = ,P (3+ N ,K = 0.,P (c+ K = 2.?-, N = 0.%\
Chapter -
8on/ing< Spe#tros#op0 an/
Magnetism in Transition9Metal
Complexes
-70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%#
-7# 9istorical de/elopment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%2
-72 The crystal Leld theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #%2
-7, The electronic energy le/els o. transition2metal complees . . . . . . . . . . . . #%-
-7,7# The 6ea42Leld scheme .or d
2
(eample o.
,
D in an octahedral Leld+ . #%$
-7,72 The 6ea42Leld scheme .or d
2
(inclusion o.
,
!+ . . . . . . . . . . . . . . .
-7,7, The d
2
energy le/els .or 6ea4, strong and intermediate
#$0
octahedral Lelds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #$#
-7,7* The strong2Leld scheme .or d
2
in an octahedral Leld . . . . . . . . . . . #$,
-7,75 Spin2or3it coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . #$5
-7* The electronic spectroscopy o. transition2metal complees . . . . . . . . . . . . #$?
-75 !airing energiesP lo62spin and high2spin complees . . . . . . . . . . . . . . . . . #$-
-7? The magnetism o. transition2metal complees . . . . . . . . . . . . . . . . . . . . . #$-
-7- Co/alency and the ligand Leld theory . . . . . . . . . . . . . . . . . . . . . . . . . . #$$
-7% Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20,
!ro3lems .or Chapter - . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#2
+1. INTR23UCTI2N
The colours and magnetic properties o. the comple compounds o. the transition2metal
ions presented a great challenge to the theory o. the chemical 3ond and, although the
pro3lem is no6 6ell understood in principle, 0uantitati/e interpretation o. the many su3tle
e..ects continues to engage the theoretician, not least on account o. their signiLcance
in 3iology and technological applications7 "ne thin4s, .or eample, o. transition2metal
catalysts, the 3iological .unctions o. metallo2proteins, magnetic storage de/ices and up2
con/erters7 9istorically, the interpretation o. these phenomena has 3een 3y means o. ligand
Leld (LD+ theory, 3ut density .unctional theory and UL scattered26a/e methods are no6
seeing increasing application7 The 6ords Qligand Leld theoryG con/ey to the practitioners
a range o. methods, /arying 6idely in their sophistication, o. applying e..ecti/ely the
same theory7 The essentials o. the theory are its origins in crystal Leld (CD+ theory,
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
#%2 Transition2Cetal Complees
etensi/e and sometimes ad/anced use o. group theory and the treatment o. the interaction
3et6een metal ion and ligand as co/alent as 6ell as electrostatic7 A 3rie. outline o. the
de/elopments 6hich ha/e led to the present state o. the art 6ill ma4e these points clearerP
3ut Lrst a comment on the use o. group theory and matri diagonalisation7
The theory o. the transition2metal ions relies hea/ily upon group theory and many
ecellent descriptions o. the su3@ect 6hich incorporate the re0uired group theory are
a/aila3le7
#
At there.ore appears superOuous to include group theory here and little or no
appeal to it 6ill 3e made in the .ollo6ing chapter7 The use o. group2theoretical sym3ols
to identi.y electronic states should present no pro3lemsP the reader 6ho has no 4no6ledge
o. the su3@ect may regard these sym3ols simply as la3els7
An 6hat .ollo6s 6e shall also ma4e .re0uent appeal to the concept o. determining
energies 3y setting up and diagonalising the 9amiltonian matri .or a pro3lem7 :eaders
un.amiliar 6ith this idea should read Appendi , 3e.ore going 3eyond Section -7#7
+1% HIST2RICA5 3EVE52!MENT
An #$2$, J7 Bec0uerel proposed that the central metal ion in a transition2metal comple
6as su3@ect to an electrostatic Leld originating .rom the surrounding ligands7 An the same
year, 9ans Al3recht Bethe (#$0? I + used symmetry and group theory to place
Bec0uerelGs idea on the Lrm theoretical .oundation 6e no6 call CD theory7 Just three
years later, in
#$,2, John 9as3rouc4 8an 8lec4 (#%$$ I #$%0+ demonstrated the po6er o. the ne6
theory 6hen he interpreted the paramagnetism o. the Lrst2ro6 transition2metal
complees and the rare earths 6ith good 0uantitati/e accuracy7 8an 8lec4 and his co2
6or4ers made many other seminal contri3utions to the de/elopment o. the theory and its
applications o/er the .ollo6ing decade7
A /alence 3ond approach to the pro3lem 6as introduced in the #$*0s 3y Linus !auling,
3ut it pro/ed less success.ul than the CD theory in the interpretation o. electronic spectra
and 6e shall not pursue it .urther here7 At is descri3ed in detail in !aulingGs masterpiece,
-he Nat1re of the Chemical /ond7
2
With the gro6th o. the molecular or3ital (C"+ theory in the second hal. o. the 20th
century, the time appeared ripe to tac4le the most o3/ious shortcoming o. the CD theory7
The interaction 3et6een ligand and central metal ion is clearly more than a purely elec2
trostatic oneP there is also a signiLcant element o. co/alency 6hich should 3e amena3le
to a C" treatment7 The range o. theories 6hich gre6 .rom this seed carry the collecti/e
name o. ligand Leld theory7
+1& THE CRYSTA5 6IE53 THE2RY
Cany o. the complees o. the transition metal ions are /ery symmetrical7 Bethe sho6ed
ho6 the symmetry could 3e elegantly eploited 3y means o. group theory to determine the
6ay in 6hich a purely electrostatic Leld .rom the surrounding ligands could remo/e the
L/e2.old degeneracy o. the partially occupied metal d or3itals7 As noted a3o/e, there are
many ecellent accounts o. this su3@ect7
#
As an illustration o. the 0uantitati/e e..ect o. a
crystal Leld on L/e d or3itals 6e shall calculate the matri elements o. an octahedral Leld7
An electron 6ith charge e and polar coordinates r, # and $ and a point charge 0
at r
0
, #
0
and $
0
is sho6n in Digure -7#7 The atomic nucleus is at 0,0,0 and the distance
0
0
0

The Crystal Dield Theory #%,

0
r
0
0
0
.
0
d
;ucleus
e
r 0 .
6ig;re +1% An electron in the Leld o. a negati/e electrostatic charge
3et6een the point charge and the electron is d7 We 6ish to calculate the energy o. each o.
the L/e d2electron distri3utions in the electrostatic Leld o. an array o. si such charges,
0, located at the /ertices o. a regular octahedron7 We shall arrange our results in the .orm
o. a matri, i7e7 6e shall calculate the matri elements o. the crystal2Leld 9amiltonian,
9

c.
7 Dor the single charge in Digure -7# 6e re0uire1
G
n

l

m

|0e,d |G
nlm
= 0e G
n

l

m

|#,d |G
nlm

.or all possi3le com3inations o. t6o d2or3itals7 The 3rac4ets, | and | , imply integra2
tion o/er the electronic coordinates r, # and $7 We use m rather than m
l
to reduce the
compleity o. the notation 6here there is no possi3ility o. con.usion7
"ur Lrst step is to epress the in/erse distance (#,d + in terms o. the spherical harmonics
(Appendi 5+7 R
4L
!# $" descri3es the position o. the electron, .or 6hich the co2ordinates
# and $ can /ary o/er their 6hole ranges, and R
4L

!#
0
$
0
" that o. the charge 6hich is
stationary at the point r
0
#
0
$
0
7 The result is1
,
#

*( r
4
L
=+
4

R
4L
R

(-727#+
d
=
4=0
24 + #

r
4
+
#

L=4
!# $"

4L
!#
0
$
0
"
6here 6e ha/e assumed that the charge is .urther .rom the nucleus than the electron at all
points o. the latterGs distri3ution, i7e7 r
0
is al6ays greater than r7 This is not essential 3ut
it simpliLes the present pro3lem 6hile retaining the essentials o. the method7 Anserting
the epression .or #,d , our matri element 3ecomes1

0e


*( #
L=+4
G
n

l

m



G
nlm
4
n

l

m

4L
0 0
nlm


d

= 0e
4=0
24 + #

r
4
+
#

G
L=4
|r R
!# $"

R
4L
!# $ "
|
G
(-727,+
Because the 3rac4ets, | and | , imply integration o/er the electronic coordinates r, #
and $, 6e can ta4e R
4L

!#
0
$
0
" outside the integration and 6rite1

0e


*( #
L=+4
G
n

l

m



G
nlm 7 7

4
n

l

m

4L
nlm


d

= 0e
4=0
24 + #

r
4
+
#

L=4
R
4L
!# $ " G
|r R
!# $"|G
L=+4
= 0e



A
4L

G
n

l

m

|r
4
R
4L
!# $"|G
nlm

(-727*+
4=0 L=4
+
0
4L
6here
*(
A
4L

24 #
#
r
4+# R

!#
7
$
7
" !-.2.5"
But each 6a/e .unction, G
nlm
, can 3e 6ritten (Section 57*+ as a product o. a spherical
harmonic !R
lm
!# $"" and a radial part (:
nl
(r++ and 6e can separate the radial and
angular integrations7 We then ha/e, simpli.ying the notation 3y dropping the (# , $+ .rom
R
lm
!# $"1

G
n

l

m

|r
4
R
4L
|G
nlm

=

:
n

l

|r
4
|:
nl

R
l

m

|R
4L
|R
lm

r
4

4L
(-727?+
6here r
4
is the epectation /alue o. the 4th po6er o. the distance o. the electron .rom
the nucleus and
4L
stands .or the angular integral7 We no6 eamine the angular integral
in detail in order to ma4e use o. symmetry and the properties o. the spherical harmonics
to reduce the sums o/er L and 47
Dor d or3itals l

=
l
=
2 and, as 6e 4no6 .rom Chapter , ('0uation (,7?7#++, the com2
3ination (coupling+ o. R
2m
!# $" 6ith R
2m

!# $" gi/es the .unctions R
l

m

!# $",
6here !2 2" l

!2 + 2", i7e7 l

can only ta4e the integer /alues 0 to *7 The angular
integral then reduces to a sum o. terms o. the .orm R
l

m

|S
4L
and since the spherical
harmonics
are a set o. orthogonal .unctions, it 6ill 3e non2Kero only .or /alues o. 4 o. 0, #, 2, ,
and *7
A .urther property, the parity, o. the integral

R
2m

|
R
4L
|
R
2m

can no6 3e used to
limit the possi3le /alues o. 4 e/en .urther7 Dor an integral to 3e non2Kero the integrand,
S
2m


R
4L

R
2m
in our case, must 3e e/en7 The parity o. a spherical harmonic R
lm
is
odd
or e/en depending on 6hether its lo3es change sign or retain their sign on in/ersion in
the origin o. coordinates so that the .unction is odd 6hen l is odd and e/en 6hen l is
e/en or Kero7 The d or3itals (l = 2+ are e/en (see Digure 57?+7 At .ollo6s there.ore, since
odd odd = e/en e/en = e/en 6hile odd e/en = odd, that 6hen 4 is odd,
4L
is
Kero and /alues o. 4 = # or , result in an integral o. Kero7 These /alues o. 4 can there.ore
3e neglected7
Thus our d2electron matri element can 3e epressed as a sum o. L.teen terms1

0e

L=+2 L=+*
G
n

2m


n2m
00
0
00 2L
2
2L *L
*
*L
d
G
= 0e
A r
+ A r
L=2
+ A r
L=* (-727-+
This epression can 3e used to calculate the d2electron matri elements .or any arrange2
ment o. charges surrounding a metal ion7 'ach o. the surrounding charges 6ill gi/e a
contri3ution o. the a3o/e .orm to each matri element7 The contri3ution .rom each charge
6ill 3e characterised 3y the di..erent /alues o. the A
4L
corresponding to the particular
/alues o. r
0
, #
0
and $
0
.or that charge7 The /alues o. the
4L
6ill 3e unchanged7
But 6here the disposition o. the surrounding charges is highly symmetrical the num3er
o. terms in the summation can 3e reduced .urther 3y placing restrictions on the possi3le
/alues o. L, as 6ill no6 3e demonstrated .or the case o. an octahedral Leld7 An octahedral
comple 6ith identical charges o. 0 at the ends o. the three Cartesian aes is sho6n in
Digure -727 The relationship 3et6een the polar and Cartesian coordinate systems is sho6n
in Appendi -7
Since the si charges are identical and the electron density o. a d2electron 6a/e .unction
(in its comple .orm+ is cylindrically symmetrical 6ith respect to rotation a3out the N
ais, the contri3ution to a matri element o. the charge at
+
F (polar coordinates r
0
, (,2,
0+ 6ill 3e e0ual to that o. the charge at
+
R !r
0
(,2 (,2"7 Thus, the /alues o. the A
4L


+N
R
F
+F
+R
N
6ig;re +1& An atom surrounded 3y an octahedral array o. negati/e electrostatic charges
at these t6o positions must 3e e0ual7 Since the only di..erence 3et6een the t6o positions
is in the /alue o. $
0
, 6e need eamine only that part o. the epression .or A
4L
6hich is
!$
0
"
=
ep!

iL$
0
"
=
cos L$
0
+
i sin L$
0
7 We ha/e1
at + F A
4L
!0" = cos 0 + i sin 0
and at + R A
4L
!L(,2" = cos L(,2 + i sin L(,2
The t6o /alues o. A
4L
can only 3e e0ual 6hen L( H2 is e0ual to Kero or an integer
multiple o. 2( 7 There.ore, L = 0 * % . . . , and since the upper limit o. |L| is * 6e
ha/e no6 restricted the possi3le /alues o. L to @ust three, 0 and *, gi/ing1

0e
G
n

2m

n2m
00
0
00 20
2
20 *0
*
*0
*
**
** **
*
**

d

G
= 0e A r + A r + A r + A r + A r
Durthermore, simple e/aluation sho6s that A
**
= A
*

*
.or each o. the .our possi3le
/alues o. $
0
!0 (,2 ( " so that1

0e
G
n

2m
n2m
00
0
00 20
2
20 *0
*
*0 **
*
** **
d

G
= 0e A r + A r + A r + A r ! + "
We are no6 in a position to calculate and ta3ulate (Ta3le -7#+ the /alues o. A
4L
and

4L
, 6hich 6e need to e/aluate the re0uired matri elements7 The /alues o. A
4L
can 3e
readily o3tained 3y su3stituting appropriate /alues o. #
0
and $
0
into '0uation (-7275+7 At
is con/enient to sum the columns o. A
4L
/alues in the ta3le 3ecause, .or any particular
matri element, the angular integral,
4L
, is independent o. the position o. the charge7
An e/aluating and ta3ulating the angular integrals,

R
2m

|
R
4L
|
R
2m

, it is use.ul to recall
that the integration o/er $ is Kero unless m
+
L

m

=
0 (see Bo -7#+ and, there.ore,
that 6e ha/e only diagonal matri elements, ecept 6here L = *7 By 6riting out the
spherical harmonics in their .ull alge3raic .orms (Appendi 5+ and a rather tedious, 3ut
straight2.or6ard, integration (Bo -7#+ 6e o3tain Ta3le -727
At no6 remains to com3ine the results o. Ta3les -7# and -72 to o3tain the re0uired
matri elements7 We Lnd the .ollo6ing, 6here

?0er
#
and

0er
*
r
5
7
0 0
4 = 0 4 = 2 4 = *
R
20
|R
40
|R
20
#,2

(

!5,( ",- ,,-

(
R
2#
|R
40
|R
2#

#,2

(

!5,( ",#*
2,-

R
22
|R
40
|R
22

#,2

!5,( ",- #,#*

(

R
22
|
R
4*
|
R
22

0 0

!5,#*(




Ta?le +1% 8alues o. A
4L
.or an octahedral comple
#
0
$
0
A
00
A
20
A
*0
A
**
+F (,2 0 2

( r
0

#
+R (,2 (,2 2

( r
0

#
+N 0 0 2

( r
0

#
F (,2 0 2

( r
0

#
R (,2 (,2 2

( r
0

#
N ( 0 2

( r
0

#
!(,5" r
0

,
! (,*" r
0

5
!,5(,2%%" r
0

5
!(,5" r
0

,
! (,*" r
0

5
!,5(,2%%" r
0

5
2

!(,5" r
0

,
2

!(,," r
0

5
0

!(,5"

r
0

,
! (,*"

r
0

5
!,5(,2%%"

r
0

5
!(,5" r
0

,
! (,*" r
0

5
!,5(,2%%" r
0

5
2

!(,5" r
0

,
2!

(,," r
0

5
0
Sum #2

( r
0

#
0 -!

(,," r
0

!,5(,#%" r
0

5
Ta?le +1& 8alues o. the non2Kero angular integrals .or an octahe2
dral comple
(
"
The 9amiltonian matri .or the L/e d or3itals in an octahedral crystal Leld7
9

c.
G
20
|
|G
20

+
|G
2#

0
|G
2+#

0
|G
22

0
|G
2+2

0

G
2#
|
0 2 ,, 0 0 0

G
2+#
|
0 0 2 ,, 0 0

G
22
|
0 0 0 + ,? 5 ,?

G
2+2
|
0 0 0 5 ,? + ,?
"n eamining the a3o/e matri 6e see that the term occurs in e/ery diagonal
element7 At represents a uni.orm increase in energy 6hich all L/e d or3itals eperience as
a result o. the surrounding si negati/e charges7 A. 6e set this common term aside .or a
moment, 6e Lnd that the diagonal elements ha/e the /alues !G
20
"

2 H, (G
2#
+ and
H? (G
22
+7 The o..2diagonal matri element 6hich connects the or3itals 6ith m
=
2
is 5 H? and 6hen 6e diagonalise the 2 2 matri 6e Lnd eigen/alues o. and 2 H,7
The .ollo6ing signiLcant results o. the .oregoing calculation may no6 3e noted1
The e..ect o. the octahedral Leld is to raise the energy o. all the d or3itals to a ne6
centre o. energetic gra/ity at 7
Core importantly, it splits the or3ital energies into t6o groups, one t6o.old degenerate
and one three.old7 Dor the dou3ly degenerate (group theoretical sym3olP e
g
+, E =

+
and .or the triply degenerate (group theoretical sym3olP t
2g
+ E
=


2 H,7
The energy2le/el splitting o. 5 H, is usually gi/en the sym3ol and, since it is such
common practice, 6e shall epress energies in terms o. rather than here7 The ne6,
raised centre o. gra/ity is not changed 3y the splitting7
The 'lectronic 'nergy Le/els o. Transition2Cetal Complees #%-
y
Since there is an o..2diagonal matri element 3et6een G
22
and G
2+2
these t6o .unc2
tions are mied in e0ual proportions 3y the crystal Leld to gi/e the or3itals 6hich
6e call G
y
and G

y
2 7 These are the one2electron eigen.unctions o. the 9amiltonian
operator 6hen it includes the octahedral crystal Leld7
There is no o..2diagonal matri element connecting the t6o .unctions G
2

#
and G
2
+
#
so these .unctions are not mied 3y an octahedral Leld7 9o6e/er, 6e generally Lnd
it con/enient to thin4 o. them in terms o. the t6o mied eigen.unctions G
K
and G
yK
6hich ha/e the same energy as G
2

#
and G
2
+
#
7
The e
g
or3ital set 6ith energy + , H5 is1
G
K
2 = G
20
and G

2 2 = !#,

The t
2g
or3ital set 6ith energy 2 H5 is1
2" !G
22
+ G
2+2
"
G
y
= !i,

2" !G
2
G
yK
= !i,

2" !G
2
2
G
#
+ G
2+2
2+#
" G
K
"
= !#,

2" !G
2#
G
2+#
" and
A. 6e imagine the d or3itals in their real .orm (Digure 57?+ then it is easy to see,
0ualitati/ely, 6hy those .or 6hich the lo3es point directly to6ards the point charges,
G
K
2 and G

y
2 , are raised more in energy that those 6here the lo3es point 3et6een
the charges, G
y
G
K
and G
yK
7 At is .ar .rom o3/ious 6hy the energies o. the G
K
2 and
G

y
2 , are raised e0ually, 3ut our 0uantitati/e calculation sho6s that this is indeed
the case7
An principle, an attempt might 3e made to e/aluate the matri elements eactly7 But this
is /ery di.Lcult on account o. our poor 4no6ledge o. the electron distri3ution 6hich
is re0uired to e/aluate the terms in r
*
7 Durthermore, the point charge model is a
/ery
approimate one and it is unli4ely that the 0uantitati/e results o3tained 6ould @usti.y
the e..ort o. calculating them7 The CD model is there.ore used in a 0ualitati/e manner
as eamples o. its applications 3elo6 6ill sho67
Similar calculations can 3e carried out .or any num3er and disposition o. charges
around a central metal ion7 The results o. such calculations .or e0ual charges placed at
the /ertices o. a cu3e, an octahedron and a tetrahedron are illustrated in Digure -7,7 ;ote
that the increase in the centre o. gra/ity is directly proportional to the num3er o. charges
so that cu3e 1 octahedron 1 tetrahedron = * 1 , 1 27 The splittings o. the le/els are
not simply related to the num3er o. chargesP cu3e 1 octahedron 1 tetrahedron, are
in the ratio % 1 $ 1 *7 The displacement o. the triply degenerate le/els (t+ .rom the
centre o. gra/ity is al6ays 2 H5 and that o. the dou3ly degenerate le/els (e+ is al6ays ,
H5, so the centre o. gra/ity is maintained7 ;ote ho6e/er, that in the cu3e and the
tetrahedron E!t" R E(e+ 6hereas in the octahedron E!t" P E(e+7
+1' THE E5ECTR2NIC ENERY 5EVE5S
26 TRANSITI2N9META5 C2M!5EDES
The CD theory, as 6e ha/e descri3ed it a3o/e, is a one2electron theory 6hich immediately
pro/ides a 0ualitati/e interpretation o. the .act that most transition2metal complees are
Cu3e
"ctahedron Tetrahedron
'nergetic c o. g
t
Cu3e
e
'nergetic c o. g
e
"ctahedron
t
'nergetic c o. g
t
Cu3e "ctahedron Tetrahedron
Tetrahedron
e
6ig;re +1' d2'lectron energy le/els Lelds in cu3ic, octahedral and tetrahedral symmetry
coloured, i7e7 they a3sor3 radiation in the /isi3le region 6hich lies at the lo62energy
end o. the electronic spectral range7 Dor eample, an a0ueous solution o. the Ti
,
+
ion
(conLguration1 Ar ,d
#
+ is red and 6e ascri3e the colour to the a3sorption o. green light 3y
a transition o. the single d2electron .rom the t
2g
le/els to the e
g
in the octahedral comple
ZTi(9
2
"+
?
\
,
+
7 This idea can 3e etended to ions 6ith more electrons 3ut, as 6e ha/e seen
in Chapter 5, 6e cannot descri3e the electronic spectra o. atoms 6ithout considering the
e..ects o. inter2electronic repulsion and spin2or3it coupling, and this is e0ually true o.
ions7 Durthermore, 6e ha/e here the additional complication o. the crystal Leld7 That is,
the 9amiltonian operator .or the pro3lem is o. the .orm1
9

= 9

0
+ 9

er
+ 9

S"
+ 9

c.
in 6hich 9

0
represents the 4inetic energy o. the electrons on the central ion and
their attraction to the nucleus o. the ion, 9

er
is the inter2electronic repulsion, 9

S"
the
spin2or3it coupling and 9

c.
the crystal Leld7 As in the case o. the .ree atom 6here
there 6as no 9

c.
, 6e ha/e to decide the order in 6hich 6e apply terms 2, , and * to
correct 9

0
7 At
turns out that, o. the se/eral possi3ilities, only three are important in practice7
An the rare earth co1%ling scheme, 6here 9

S"
is large, 6e diagonalise the matrices o.
9

er
and 9

S"
3e.ore using 9

c.
7 Thus, in this case 6e determine the energy le/els o.
the
.ree ion as eactly as possi3le, 3e.ore considering the pertur3ation o. those le/els 3y the
crystal Leld7 !ro3lems o. this type are .e6 in chemistry and 6e shall not consider them
.urther here since the other t6o possi3ilities are much more important7
An the 0ea;+Celd co1%ling scheme, 9

c.
is applied as a pertur3ation to the terms o. the
.ree2ion 6hich result .rom 9

0
+
9

er
and the spin2or3it coupling, 9

S"
, is added
last7
An the strong+Celd co1%ling scheme the one2electron or3itals o. the central ion are
Lrst com3ined under the inOuence o. 9

c.
, and then 9

er
and 9

S"
are introduced, in
that
order7 Thus, in the t6o schemes 6hich are o. most interest to chemistry, the e..ect o.
spin2or3it coupling is introduced last7 This is reOected in our treatment here in that in
Sections -7,7# to -7,7* 6e Lrst study the e..ects o. 9

c.
, and 9

er
lea/ing the
introduction
o. 9

S"
until Section
-7,757
+

2
+1'1% T$e wea>9Bel/ s#$eme "or /
&
Fexample o"
'
6 in an o#ta$e/ral Bel/G
An the 6ea42Leld approach 6e Lrst determine the terms o. the .ree ion using the methods
in Chapter 57 We then calculate the e..ect o. the crystal Leld upon these terms and 6e are
usually most interested in the term o. highest multiplicity 3ecause, according to 9und,
this 6ill 3e the ground term 6ith the lo6est energy7 An the case o. the
,
D arising .rom
d
2
6e can 6or4 6ith the 5
S
=
# component o. the triplet .or 6hich the re0uired 6a/e
.unctions are (Appendi #0+1
|, , = | + 2
+
+#
+
!#,

2" {|G
2 2
!#"
G
2+#
!2" G
2+#
!#" G
2+2
!2" }
|, 2 = | + 2
+
0
+

|, # =
!2,5"
| +
#
+
0
+
+
!,,5"
| +
2
+

#
+

|, 0 = !2,

5" | + #
+
#
+
+ !#,

5" | + 2
+
2
+

|, # = !2,5" |0
+
#
+
+

!,,5" | + #
+
2
+

|, 2 = |0
+
2
+

|, , = | #
+
2
+

;ote that all ;ets on the right2hand sides o. the a3o/e e0uations are t6o2electron Slater
determinants (Appendi ?+ characterised 3y the m /alues o. the occupied d2or3itals7 A
superscript
+
sign indicates that the electron has m
s
= +
#
7 'ach determinant can 3e
epanded as a di..erence o. t6o or3ital products as has 3een illustrated a3o/e .or the
case o. | + 2
+
+#
+
7 The su3scripts on G are the l and m /alues 6hich characterise that
or3ital7
The calculation o. the matri elements o. 9

c.
is illustrated 6ith the eample o. the
element, , ,|9

c.
|, , in Bo -727
The complete matri is .ound to 3e1
9

c.
|, +, |, # |, , |, +# |, +2 |, 2 |, 0
, +,| , ,#0

#5 ,#0 0 0 0 0 0
, #|

#5 ,#0 ,#0 0 0 0 0 0
, ,| 0 0 , ,#0

#5 ,#0 0 0 0

,
+
#
|
0 0

#5 ,#0

,#0 0 0 0
, +2| 0 0 0 0 - ,#0 ,2 0
, 2| 0 0 0 0 ,2 - ,#0 0
, 0| 0 0 0 0 0 0 , ,5
The eigen/alues o. this matri are1
, H5, three.old degenerate1 group theoretical designation,
,
T
#
7
+ H5, three.old degenerate1 group theoretical designation,
,
T
2
7
+
? H5, singly degenerate1 group theoretical designation,
,
A
2
7
At is use.ul to note here that the presence o. three o..2diagonal elements in the a3o/e
matri means that the three pairs o.
,
D 3asis states |, +, and |, # |, +2 and
|, 2 |, +# and |, , are mied 3y the Leld in proportions 6hich depend upon the
/alue o. 7 "ne 3asis state, the |, 0 6hich is a component o. the
,
T
#
, is not mied

3y the Leld and 6e shall Lnd this use.ul 6hen 6e ta4e account, as 6e do no6, o. the
presence o. another state o.
,
T
#
symmetry .ormed 3y the d or3itals, the
,
!7
+1'1& T$e wea>9Bel/ s#$eme "or /
&
Fin#l;sion o"
'
!G
The electron conLguration d
2
gi/es rise to t6o sets o. triplet states,
,
! and
,
D, and
in accordance 6ith 9undGs rules, E(
,
!+ is greater than E(
,
D+7 9o6e/er, the energy
gap 3et6een the t6o is not, in general, so large that 6e can ignore the
,
! le/elsP
especially in the interpretation o. spectra7 There.ore, 6e must no6 eamine the e..ect
o. the octa2
hedral crystal Leld on the
,
! state7 =sing the same notation as a3o/e, the three
|
L 5
L

components o. the state ha/ing 5
S
=
#.0 may 3e 6ritten1
|# # = !2,5" |2
+
#
+

!,,5" |#
+
0
+

|# 0 = !2,

5" |2
+
2
+
!#,

5" |#
+
#
+

|# # = !2,5" |#
+
2
+

!,,5" |0
+
#
+
.
The , , matri o. 9

c.
in this 3asis can 3e constructed in eactly the same manner as
that used a3o/e .or
,
D7 9o6e/er, 6e Lnd only three e0ual diagonal elements o. , 6hich
6e neglect, and no elements containing appear7 This should come as no surprise7 A
! state has the same electron distri3ution as a p or3ital and i. 6e thin4 o. the three real
p or3itals (Chapter 5+ it is clear that each one points in an identical manner to t6o o.
the si charges .orming the octahedral Leld7 The triple degeneracy o. p or3itals or a !
state is not li.ted 3y an octahedral Leld, as the symmetry designation
,
T
#
conLrms7 But
there are matri elements o. 9

c.
3et6een components o. the
,
! and
,
D states and so
our
- - matri .or the latter should 3e etended to #0 #0 in order to include the .ormer7
Dortunately, this is unnecessary7 A. 6e re0uire only the energies o. the mied
,
! and
,
D
states, 6e can ma4e use o. the .acts that the Leld does not mi the |, 0 component o.
the
,
D 6ith any other component o. that state and the |#,0(
,
!+ interacts solely 6ith the
|
, 0

component o. the
,
D state7 There.ore, 6e need to e/aluate only the matri element

,,0(
,
D+
|
9

c.
|
#,0 (
,
!+
7
=sing the 6ell2tried methods 6e Lnd1
9

c.
|, 0!
,
9 " |# 0!
,
P "
, 0!
,
9 "| , ,5 +2 ,5

# 0!
,
P "
| +
2 ,5 0
+

6here is the com3ination o. electron repulsion integrals 6hich are responsi3le .or the
di..erence in energy o. the
,
! and
,
D states (see Bo -7,+7 At is interesting to determine
the
eigen/alues o. this matri at the 6ea42Leld etreme, = 0, and the strong2Leld etreme,
7 When = 0 the eigen/alues are 0 and , i7e7 the separation o. the t6o states is,
as 6e 6ould epect, the same as it 6ould 3e in the .ree gaseous ion7 When 6e can
neglect and Lnd that the eigen/alues are * H5 and + H57 We can conLrm that these
are the epected strong2Leld eigen/alues 3y noting that, in an octahedral crystal Leld, the
energies o. the L/e d or3itals split into t6o groups, e
g
at + , ,5 and t
2g
at 2 H57
;eglecting the common contri3ution to the energy, , 6e see that the lo6est possi3le
energy o. our d
2
system in a strong crystal Leld occurs 6hen 3oth electrons occupy a
'
n
e
r
g
y

(
a
r
3
i
t
r
a
r
y

u
n
i
t
s
+
'
n
e
r
g
y


(
#
0
,

c
m

#
+
A
= 0
= 0
,
! #070
-75
570
,
2
(e
g
+
#
(e
g
+
#
275
,
D 070
275
570
070 075 #70
,
T
#
(!+
,
T
2
,
T
#
(D+
075
(t
2g
+
#
(e
g
+
#
(t
2g
+
#
(t
2g
+
#
070
Wea4 .ield
/ /
Strong .ield
6ig;re +1( Correlation diagram o. d
2
in an octahedral Leld
50
,
A
2
*0
,
T
#
(
,
!+
,0
,
T
2
20
#0
,
T
#
(
,
D+
0
0 5 #0 #5 20 25
Crystal .ield (+ (#0
,
cm
#
+
6ig;re +1) An "rgel or Tana3e2Sugano diagram .or d
2
di..erent t
2g
or3ital 6ith parallel spins, gi/ing E{!t
2g
"
#
!t

2g
"
#
} = * H57 A. 6e ha/e one
electron in a t
2g
and one in an e
g
the energy is E{!t
2g
"
#
!e
g
"
#
} = 2 ,5 + , ,5 = + ,57 We
should also note that E{!e
g
"
#
!e

g
"
#
} = +? ,57 We no6 ha/e the theoretical analysis
re0uired to determine the triplet energy le/els o. a d
2
ion in an octahedral crystal Leld
o. any magnitude and .or any /alue o. the
,
!
,
D splitting7 The results are illustrated in
Digures -7* and -75 6hich sho6, in di..erent 6ays, ho6 the energies depend on and 7
+1'1' T$e /
&
energ0 leAels "or wea>< strong an/ interme/iate
o#ta$e/ral Bel/s
Dirst, 6e summarise our epressions .or the energies7
An the intermediate region, the energies o. the
,
D states 6hich do not mi 6ith
,
! are1
E!
,
A
2
1
,
D" = +? ,5 and E!
,
T
2
1
,
D" = + ,5
The energies o. the interacting
,
! and
,
D states, o3tained 3y diagonalising the
interac2 tion matri a3o/e, are1
# # 2 2
#
E!
,
T
#
1
,
!"
= +
!

, ,5"
+ {
!Z, ,5\

"
+
, ,5
+
!2 ,5"
}
2
2 *
# # 2 2
#
E!
,
T
#
1
,
D"
= +
!

, ,5"
{
!Z, ,5\

"
+
, ,5
+
!2 ,5"
}
2
2 *
So that in the strong2 and 6ea42Leld limits 6e ha/e1
Wea42Leld limit Strong2Leld limit
= 0 = 0 = 0 = 0
E!
,
!" = E{!e
g
"
#
!e
g

"
#
} = +? ,5
E
{
!e
g
"
#
!t
2g
"
#
} = +
,5
E!
,
D"
=
0 E
{
!t
2g
"
#
!t
2g

"
#
} =
* ,5
An Digure -7* the energies o. the .our d
2
states, calculated using the epressions a3o/e,
are plotted against , in the le.t2hand hal. o. the diagram and against , in the right2
hand hal.7 The .ar le.t is the 6ea42Leld limit 6here = 0, 6hile the .ar right corresponds
to the strong2Leld limit 6here = 0, and the Lgure represents all possi3le relati/e /alues
#
o. the t6o parameters7 The energies ha/e 3een di/ided 3y 0.# {#.0 + H
2
} 2
on the le.t and
#
3y 0.2
{
#.0
+
!#,H "
2
} 2
on the right, 6here H
=
2 , 7 The .actors 0.# and 0.2 are
chosen to ma4e the total span o. energy le/els at 3oth etremes o. the diagram the same7
The .actors in parentheses ensure that le/els meet at = 7 Lo6
5
has measured the
electronic spectrum o. 8
,
+
ions (conLguration1 Ar ,d
2
+ in an aluminium oide host and
Lnds prominent 3ands at #- *00, 25 200 and ,* 500 cm

#
7 This is a d
2
ion
octahedrally
coordinated 3y oide ions and represents eperimental data 6hich may 3e interpreted
using Digure -7*7
We proceed as .ollo6s7 The energies o. the three 3ands o3ser/ed 3y Lo6 are in the
approimate ratios # 1 #75 1 2 and 6e there.ore see4 a position on the horiKontal ais
o. Digure -7* 6here the energy gaps 3et6een the lo6est le/el and the three a3o/e it
are
in these ratios7 We Lnd it on the strong2Leld side o. the diagram 6here , 0.557
This assigns the spectrum and gi/es us the ratio o. to 7 By noting that the energy
gap 3et6een the
,
A
2
and
,
T
2
states is , 6e Lnd their approimate a3solute /alues to
3e #- #00 and $*00 cm

#
7 The 6ord a%%roximate is used .or three reasons7
Dirstly, since 6e ha/e three energy di..erences and t6o un4no6ns, the pro3lem is o/er2
determined and slightly di..erent /alues o. the parameters 6ould 3e o3tained 3y using
the data in a di..erent 6ay7 Secondly, the o3ser/ed 3ands are 3roadened 3y /i3rational
e..ects and the position o. the pure electronic transition cannot 3e determined to 3etter
than

500 cm

#
7 Thirdly, and most importantly, this simple CD model does not @usti.y
more eact analysisP the agreement o. theory 6ith eperiment is already 0uite remar4a3le
and the ma@or aim o. assigning the spectrum has 3een achie/ed7
A second diagrammatic 6ay o. analysing the spectrum o. a d
2
ion in an octahedral
en/ironment is sho6n in Digure -757 <iagrams o. this type 6ere Lrst deri/ed 3y Tana3e
and Sugano and 3y "rgel in #$5*H57 Digure -75 is a reproduction o. part o. the Tana3e
and Sugano diagram .or d
2
7 The e..ect upon the triplet state energies o. increasing at a
constant /alue o. ($500 cm

#
in this Lgure+ is sho6n in 6a/e num3er units7 The energy
o. the
,
T
#
!
,
D" ground state is su3tracted .rom each o. the .our energy le/els7 At
there.ore appears in the diagram as a horiKontal line o. Kero energy so that the energy
gaps to the other three states are 0uantitati/ely represented 3y their /ertical heights a3o/e
this ground state line7 A good approimation to the eperimental data, and there.ore an
assignment
o. the spectrum, is o3tained 6here

#% ,00 cm

#
7 The di..erence in the /alue o.
.ound .rom the t6o diagrams should not 3e thought signiLcant7 Since 3oth are 3ased on
eactly the same theoretical analysis, the same /alues o. the t6o parameters, and ,
could 3e deduced .rom eitherP 3ut any attempt to 3ring the results closer together 6ould
3e 0uite un@ustiLed 3y the simple model and the uncertainties inherent in the assignment
o. precise energies to 3road eperimental 3ands7
Tana3e and Sugano reported diagrams o. the a3o/e type .or d
2
to d
%
ions and repro2
ductions o. them can 3e .ound in numerous 3oo4s7 Both aes are usually graduated in
units o. :acahGs B parameter, a measure o. the electron repulsion in the ion7 Dor the d
2
case, .or eample, B = ,#57 An this 6ay a single diagram can 3e made /alid .or all ions
ha/ing the same num3er o. d electrons, in contrast to Digure -75 6hich applies only to a
d
2
ion 6ith = $500 cm

#
7
A .e6 remar4s concerning the relati/e merits o. Digures -7* and -75 are in order7 At
Lrst glance, the energy2le/el plots o. Digure -75 appear to 3e straight lines, and the .act
that the energies o.
,
A
2
and
,
T
2
depend only on suggests that they should indeed
3e linear7 The energies o. the t6o
,
T
#
states depend on as 6ell as and are
there.ore epected to 3e cur/es7 9o6e/er, 3ecause 6e ha/e made
,
T
#
(D+ a 3ase line its
cur/ature has 3een superimposed upon the plots o. the other three energies7 But the
cur/ature is slight7 Core important is the .act that Digure -75 sho6s energies as a
.unction o. 3ut 6ith a Led, pre2selected /alue o. and there.ore applies .or that
/alue o. only7 This o3@ection does not apply to Tana3e2Sugano diagrams in general,
nor to Digure -7* in 6hich all possi3le relati/e /alues o. and are sho6n in the one
Lgure7 The dra63ac4 is that only relative /alues are represented and the diagram conceals
the linear dependence o. some states on 7
+1'1( T$e strong9Bel/ s#$eme "or /
&
in an o#ta$e/ral Bel/
The po6er and ready a/aila3ility o. digital computers ha/e made it easy to calculate the
energy le/els o. a d
2
ion in an octahedral Leld .or any com3ination o. parameters, e/en
6hen the singlet states are included7 At 6as not al6ays so7 Durthermore, 6hen under2
standing as 6ell as a 0uantitati/e analysis is sought, a thought.ul, alge3raic approach to a
pro3lem has much to recommend it and so 6e no6 approach the pro3lem .rom the strong2
Leld end7 An the strong2Leld approimation to the d
2
pro3lem 6e Lrst diagonalise 9

c.
and o3tain the real d or3itals 6ith energies + , ,5 and 2 ,5, as in Section -727
A. 6e then .ocus our attention on the states o. highest multiplicity, i7e7 states in 6hich
the t6o d electrons occupy di..erent or3itals 6ith their spins parallel, 6e see that 6e can
.orm the .ollo6ing conLgurations1
!t
2g
"
#
!t
2g

"
#
E = 2 ,5 2 ,5 = * ,5 E!
,
T
#
1 t
2g
2
"
!t
2g
"
#
!e
g
"
#
E = 2 ,5 + , ,5 = + ,5 E!
,
T
#
1 t
2g
e
g
" and E!
,
T
2
"
!e
g
"
#
!e
g

"
#
E = , ,5 + , ,5 = +? ,5 E!
,
A
2
"
2
2
The uni.orm rise in energy o. 2 has 3een neglected and the t6o states o. T
#
symmetry
are distinguished 3y the electron conLgurations .rom 6hich they originate7 ;ote that t6o
distinct states,
,
T
#
and
,
T
2
, arise .rom the conLguration !t
2g
"
#
!e
g
"
#
7 These states also
di..er in energy 6hen electron repulsion is included due to the di..erent spatial
distri3utions o.
the K
2
and
2

y
2
d2or3ital 6a/e .unctions (see Bo -7,+7
We no6 ha/e to introduce the pertur3ation o. the inter2electronic repulsion represented
3y 9

er
7 This 6ill change the energies o. the electronic states and 6e can calculate
this
change 3y epressing each conLguration as a Slater determinant in 6hich the real d
or3itals are epressed in terms o. the G
lm
7 The calculation is 0uite straight.or6ard 3ut
tedious and 6e 6ill not do it here7 At is 6ell descri3ed 3y Ballhausen7
#
We Lnd that the
electron repulsion raises the energy o. each state as sho6n in the matri 3elo67 Since
6e are only interested in energy di..erences, a constant term (:acahGs A+ 6hich arises in
each diagonal has 3een omitted7 Anterelectronic repulsion may also cause states to mi,
a phenomenon 4no6n as conLguration interaction7 9o6e/er, group theoretical principles
tell us that states o. di..erent symmetries cannot 3e mied 3y an operator li4e 9

er
,
6hich
has the .ull symmetry o. the system, and 6e there.ore epect that there 6ill 3e miing
only 3et6een the t6o states o. T
#
symmetry7 The complete energy matri, including the
crystal Leld 3ut 6ith 2 + A omitted .rom each diagonal element, is1
9

er
E!
,
T
#
1 t
2g
2
" E!
,
T
#
1 t
2g
e
g
" E!
,
T
2
" E!
,
A
2
"
E!
,
T
#
1 t
2g
2
"
* ,5 ,, 2 ,5 0 0
E!
,
T
#
1 t
2g
e
g
"
2 ,5 + ,5 + * ,#5
0 0
E!
,
T
2
" 0 0
+ ,5 % ,#5
0
E!
,
A
2
" 0 0 0
+? ,5 % ,#5
The eigen/alues o. the 2 2
,
T
#
matri are , ,#0 ,,0
#
{
2
+
2
+ ? ,
#
5
} 2
7 We can chec4 this result 3y noting that at Kero electron repulsion (
=
0+ the
,
T
#
eigen/alues are * ,5 and + ,5, 6hile at Kero Leld ( = 0+ their energy separation
is 7 These are the correct limiting results7 The s0uare root in the a3o/e energies ma4es
their use in assigning spectra and determining the /alues o. the parameters and a
little di.Lcult7 But in the strong Leld regime 6here terms in the energy 6hich
in/ol/e ! , "
2
or higher po6ers may 3e neglected and 6e can approimate the s0uare
root as .ollo6s1
# #
{

2
+

2
+
? ,5
} 2 =

{
#
+
! , "
2
+
? ,5
} 2
#


{
#
+
? ,5
} 2

{
#
+
#

? ,5
} =

+
, ,5
With this approimation E!
,
T
#
1 t
2g
2
" = * ,5 + ,5 and the energy di..erences, in
ascending order, 6hich might 3e compared 6ith eperimental data, are1
E!
,
T
2
" E!
,
T
#
1 t
2g
2
" = ,5
E!
,
T
#
1 t
2g
e
g
" E!
,
T
#
1 t
2g
2
" = + , ,5
E!
,
A
2
" E!
,
T
#
1 t
2g
2
" = 2 ,5.
Aleander and Gray
?
ha/e reported 3ands at 22 -00 cm

#
and 2- 200 cm

#
in the spec2
trum o. the comple, ,d
2
ion Z8(C;+
?
\
,

7 A. 6e assign the Lrst o. these 3ands to the

'
n
e
r
g
y

(
#
0
,

c
m

#
+
E!
,
T
#
1 t
2g
2
" E!
,
T
2
" transition and the second to the E!
,
T
#
1 t
2g
2
" E!
,
T
#
1 t
2g
e
g
"
6e readily Lnd 2, %00 cm

#
and 5?00 cm

#
7 The large /alue o. , sho6s
that 6e really are in the strong2Leld regime and @ustiLes the a3o/e neglect o. ! , "
2
and
higher po6ers7 With these /alues o. and 6e predict that the E!
,
T
#
1 t
2g
2
" E!
,
A
2
"
3and should lie at a3out *? 500 cm

#
6here it is hidden under much stronger 3ands due
to other electronic transitions7
+1'1) Spin9or?it #o;pling
The Lnal inOuence upon energy le/els is that o. spin2or3it coupling 6hich, .or the tran2
sition metals o. the Lrst series, is much smaller than the crystal Leld or the electron
repulsion7 At 3ecomes increasingly important as 6e descend the periodic ta3le and espe2
cially 6hen 6e encounter the rare earths7 As an illustration 6e consider the e..ect o.
increasing spin2or3it coupling on the conLguration d
2
in a strong crystal Leld (Digure -7?+7
"n the le.t the .our triplet energy le/els are plotted7 The matri o. all *5 possi3le d
2
states
has 3een diagonalised 6ith = 5?#0, = 2, %00 and the spin2or3it coupling constant,
V
d
= 0 2000 cm

#
7 These /alues o. the parameters 6ere chosen so as to reproduce the
spectrum o. Z8(C;+
?
\
,

discussed a3o/e at lo6 /alues o. V
d
7 The energy o.
,
T
#
!
,
D"
6hen
V
d
= 0 has 3een set to Kero and, in order to include all #, distinct le/els in one diagram,
#$ 000, 20 000 and ,- 000 cm

#
ha/e 3een su3tracted .rom the energies o. the
,
T
2
,
,
T
#
and
,
A
2
states respecti/ely7 All
,
T le/els 3eha/e 0ualitati/ely as i. they 6ere
,
!, that
is they gi/e rise to states ha/ing Q != L + S" /alues o. 2, # and 0 .or non2Kero V
d
, and
the
52.old degeneracy o. the Lrst is li.ted .urther 3y the crystal Leld7 The de/elopment o. the
le/els as V
d
is increased .rom Kero to 2000 cm

#
is sho6n 6ith the Q /alues, and degen2
eracies (2Q + #+ on the right7 ;ote that at lo6 /alues o. V
d
the L/e2.old degeneracy o.
the states 6ith Q = 2 is scarcely li.ted and in this range the le/els in each group o3ey an
approimate Landeb inter/al rule, i7e7 E!Q = 2" E!Q = #" 2{E!Q = #" E!Q = 0"}7
An order to assess the e..ect o. spin2or3it coupling on electronic spectra 6e Lrst note
that the ranges o. the eperimentally determined /alues o. V
nd
are 50 I %50, 200 I
#$00 and ,00 I 5000 cm

#
.or n = ,, * and 5 respecti/ely
*
6hilst eperimental 3and 6idths
#070
,
A
2
I ,-70
(e+
#
(e+
#
,
J = #
2
#070
%70
,
T
#
(
,
!+ I 2070
,
J = 2
%70
?70
*70
270
070
270
(t
2
+
#
(e+
#
,
T
2
(
,
D+ I #$70
(t
2
+
#
(e+
#
,
T
#
(
,
D+
(t
2
+
#
(t
2
+
#
070 075 #70
,
J = #
#
J = 0
2
J = 2
,
,
J = #
#
J = 0
#
J = 0
,
J = #
,
J = 2
2
#75 270
?70
*70
270
070
270
Spin2or3it coupling constant K
d
(#0
,
cm
#
+
6ig;re +1* The e..ect o. spin2or3it coupling on the strong2Leld triplet states o. d
2
typically lie 3et6een #000 and *000 cm

#
7 Thus, the splittings in Digure -7? attain the
order o. magnitude o. typical 3and6idths only on the right2hand side o. the diagram
6here V
d
= 2000 cm

#
7 Such /alues o. V
d
are not .ound until the end o. the second
transition metal series and in the third7 The result is that it is rare to see e/idence o.
spin2or3it coupling in the .orm o. 3and splittings in electronic spectra7 By miing states
o. di..erent multiplicity, spin2or3it coupling also causes 3rea4do6n o. the strict S = 0
selection rule (see Section 57##+ 3ut this e..ect also re0uires that V
d
ha/e a su3stantial
/alue and spectral 3ands made allo6ed in this manner are rarely o3ser/ed 6ith light
transition metals7 9o6e/er, Aleander and Gray
?
o3ser/ed t6o such 3ands,
,
T
#g

#
T
2g
at #* ?00 cm

#
and
,
T
#g

#
T
#g
at #$ 200 cm

#
, in their spectrum o. >
,
8(C;+
?
7
Dor 8
,
+
V
d
%?0 cm

#
7
Thus .ar in our account o. the theory o. the electronic structure and 3onding in
transition2metal complees 6e ha/e gi/en a .airly detailed analysis o. d
2
systems7 An
a non2specialised /olume such as this, space does not permit a similar treatment o. d
,
to
d
#0
.or 6hich 6e must re.er the reader to the 3i3liography7
#*
We ha/e 3een dra6n into
a consideration o. electronic spectra 3ecause spectral data pro/ide the most direct 6ay o.
determining and , the essential parameters o. the CD model7 ;o account o. the theory
o. the transition2metal ions 6ould 3e complete 6ithout some re.erence to their electronic
spectroscopy7 But this is a /ast and complicated su3@ect 6hich is 6ell treated in a num3er
o. specialist /olumes
*-
and here 6e can only dra6 attention to a .e6 signiLcant points7
+1( THE E5ECTR2NIC S!ECTR2SC2!Y
26 TRANSITI2N9META5 C2M!5EDES
Thus .ar 6e ha/e compared the positions o. calculated and o3ser/ed electronic transitions
6ithout as4ing 6hether or not those transitions 6ere su.Lciently intense to 3e seen7 Since
6e ha/e 3een concerned eclusi/ely 6ith d electrons, the states in/ol/ed must all 3e o.
e/en parity and the transitions, all d d, 3et6een states o. the same parity7 Spectroscopic
selection rules are discussed in detail in Sections 57##, %7* and %75, so it su.Lces here to
say that transitions 3et6een states o. the same parity are strictly .or3iddenP the Laporte
rule7 The .act that these d d 3ands, though rather 6ea4, are indeed o3ser/ed is due to
the loss o. parity 6hich can arise in either a static or a dynamic manner7 A. the ligand
en/ironment is not strictly octahedral, e7g7 3ecause o. a slight static distortion, then the
centre o. symmetry o. the comple as a 6hole may 3e lost and 6ith it the deLniti/e
e/en parity o. the d or3itals and states7 A d d transition may then 3ecome 6ea4ly
allo6ed, .re0uently 3ecause the lo6ered symmetry allo6s p and d or3itals to mi7 This
is particularly true o. tetrahedral complees7 The tetrahedron has no centre o. symmetry
and the d d transitions o. tetrahedral complees are in/aria3ly more intense than those
o. their octahedral counterparts7 The loss o. symmetry need not 3e permanent and staticP
/i3rations can ha/e the same e..ect o. ma4ing a transition partially allo6ed7
The CD model is concerned solely 6ith the energies o. the d2electron states 3ut the
intense colours o. many transition2metal complees, e7g7 the purple colour o. ZCn"
*
\

and
the 3lood red o. ZDe(C;S+
?
\
,

, arise not .rom d d transitions, 6hich as 6e ha/e seen

a3o/e are normally /ery 6ea4, 3ut .rom charge+transfer transitions in 6hich electrons
are trans.erred .rom the ligands to the metal (LCCT+7 ZDe(2,2

23ipyridine+
,
\
2
+
sho6s a
strong a3sorption at 522 nm due to the re/erse process, a metal2to2ligand charge trans.er
The Cagnetism o. Transition2Cetal Complees #$-
(CLCT+7 Transitions o. this type are .urther e/idence o. co/alency and re0uire a molecular
or3ital treatment .or their 0uantitati/e understanding7
Apart .rom in Section -7,75, 6e ha/e re.erred only to transitions 3et6een states o.
the same multiplicity, triplet states in the case o. d
2
7 d d transitions 6hich in/ol/e a
change o. multiplicity, triplet to singlet in the case o. d
2
, are dou3ly .or3idden and are
/ery 6ea4 indeed7 But as spin2or3it coupling gro6s in the *d and 5d series o. metals,
and especially in the rare earths, nominally spin2.or3idden transitions gain in intensity
3ecause o. the loss o. a clearly deLned multiplicity .or each state7 The multiplicity o.
the ground state o. a transition2metal comple is not only important .or the electronic
spectroscopy o. the compound, there are other interesting conse0uences, some o. 6hich
6e eplore in the net t6o sections7
+1) !AIRIN ENERIESK 5249S!IN AN3 HIH9S!IN C2M!5EDES
Consider the au.3au principle as applied to a d
*
comple in a strong octahedral Leld7
Dollo6ing 9undGs rules, the Lrst three electrons 6ill 3e placed in the triply degenerate
t
2g
or3itals 6ith their spins parallel7 An placing the .ourth electron 6e ha/e a choice
3et6een dou3le occupation o. a t
2g
or3ital, gi/ing a triplet state, or the use o. an empty
e
g
or3ital gi/ing a 0uintet7 The actual or3ital occupation 6ill 3e that o. lo6er energy
6hich depends upon the relati/e magnitudes o. the interelectronic repulsion in a dou3ly
occupied t
2g
or3ital and the energy gap, , 3et6een the t
2g
and e
g
or3itals7 Calculation
sho6s that1
e
g

t
2g

'nergy
5
'
=
?A

2#B
+
'nergy
,
T
#
=
?A

#5B
+
5C
An these e0uations the electron repulsion energy is 6ritten in terms o. :acah parameters,
A, B and C
*
(Bo -7,+ and 6e do not re0uire to del/e into the eact .orm o. these integrals
to see that 6hen = ?B + 5C the energies o. the t6o states are e0ual7 Similar e0ualities
arise in the d
5
, d
?
and d
-
cases so that a large crystal2Leld splitting causes electron spins
to pair 6hilst small /alues o. lead to the maimum num3er o. unpaired spins7 The
corresponding complees are re.erred to as lo0+s%in and high+s%in respecti/ely7 Though
the conse0uences o. the t6o possi3ilities .or electron pairing can 3e detected in the spectra
o. the comple and in many o. its other physical and chemical properties, the e..ect is
most mar4ed in its magnetic 3eha/iour 6hich is largely determined 3y the num3er o.
unpaired electrons7
+1* THE MANETISM 26 TRANSITI2N9META5 C2M!5EDES
The .ollo6ing .ormula .or the magnetic moment (T+ o. a molecule in Bohr magnetons is
discussed in Section #2721
#
T
total
=
Z
{
L!L
+
#"
} +
*
{
S!S
+
#"
}
\
2
T
B
At is appropriate .or situations in 6hich the multiplet splittings that result .rom spin2
or3it coupling are small compared 6ith ;- and should there.ore 3e applica3le to the
#$% Transition2Cetal Complees
2 # # #7-, ,700
f
2 # # #7-, ,700
f
, - , ,7%- 5720
f
, % 2 27%, *7*- 2.% ,.5
2 $ # #7-, ,700 #.- 2.2
Ti
,+ #
2
8
*
+
8
,
+
Cr
,
+
Cr
2
+
#
#
,
2
Cn
2
+
5
De
,
+
5
2
transition2metal ions .rom Ti
,
+
to Cu
2
+
.or 6hich the spin2or3it coupling constant, V
d
, is
small7 L and S are the total or3ital and spin angular momenta respecti/ely7 An Ta3le -7,
the a3o/e .ormula is used to calculate the magnetic moments o. the .ree transition2metal
ions o. the Lrst transition series and the results are compared 6ith the measured moments
.or the octahedrally co2ordinated ions in their high2spin states7 The T
S
(spin2only+ /alues
6ere calculated 3y setting L = 07 The conLgurations mar4ed f are those .or 6hich there
can 3e an or3ital contri3ution to the magnetic moment (see 3elo6+ n = num3er o. d
electrons, n

=
num3er unpaired7
Comparison o. the theoretical and eperimental data in Ta3le -7, re/eals that, in many
cases, the eperimental magnetic moment is 0uite close to the spin2only /alue, i7e7 the
electronic or3ital angular momentum appears to contri3ute /ery little to the total magnetic
moment o. a ,d
n
transition2metal ion7 This has the important, and particularly use.ul, con2
se0uence that T
ep .
gi/es a /ery direct indication o. the num3er o. unpaired electrons7 The
reason .or the small contri3ution .rom the or3ital motion o. the electrons is that this has
3een 71enched 3y the interaction o. the metal d2electrons 6ith the ligands7 An our model
this interaction is purely electrostatic, 3ut the .act that the 0uenching is in many cases so
complete strongly suggests that there is co/alent 3onding 3et6een ligand and metal7 The
latter pro/ides an e/en 3etter 0uenching mechanism since it pre/ents the electrons .rom
circulating the metal nucleus 3y loc4ing them into localised chemical 3onds7
Though the lac4 o. an or3ital contri3ution to the magnetic moment is readily 0ual2
itati/ely understanda3le, it is o. interest to en0uire 6hether 6e can place the concept
o. 0uenching on a Lrmer theoretical 3asis in order to understand 6hy, in some cases at
least, signiLcant or3ital contri3utions to the magnetic moment remain7 An pursuit o. this
o3@ecti/e 6e Lrst recall the matri o. the L/e d or3itals in an octahedral crystal Leld
Ta?le +1' Calculated magnetic moments, in Bohr magnetons, o. the ground
states o. some .ree transition2metal ions and the eperimental magnetic moments
.or the octahedrally co2ordinated ions in their high2spin conLgurations
Aon S L n n

T
S
T
total
T
ep
#.- #.%
2
#.-

#.%
, 2 2 27%, *7*- 2.?

2.%
f
2
, , , ,7%- 5720 ,.-

,.$
2 * * *7$0 57*% *.- *.$
Cn
,
+
2 2 * * *7$0 57*% *.$

5.0
2
0 5 5 57$2 57$2 5.?

?.#
2
0 5 5 57$2 57$2 5.-

?.0
De
2
+
2 2 ? * *7$0 57*% 5.# 5.5
f
Co
,
+
2 2 ? * *7$0 57*% ca7 57*
f
Co
2
+
,
2
;i
2
+
#
Cu
2
+
#
*.# 5.2
f
The conLgurations mar4ed f are those .or 6hich there can 3e an or3ital contri3ution to
the magnetic moment, see tet7 n = num3er o. d electrons, n

= num3er unpaired7
97L7 SchlaM.er and G7 Gliemann, /asic Princi%les of Ligand 9ield -heory7 #$?$, John
Wiley & Sons LtdP reprinted 6ith permission7
(Section -72+ and the remar4s .ollo6ing it7 The t6o d or3itals, ha/ing m /alues o. +2
and 2, 6ere .ound to ha/e eactly the same diagonal matri element ( + ,?+ and
to 3e connected, and hence mied, 3y an o..2diagonal matri element o. 5 ,?7 Since
the diagonal elements are e0ual, the resulting mied 6a/e .unctions, d
y
and d

y
2 , 6ill
each contain e0ual parts o. m = +2 and m = 2 and 6ill there.ore ha/e no K2component
o. or3ital angular momentum7 Since there are no other o..2diagonal matri elements,
the remaining three d or3itals 6ill retain their K2components o. angular momentum o.

#h,2( and 07 An an octahedral Leld, the description o. these or3itals as d

K
, d
yK
and
d
K
2 rather than as d
+#
, d
#
and d
0
is a matter o. choice, not o. necessity7 There.ore,
6hen a magnetic Leld is applied along the K2direction the d
#
6ill 3e slightly lo6er in
energy than the d
+#
, 3ecause o. the Leld produced 3y the or3iting electron, and i. the
conLguration is such that it is possi3le to place more electrons in d
#
than in d
+#
an
or3ital contri3ution to the total magnetic moment o. the material may result7 But note
that this potential or3ital moment can still 3e 0uenched 3y .orces not considered in our
simple electrostatic interaction matri7 Adenti.ying the t6o groups o. degenerate d or3itals
in the octahedral Leld 3y their group2theoretical sym3ols, the conLgurations 6hich can
mani.est an or3ital contri3ution to the magnetic moment are, .or high spin, i7e7 minimum
possi3le electron pairing1 (t
2g
+
#
, (t
2g
+
2
, (t
2g
+
*
(e
g
+
2
and (t
2g
+
5
(e
g
+
2
7 These conLgurations
are mar4ed f in Ta3le -7,7 An the lo6 spin conLgurations 6ith maimum spin pairing
the conLgurations (t
2g
+
*
and (t
2g
+
5
may contri3ute or3ital moments7 When 6e compare
the high2spin predictions 6ith the a3o/e ta3le 6e see that the ions 6ith si and se/en d
elec2 trons are indeed those 6here the highest eperimental moments match T
total
most
closely7 The minimal or3ital contri3utions to the ions 6ith one or t6o d electrons are
thought to 3e due to de/iations o. the complees .rom eact octahedral geometry7 This
may 3e a result o. .orces in the crystal lattice (all the measurements in Ta3le -7, 6ere
made on solids+ or they may 3e due to a Jahn2Teller e..ect, the origin o. 6hich space
does not allo6 us to pursue .urther here7 An either case, a small distortion lin4s the d
+
#
and d

#
or3itals 6ith a small o..2diagonal matri element and causes them to mi .orming d
K
and
d
yK
, 6here3y the K2component o. their or3ital angular momentum is lost7
As a last 6ord on the comple su3@ect o. or3ital contri3utions to magnetic moment
6e might note that, i. spin2or3it coupling is signiLcant, in conLgurations ha/ing less than
L/e electrons the spin and or3ital angular momenta are antiparallel in the state o. lo6est
energy so the or3ital contri3ution has to 3e su3tracted .rom the spin contri3ution7 The
re/erse is the case 6here the num3er o. d electrons is greater than L/e7
+1+ C2VA5ENCY AN3 THE 5IAN3 6IE53 THE2RY
As early as #$,5, 8an 8lec4 recognised that any 6idely applica3le theory o. transition2
metal complees 6ould ha/e to include the e..ects o. co/alent interaction 3et6een metal
and ligand, e/en though compelling eperimental e/idence .or it 6as una/aila3le at that
time7 An the #$50s, ho6e/er, Lrstly electron paramagnetic resonance ('!:+ and then
nuclear magnetic resonance (;C:+ measurements le.t no room .or dou3t and pro/ided
0uantitati/e e/idence7 The essential nature o. the e/idence is easy to eplain7 An the case
o. '!: spectroscopy,
%
6e measure the a3sorption o. radiation (in the micro6a/e region+
3y one or more unpaired electrons in a magnetic Leld 6here the energies o. electrons
# #
ha/ing m
s
= +
2
and m
s
=
2
are di..erent7 Apart .rom the magnetic Leld imposed 3y
the spectrometer, the electron sees other Lelds, in particular the Lelds due to the magnetic
nuclei (Chapter #0+, 6hich it /isits as it ma4es its peregrinations through the molecule7
These Lelds cause splittings, 4no6n as Cne str1ct1re, in the spectra and the magnitude o.
a particular splitting is proportional to the product o. the nuclear magnetic moment and
the pro3a3ility that the unpaired electron 6ill 3e .ound at that particular nucleus7
]
An this
6ay the interaction o. unpaired electrons .rom the Cn
2
+
ion 6ith D

ions in CnD
2
6as
o3ser/ed and measuredP to mention @ust one o. many similar eperiments7 Clearly, such a
hyperLne interaction is only possi3le i. there is miing o. metal and ligand atomic or3itals
to .orm molecular or3itals, i7e7 co/alency7 The ;C: e/idence is similarly direct and 6ill
not 3e discussed here7 Thus, co/alency cannot 3e denied, 3ut the great success o. the
simple CD theory also leads us to epect that there 6ill 3e important similarities 3et6een
the results o. an C" theory o. transition2metal complees and those o. the crystal Leld,
and indeed there are7
We can illustrate this point 3y applying the C" theory, in linear com3ination o.
atomic or3itals (LCA"+ .orm, to a simple, hypothetical, octahedral comple, C9
?
, in
6hich the d2or3itals o. the central metal ion .orm co/alent 3onds 6ith the #s or3itals o.
si surrounding hydrogen atoms placed e0ually distant .rom the metal atom at , y
and K (Digure -7-+7
"ur calculation 6ill use a /ery simple C" theory, 0uite li4e the 9uM c4el procedure
(Section #27#+ 3ut, 3ecause the interactions 3et6een the metal ,d or3itals and the sur2
rounding hydrogen #s or3itals, $
i
, are not all e0ual, 6e shall Lnd it necessary to use the
,d | #s o/erlap to estimate the 3onding 3et6een them7 We ta4e the d or3itals in their real
.orms and 6e note immediately that those .or 6hich the lo3es lie *et0een the Cartesian
aes, i7e7 d
K
, d
yK
and d
y
ha/e Kero o/erlap, and hence Kero interaction 6ith the hydrogen
atoms7 This is 3ecause each hydrogen #s or3ital has an e0ual and opposite o/erlap 6ith
the lo3es o. the a3o/e d2or3itals 6hich lie on either side o. it (Digure -7%+7 By contrast, the
d

y
2 and d
K
2 or3itals, 6hich are directed along the Cartesian aes, o/erlap strongly 6ith
their neigh3ouring hydrogen #s or3itals7 We can already see here the 3asis o. a distinction
+N 95
R
F
9*
9,
9# 92
+F
+R
N
9?
6ig;re +1+ "ctahedral C9
?
molecule
]
The phrase Qat the n1cle1s G may appear a little strange, 3ut 6e are tal4ing here not o. the dipole2dipole 3ut the Dermi2contact
interaction .or 6hich the electron has to ha/e a Lnite pro3a3ility o. actually 3eing at the nucleus o. the atom in 0uestion7
Carrington and CcLachlan
%
gi/e a nice treatment o. the theory in/ol/ed7 See also Section *7$7
9

d

2
y
2 d
K
2 $
#
$
2
$
,
$
*
$
5
$
?
d

2
y
2 Ed 0


,K


,K
0 0
d
K
2 0 Ed K K K K 2K 2K

,K

,K
N
R

+
+
+ F
+

+
F
+
+
+
+

I
+

"/erlap o. d
K
6ith
9#, 9,, 95 and 9?
6ig;re +1, Atomic or3ital o/erlap in C9
?
"/erlap o. d

2
y
2
6ith
9#, 92, 9, and 9*
3et6een these t6o sets o. d or3itals 6hich is central to the success o. the CD theory7 The
o/erlaps 6hich 6e re0uire may 3e epressed in terms o. an ar3itrary parameter, ' , as
.ollo6s1
d
K
2 |$
#
= d
K
2 |$
2
= d
K
2 |$
,
= d
K
2 |$
*
= '
d
K
2 |$
5
= d
K
2 |$
?
= 2'

d

2
y
2
|
$
#
=
d

2
y
2
|
$
2
=
d

2
y
2
|
$
,
=
d

2
y
2
|
$
*
=

,'
And 6e assume that the interactions, 6hich 6e epress in the .orm o. a 9amiltonian
energy matri (Appendi ,+, are proportional to these o/erlaps1
,K ,K
$
#
Es 0 0 0 0 0
$
2

,K

K 0 Es 0 0 0 0
$
,

,K K 0 0 Es 0 0 0
$
*

,K

K 0 0 0 Es 0 0
$
5
0 2K 0 0 0 0 Es 0
$
?
0 2K 0 0 0 0 0 Es
An this matri, Ed and Es are the energies o. the metal d or3itals and hydrogen #s
or3itals respecti/ely7 The o..2diagonal elements are the interaction energies epressed in
terms o. a parameter K , proportional to ' , 6hich, .or our present purposes, 6e do not
need to 0uanti.y .urther7 When the matri is diagonalised (Bo -7*+ 6e Lnd .our
eigen/alues o. Es7 The eigen.unctions that correspond to these eigen/alues are
com3inations o. hydrogen
#s or3itals 6hich do not ha/e the correct symmetry, e
g
or t
2g
, to com3ine 6ith any o. the
metal d or3itals7 We also Lnd t6o eigen/alues o.1
Ed
+
Es


!Ed

Es"
2
+
*%K
2
and t6o o.1
E
3
=
E
a
=
2
Ed + Es +

!Ed Es"
2
+ *%K
2
2
These energies are those o. the 3onding, E
3
, and anti3onding, E
a
, molecular or3itals
.ormed 3y interaction o. the metal d

y
2 and d
K
2 or3itals 6ith com3inations o. the hydro2
gen #s or3itals o. the hydrogen atom ligands 6hich ha/e the same symmetry7 Since the
d or3itals are 3oth o. e
g
symmetry the molecular or3itals must also 3e o. e
g
symmetry7
The symmetry is conLrmed 3y the .act that 6e ha/e a degenerate pair o. 3onding and a
degenerate pair o. anti23onding or3itals7 As 6e ha/e seen a3o/e, the hydrogen atoms o.
our C9
?
molecule o..er no or3itals suita3le .or com3ination 6ith metal d or3itals o. t
2g
symmetry, so the d
K
, d
yK
and d
y
or3itals o. the metal ta4e no part in the 3onding and
remain triply degenerate 6ith energy Ed, 6hich lies 3et6een the 3onding and anti3onding
e
g
molecular or3itals7 9o6e/er, 6here the ligands ha/e /alence p or3itals interaction 6ith
the d
K
, d
yK
and d
y
or3itals o. the metal is possi3le and triply degenerate 3onding and
anti3onding molecular or3itals result7 Thus the C" model reproduces all the essential
.eature o. the CD7 "ur results .or the C9
?
comple are illustrated in Digure -7$7
Thus .ar, the energy2le/el scheme a3o/e reOects the CD scheme 0uite 6ell 3ut a
pro3lem arises 6hen 6e as4 6hich energy le/els are occupied and 6hich unoccupied7
Si hydrogen atoms pro/ide si electrons, .our o. 6hich 6ould Lll the lo6est pair o. e
g
le/els lea/ing t6o .or the three t
#u
and the a
#g
le/els7 There.ore, at least se/en d electrons
.rom the metal are re0uired 3e.ore any enter the t
2g
and e
g
le/els, the occupation o. 6hich
is central to the CD model7 "ur simple C" model o. C9
?
appears to 3e at odds 6ith
the CD description7 But 6e should recall that in the ma@ority o. simple transition2metal
complees the ligands each donate t6o electrons to the structure7 These t6o electrons are
usually a lone pair, as 6e see /ery clearly in the coordination complees o. 6ater and
ammonia7 A. 6e assume that the hydrogen #s or3itals 6e ha/e used are, in e..ect, lone
pair or3itals containing t6o electrons, all the essentials, including the symmetry, o. the
energy2le/el scheme (Digure -7$+ remain unchanged, 3ut 6e no6 ha/e #2 ligand electrons
at our disposalP @ust enough to Lll the si lo6est le/els, i7e7 e
g
, t
#u
and a
#g
7 Any
metal d electrons must then occupy the t
2g
and e
g
le/els, in ecellent correspondence
6ith the CD model7
The pairs o. 3onding and anti3onding 6a/e .unctions .or the energy le/els o. e
g
symmetry 3ear closer scrutiny7 They arise .rom t6o identical 2 2 matrices (see Bo -7*+
and there.ore ha/e the same .orm in 3oth cases7 Ta4ing, as our eample, the com3ination
'nergy
e
g
2 anti3onding molecular or3itals
, uncom3ined metal d or3itals
t
2g
5 metal d or3itals
? hydrogen #s atomic or3itals
t
#u
+ a
#g
* uncom3ined hydrogen #s or3itals
e
g
2 3onding molecular or3itals
? 9
C9
?
C
6ig;re +1- Colecular or3ital energy2le/el scheme .or C9
?
Bi3liography and Durther :eading 20,
o. ligand or3itals,
eg!K
2
"
, 6hich 3onds to the d
K
2 metal or3ital, 6e can 6rite the 3onding
and anti3onding molecular or3itals in the .orms1

3onding
= =d
K
2 + [
eg!K
2
"
and
anti3onding
= [ d
K
2 =
eg!K
2
"
6here =
2
+ [
2
= #.0 i. or3ital o/erlap 3et6een the d or3itals and the hydrogen #s or3itals
is neglected in the normalisation7 At one etreme 6here [ = #.0 and = = 0.0 6e ha/e
the CD theory7 The lo6er2energy C",
3onding
, is composed solely o. ligand or3itals,

eg!K
2
"
, and the higher2energy C",
anti3onding
, is a pure d
K
2 or3ital o. the metal7 The
three uncom3ined metal d or3itals o. t
2g
symmetry lie immediately 3elo6 the latter7
When [ = #,

2 ([ and = 6ill only 3e eactly e0ual to #,

2 6hen Ed = Es+
6e ha/e !aulingGs co/alent /alence 3ond description
2
6ith metal d2or3itals and ligand
or3itals contri3uting approimately e0ually to the t6o molecular or3itals7 An principle, a
high20uality C" calculation 6ill determine @ust 6here 6ithin this range o. possi3ilities a
particular comple lies7 But e/en today C" or <DT calculations 6ith such a large num3er
o. electrons present considera3le pro3lems7 Comprehensi/e pac4ages 3y means o. 6hich
these theories can 3e applied to transition metal complees are a/aila3le 3ut their modi
o%erandi re0uire care.ul study i. they are to 3e used 6ith conLdence and the limitations
on their results understood7
An an important semi2empirical de/elopment, :oald 9o..man proposed his Qetended
9uM c4el theoryG7 Catri elements analogous to Es, Ed and K a3o/e are represented
3y parameters the /alues o. 6hich are o3tained 3y Ltting the results o. trial calculations to
eperiment7 The inter2or3ital 3onding interactions are determined 6ith re.erence to the
corresponding o/erlaps as 6e ha/e done .or K a3o/e, 3ut in a more sophisticated manner7
'lectron repulsion is not considered eplicitly7 Though purists ha/e sometimes 3een rather
scathing a3out the theory, it has .ound 6idespread application and acceptance in the semi2
0uantitati/e interpretation o. some o. the /ast 0uantity o. data 6hich organo2metallic
chemists in particular ha/e generated in the last 50 years7
+1, 8I85I2RA!HY AN3 6URTHER REA3IN
#7 97L7 SchlaM.er and G7 Gliemann, /asic Princi%les of Ligand 9ield -heory, Wiley2
Anterscience, London, #$?$7
D7A7 Cotton, Chemical A%%lications of .ro1% -heory, 2nd edn, Wiley2Anterscience, ;e6 Ror4,
#$-#7
C7J7 Ballhausen, :ntrod1ction to Ligand 9ield -heory, CcGra629ill, ;e6 Ror4, #$?27
S7B7 !iepho and !7;7 SchatK, .ro1% -heory in S%ectrosco%y, Wiley2Anterscience, ;e6 Ror4,
#$%,7
Z9elp.ul introductions to group theory may 3e .ound in1
S7D7A7 >ettle, Symmetry and Str1ct1re, 2nd edn, Wiley, ;e6 Ror4, #$$57
G7 <a/idson, .ro1% -heory for Chemists, CacCillan, London, #$$#7\
27 L7 !auling, -he Nat1re of the Chemical /ond, 2nd edn, Cornell =ni/ersity !ress, Athaca, #$*07
,7 97 'yring, J7 Walter and G7'7 >im3all, 31ant1m Chemistry, Wiley, ;e6 Ror4, #$**7
*7 J7S7 Gri.Lth, -he -heory of -ransition+5etal :ons, Cam3ridge =ni/ersity !ress, #$?#7
57 W7 Lo6, Oeit. %hysi;. Chem., %', #0- (#$5-+7
?7 J7J7 Aleander and 97B7 Gray, Q. Amer. Chem. Soc., -., *2?0 (#$?%+7
-7 A7B7!7 Le/er, :norganic Electronic S%ectrosco%y, 2nd edn, 'lse/ier, ".ord, #$%*7
%7 A7 Carrington and A7<7 CcLachlan, :ntrod1ction to 5agnetic Resonance, 9arper & :o6,
London, #$?-7
20* Transition2Cetal Complees
*5 *5
2
#

(
#
,5

+2
82D +1% Cal#;lation o" an ang;lar integral
'ample o. the e/aluation o. an angular integralP R
22
|R
**
|R
2+2
A7
Since R| re0uires that 6e ta4e the comple con@ugate o. R 6e ha/e1
and
R
2

2
| = |S
2
+
2
=
2
+
2
!# "
+
2
!$" =

#5
sin
2
*
#
#

2(
ep!2i$"
R
*

*
=
*

*
!# "

*
!$" =
There.ore the integral A is1
, ,5
sin
*
#?
#
#

2(
ep!

*i$"
*5

,5 # #

(
%

2(
A
=
25?

2(

2(
sin
0
# sin # d#
0
ep!0" d$
The integration o/er $ gi/es a multiplicati/e .actor o. 2( 7
At is perhaps 6orth noting here that, had the argument o. the eponential 3een
anything other than Kero, in$ say, then the result o. the integration 6ould 3e Kero
3ecause sin(n$+ is Kero at 0 and 2( 6hile cos!n$" = # at 3oth limits and the t6o /al2
ues cancel7 9ence the re0uirement that the m /alues o. the three spherical harmonics,
allo6ing .or a change o. sign o. the Lrst, sum to Kero7
;o6, setting

sin
2
#
=
cos
2
#

# and using the su3stitution
=
cos # d
=
sin # d# , 6e ha/e1

,5
%

#
2 *
A
=
25?

2(
sin
0
# sin # d# =
25?

2( #
!x #" d
'pansion o. the 3rac4et and integration o. the resulting polynomial in gi/es1
*5

,5 #

# * ? * *5

,5 # 25?

5
A
=
25?

2(

2
$

-
+
5

,
+
#
=
25?

2(

,#5
=
#*(
82D +1& Cal#;lation o" t$e matrix elements o" 9
)
#"
"or t$e
'
6 state o" /
&
in an
o#ta$e/ral Bel/
The calculation o. the matri elements o. 9

c.
6ill 3e illustrated 6ith the eample
o. the element, , ,|9

c.
|, , 7
'panding each Slater determinant, and noting that 6e must e/aluate 9

c.
.or each
electron and sum their contri3utions, 6e ha/e1
, ,|9

c.
|, ,
= !
#
" { G !#" G
+
#
!2" G
+#
!#" G
+
2
!2"|9

c.
!#"|G
+2
!#" G
+
#
!2"
G
+#
!#" G
+2
!2" }
2
+2
+ !
#
" { G
!#" G
+
#
!2" G
+# !#" G
+
2
!2"|9

c.
!2"|G
+2 !#" G
+
#
!2"
G
+#
!#" G
+2
!2" }
6here the l su3script, 6hich is al6ays 2 .or d or3itals, has 3een omitted to simpli.y
the notation7
But, in 0uantum mechanics all electrons are indistinguisha3le, so each o. the a3o/e
t6o terms must gi/e the same result and 6e may there.ore 6rite1
, ,|9

c.
|, ,
= G
+2
!#" G
+#
!2" G
+#
!#" G
+2
!2"|9

c.
!#"|
G
+2
!#" G
+#
!2" G
+#
!#" G
+2
!2"
'ach o. the .our com3inations o. 3ra 6ith 4et gi/es rise to a product o. t6o
integrals, one o/er each electron1
G
+2
!#" G
+#
!2"|9

c.
!#"|G
+2
!#" G
+#
!2"
= G
+2
!#"|9

c.
!#"|G
+2
!#" G
+#
!2"|G
+#
!2"
The Lrst o. these integrals epresses the interaction o. an electron in a d
+
2
A" 6ith
the crystal Leld and its /alue has 3een sho6n in Section -72 to 3e ,? (neglecting
as 3e.ore+7 The second is #70 3ecause the d or3itals are normalised7 Thus, neglecting
the rise in the d2or3ital centre o. gra/ity, 6e ha/e1
G
+2
!#" G
+#
!2"|9

c.
!#"|G
+2
!#" G
+#
!2" = + ,?
Similarly1
3ut1
G
+
#
!#" G
+
2
!2"|9

c.
!#"|G
+
#
!#" G
+
2
!2" = G
+
#
!#"|9

c.
!#"|G
+
#
!#"
G
+2
!2"|G
+2
!2" = 2 ,,
G
+
2
!#" G
+
#
!2"|9

c.
!#"|G
+
#
!#" G
+
2
!2" and
G
+#
!#" G
+2
!2"|9

c.
!#"|G
+2
!#" G
+#
!2"
are 3oth Kero 3ecause G
+#
!2"|G
+2
!2" = G
+2
!2"|G
+#
!2" = 07
As it happens,

G
+2
!#"
|
9

c.
!#"
|
G
+#
!#"

is also Kero7
An total there.ore1
, ,|9

c.
|, , = { ,? 2 ,,} = ,2.
82D +1' Cal#;lation o" t$e inter9ele#troni# rep;lsion "or some states o" /
&
The general t6o2electron repulsion integral ta4es the .orm1



2 2
a
!#"
3
!2" e ,r
#2

c
!#"
d
!2" d[
#
d[
2

a!#"*!2"
|
e ,r
#2
|
c!#"d!2"

r
# 2
r
,
r
5
# 2
# 2
There are t6o special .orms o. the integral7
The Coulom3 integral, Q (a,3+, in 6hich a = c and 3 = d, represents the mutual
repulsion o. an electron ha/ing the distri3ution
a

a
and an electron 6ith the dis2
tri3ution
3

3
7
The echange integral, @ (a,3+, in 6hich a = d and 3 = c, represents the mutual
repulsion o. the t6o o/erlap distri3utions
a

3
7
But integrals 6hich 3elong to neither o. these special cases are .re0uently encoun2
tered and all non2Kero t6o2electron repulsion integrals 3et6een d2or3ital distri3utions
are listed in the t6o ta3les 3elo67
The angular parts o. the integrals are the same 6hate/er the principal 0uantum
num3er, n7 But the radial .unctions, :
i
, and hence the radial parts o. the integrals
/ary 6ith n and .rom metal ion to metal ion, depending upon its en/ironment etc7
This dependence upon radial .unction is contained 6ithin the radial integrals, D
0
, D
2
and D
*
6hich, .or d2or3ital .unctions, are deLned as .ollo6s1

D
0
=
#
#
:
a
!#":
3
!2"
R

:
c
!#":
d
!2"r
2
r
2
dr
#
dr
2
r
2
D
2
=
*$
#
D
*
=
**#
:
a
!#":
3
!2"
P
R
r
*
:
a
!#":
3
!2"
P
R
:
c
!#":
d
!2"r
2
r
2
dr
#
dr
2
:
c
!#":
d
!2"r
2
r
2
dr
#
dr
2
in 6hich r
R
is the greater and r
P
the lesser o. r
#
and r
2
7
The D
0
, D
2
and D
*
gi/en in Ta3les B-7,7# and B-7,72 include the .actors o. #H*$
and #H**# in D
2
and D
*
respecti/ely7
An ligand Leld theory, the D
4
are usually treated as ad@usta3le parameters and they
are .re0uently ta4en in the con/enient com3inations Lrst suggested 3y :acah 6ho
deLned1
A = D
0
*$D
*
B = D
2
5D
*
and C = ,5D
*
Ele#tron rep;lsion in t$e T
%
an/ T
&
states o" t$e #onBg;ration Ft
&g
G
%
Fe
g
G
%
A (t
2g
+
#
(e
g
+
#
conLguration o. T
2
symmetry is (y+
#
(K
2
+
#
6hich 6hen 6ritten as
an epanded Slater determinant is1
!#,

2"{y!#" K
2
!2" K
2
!#"y!2"}
The mutual repulsion o. the t6o electrons is1
# 2 2 2 2 2
2

y!#"K !2"

K !#" y!2"
|
e ,r
#2
|
y!#" K !2"

K !#" y!2"

# 2 2 2 2 2 2
=
2
{
y!#" K !2"
|
e ,r
#2
|
y!#" K !2"
+
K !#" y!2"
|
e ,r
#2
|
K !#" y!2"

y!#" K
2
!2"| e
2
,r
#2
|K
2
!#" y!2" K
2
!#"y!2"| e
2
,r
#2
|y!#" K
2
!2" }
# 2 2 2 2 2 2
=
2
{
Q !y, K "
+
Q !y, K "

@!y, K "

@!y, K "
} =
Q !y, K "

@!y, K "
2
5

5
#0 #0
Which, using Ta3le B-7,7#1
= D
0
*D
2
+ ?D
*
!*D
2
+ #5D
*
" = D
0
%D
2
$D
*
"r in terms o. :acah parameters1
= A %B = A % ,#5
6here is the energy di..erence 3et6een the
,
! and
,
D states o. d
2
as deLned in
Section -7,72 and calculated 3elo67
Similarly, a (t
2g
+
#
(e
g
+
#
conLguration o. T
#
symmetry is (y+
#
!
2

y
2
"
#
6hich
6hen 6ritten as an epanded Slater determinant is1
!#,

2"{y!#"
2
y
2
!2"
2
y
2
!#"y!2"}
Dor 6hich the mutual repulsion is1
Q !y,
2
y
2
" @!y,
2
y
2
" = D
0
+ *D
2
,*D
*
!,5D
*
" = D
0
+ *D
2
?$D
*
"r in terms o. :acah parameters1 = A + *B = A + * ,#5
3etermination o"
To calculate 6e epress the
,
! and
,
D states o. d
2
as in Section -7,7# and
Appen2 di #01
,
D = | + 2
+
!#" +#
+
!2" = !

#
"{!2 #" !# 2"}
,
! =

!
2
"| + 2
+
!#" #
+
!2"

!
,
"| + #
+
!#" 0
+
!2"
=

!
2
"{!2 #" !# 2"}

!
,
"{!# 0" !0 #"}
Since all components o. a term ha/e the same energy, e/en 6hen inter2electronic
repulsion is included, 6e can ta4e any component to calculate the electron repulsion7
An each case 6e ta4e the component o. the term 6hich has the maimum 5
S
and 5
L
/alues since these ha/e the simplest 6a/e .unctions7 'ach o. the three microstates is
a 2 2 Slater determinant 6hich has 3een epanded a3o/e 6ith a simpliLcation o.
the notation 6hich assumes that the electrons in the state sym3ols are al6ays in the
order #, 27 ;o6, .or
,
D 6e ha/e1
# 2
2

!2 #"

!# 2"
|
e ,r
#2
|
!2 #"

!# 2"

# 2 2
=
2

!2 #"
|
e ,r
#2
|
!2 #"
+
!# 2"
|
e ,r
#2
|
!# 2"

!2 #"| e
2
,r
#2
|!# 2" !# 2"| e
2
,r
#2
|!2 #"
Anspection o. the a3o/e .our integrals sho6s that the Lrst t6o are 3oth Coulom3
integrals representing the repulsion o. an electron in a d
+
2
or3ital 6ith one in a
d
+
#
7 The second pair are echange integrals representing the mutual repulsion o. t6o
electron2density distri3utions 6hich are descri3ed 3y the product o. d
+
2
and d
+
#
7
There.ore1
# 2
2

!2 #"

!# 2"
|
e ,r
#2
|
!2 #"

!# 2"

= !2 #"| e
2
,r
#2
|!2 #" !2 #"| e
2
,r
#2
|!# 2" = Q !# 2" @!# 2"
We can no6 loo4 up the electron repulsion integrals in Ta3le B-7,72, 6hich is
the same as Ta3le B-7,7# 3ut 3ased upon the comple rather that the real d or3itals7
We Lnd1
and1

!2 #"
|
e
2
,r
#2
|
!2 #"
=
D
0

2D
2

*D
*
!2 #"| e
2
,r
#2
|!# 2" = +?D
2
+ 5D
*
so that the electron repulsion in the
,
D state is1 D
0
%D
2
$D
*
7
Dor the
,
! state 6e Lnd three contri3utions to the energy1
!
# 2 2
5
"
{
2

!2

#"
|
e ,r
#2
|
!2

#"

2

!2

#"
|
e ,r
#2
|
!

# 2"
}
2 2
=
5
Q !2

#"

5
@!2

#"
=
!
2
"
{
D
0
2D
2
*D
*
,5D
* } =
!
2
"
{
D
0
2D
2
,$D
* } 5
!
, 2
5
2 , ,
#0
"
{
2

!# 0"
|
e ,r
#2
|
!# 0"

2

!# 0"
|
e ,r
#2
|
!0 #"
} =
5
Q !# 0"

5
@!# 0"
=
!
,
"
{
D
0 +
2D
2
2*D
*
D
2
,0D
* } =
!
,
"
{
D
0 +
D
2
5*D
* } 5 5
and a cross2term composed o. integrals 6hich are o. neither Q nor @ type1

2

?

2 2

#0
{
2

!2

#"
|
e ,r
#2
|
!# 0"

2

!2

#"
|
e ,r
#2
|
!0 #"
}

2

?

#2
=
5
{
?D
2
+
5 ?D
*

2 ?D
2
+
#0 ?D
*
} =
!
5
"
{
,D
2
+
#5D
*
}
The total electron repulsion in the
,
! state is there.ore, D
0
+ -D
2
%*D
*
, so that1
= '!
,
!" '!
,
D" = D
0
+ -D
2
%*D
*
!D
0
%D
2
$D
*
" = #5D
2
-5D
*
;ote that in using Ta3les B-7,7# and B-7,72 the integral a(#+ 3(2+|e
2
,r
#2
|c(#+ d(2+ 1
(a+ Will al6ays 3e Kero i. the spin .unction o. or3itals a and c (electron #+ and o. 3
and d (electron 2+ are not the same7 But the spins o. the t6o electrons need not
3e the same7
(3+ 'presses the mutual repulsion o. t6o electron densities a(#+|c(#+ and
3(2+|d(2+ , and electrons are identical7
There.ore1
a!#" 3!2"| e
2
,r
#2
|c!#" d!2" = c!#" 3!2"| e
2
,r
#2
|a!#" d!2"
= a!#" d!2"| e
2
,r
#2
|c!#" 3!2" = c!2" d!#"| e
2
,r
#2
|a!2" 3!#" etc7
5ITERATURE
The monographs 3y Ballhausen
#
and Gri.Lth
*
, noted in the 3i3liography o. Chapter -,
are important sources .or readers 6ho 6ish to ta4e this su3@ect .urther7
K
2
y K yK 0 +

, 5

, "ther
K
2
y yK K 0 +

, 5

, "ther
K
2
K y yK 0
+2

, #0

, "ther

2
Iy
2
y K yK 0 +, #5 "ther

2
Iy
2
y yK K 0
, +#5
"ther
Ta?le 8+1'1% T6o2electron repulsion integrals 3et6een d or3itals in their real .orms
a 3 c d D
0
D
2
D
*
Antegral type
K
2
K
2
K
2
K
2
# +* +,? J
K K K K # +* +,? J
yK yK yK yK # +* +,? J
y y y y # +* +,? J

2
Iy
2

2
Iy
2

2
Iy
2

2
Iy
2
# +* +,? J

2
Iy
2
K
2
Iy
2
K # 2 * J

2
Iy
2
yK
2
Iy
2
yK # 2 * J
y K y K # 2 * J
y yK y yK # 2 * J
K yK K yK # 2 * J
K
2
K K
2
K # +2 2* J
K
2
yK K
2
yK # +2 2* J
K
2
y K
2
y # * +? J
K
2

2
Iy
2
K
2

2
Iy
2
# * +? J

2
Iy
2
y
2
Iy
2
y # +* ,* J
y yK yK y 0 +, +20 >
y K K y 0 +, +20 >
K yK yK K 0 +, +20 >

2
Iy
2
K K
2
Iy
2
0 +, +20 >

2
Iy
2
yK yK
2
Iy
2
0 +, +20 >
K
2

2
Iy
2

2
Iy
2
K
2
0
+
*
K
2
y y K
2
0 +*
K
2
K K K
2
0 +#
K
2
yK yK K
2
0 +#
+#5
>
+#5
>
+,0
>
+,0
>

2
Iy
2
y y
2
Iy
2
0 0
+,5
>
K K
2
K
2
Iy
2
0 2

, +#0

, "ther
yK K
2
yK
2
Iy
2
0 +2

, #0

, "ther
K K K
2

2
Iy
2
0 +

, 5

, "ther
yK yK K
2

2
Iy
2
0

, +5

, "ther
Ta?le 8+1'1& T6o2electron repulsion integrals 3et6een d or3itals in their comple
.orms
m
a
m
3
m
c
m
d
D
0
D
2
D
*
Antegral type
+2 +2 +2 +2 # +* +# Q
+2 +# +2 +# # 2 * Q
+2 +# +# +2 0 +? +5 @
+2 0 +2 0 # * +? Q
+2 0 +# +# 0 +

? 5

? "ther
+2 0 0 +2 0 +* +#5 @
+2 # +2 # # 2 * Q
+2 # +# 0 0

? +5

? "ther
+2 # 0 +# 0 +2

? #0

? "ther
+2 # # +2 0 0 +,5 @
+2 2 +2 2 # +* +# Q
+2 2 +# # 0 ? 5 "ther
+2 2 0 0 0 +* +#5 "ther
+2 2 # +# 0 0 ,5 "ther
+2 2 2 +2 0 0 +-0 @
+# +2 +# +2 # 2 * Q
+# +# +# +# # +# +#? Q
+# +# 0 +2 0 +

? 5

? "ther
+# 0 +# 0 # +2 2* Q
+# 0 0 +# 0 +# +,0 @
+# 0 # +2 0 +2

? #0

? "ther
+# # +# # # +# +#? Q
+# # 0 0 0 # ,0 "ther
+# # # +# 0 +? +*0 @
+# # 2 +2 0 0 ,5 "ther
0 +2 0 +2 # * +? Q
0 +# 0 +# # +2 2* Q
0 +# # +2 0

? +5

? "ther
0 0 0 0 # +* +,? Q
0 0 # +# 0 # ,0 "ther
0 0 2 +2 0 +* +#5 "ther
# +2 # +2 # 2 * Q
# +# # +# # +# +#? Q
# +# 2 +2 0 ? 5 "ther
2 +2 2 +2 # +* +# Q
Antegrals not listed eplicitly may 3e o3tained 3y replacing m
i
3y m
i
across a ro6 or 3y
interchanging m
a
6ith m
d
and m
3
6ith m
c
7 Also see notes in last paragraph o. tet in 3o7
d

2
y
2
eg!
2
y
2
"
2

Ed

0 0 0 0 0 0

eg!K
2
"
0 0 2

,K Es 0 0 0 0

a#g
0 0 0 0 Es 0 0 0

t#u
0 0 0 0 0 Es 0 0

t#uy
0 0 0 0 0 0 Es 0

t#uK
0 0 0 0 0 0 0 Es
y

82D +1( 3iagonalising t$e MH

*
matrix
The easiest 6ay to o3tain the eigen/alues o. the 9amiltonian matri .or C9
?
is 3y
means o. a little group theory7
The molecule 3elongs to the symmetry point group "
h
and it is not di.Lcult to
sho6 that the symmetry o. the molecule is reOected in the .ollo6ing com3inations o.
the hydrogen #s atomic or3itals7 The hydrogen atoms are num3ered as in Digure -7-
and the or3ital com3inations ha/e 3een normalised 6ith neglect o. ligand or3ital
o/erlap, i7e7

$
i
|
$
@
=
)
i@
7

a#g
=
!#,
#
?"
{
$
#
+
$
2
+
$
,
+
$
*
+
$
5
+
$
?
}

eg!
2
y
2
"
=
!
2
"
{
$
#

$
2
+
$
,

$
*
}

eg!K
2
"
=
!#,

#2"
{
$
#

$
2

$
,

$
*
+
2$
5
+
2$
?
}


t#u
=
!#, 2"
{
$
#

$
,
}

t#uy
=
!#, 2"
{
$
2

$
*
}

t#uK
=
!#, 2"
{
$
5

$
?
}
The com3inations o. hydrogen #s or3itals ha/e 3een designated 3y the symmetry
species to 6hich they 3elong, a
#g
, e
g
, t
#u
, and the metal d (
2
Iy
2
, K
2
+ or p (, y,
K+ or3itals 6hich ha/e the same symmetry and 6ith 6hich they 6ill there.ore interact7
Since 6e are not considering metal p or3itals here, the t
#u
com3inations o. hydrogen
#s atomic or3itals 6ill play no part in the 3onding o. C9
?
7 A. 6e no6 re.orm our
9amiltonian matri, replacing the ro6s and columns 6hich 6ere .ormerly headed
3y the indi/idual hydrogen #s or3itals 3y ro6s and columns representing the a3o/e
com3inations o. the hydrogen #s or3itals, 6e Lnd the .ollo6ing matri7 To do this
6e Lrst re2calculate the columns7 The column headed
a#g
, .or eample, is simply
the sum o. the si columns headed $
#
to $
?
di/ided 3y

?7 9a/ing completed the

operation .or the columns, 6e repeat it .or the ro6s and o3tain1
9

2
y
2

d
K
2 ,K
eg!K
2
" a#g t#u t#uy t#uK

eg!
2
y
2
"
2 ,K Es 0 0 0 0 0 0
d
K
2
0 0 Ed 2

,K 0 0 0 0
The use o. symmetrised sets o. ligand or3itals as 3asis .unctions results in a matri
6hich is 3loc4ed outP compare the matri 3ased on the unsymmetrised ligand or3itals
in Section -7-7 The ne6 matri is actually si separate matrices .our o. 6hich are
simply # # matrices 6ith eigen/alues o. Es7 The other t6o are identical 2 2
matrices1
9

d
K
2

eg!K
2
"
9

d

2
y
2 2 2 eg! y "
d
K
2
Ed 2

,K d

2 2 Ed 2

,K

eg!K
2
"
2

,K Es
eg!
2
y
2
"
2

,K Es
=
<
and their eigen/alues, <, can 3e .ound 3y sol/ing the characteristic e0uation (Ap2
pendi ,+1
the roots o. 6hich are1
!Ed

<"!Es

<"

#2K
2
=
0
Ed + Es

!Ed Es"
2
+ *%K
2
2
'ach identical matri gi/es t6o /alues o. < one o. 6hich corresponds to ligand2
metal 3onding (the negati/e sign 3e.ore the s0uare root+ and one to anti3onding7
An Section -7- these pairs o. degenerate le/els are designated E
3
and E
a
respecti/ely7
!R285EMS 62R CHA!TER +
#7 Sho6 that A
**
= A
**
.or $
0
= 0 ( H2 and ( 7 (A
4L
is deLned 3y '0uation
(-7275++7
27 Dollo6 the method in Section -7,7# and Bo -72 to calculate the o..2diagonal matri
element , +2|9

c.
|, 2 .or the
,
D state o. d
2
in an octahedral crystal Leld7
,7 Dollo6 the method in Section -7,72 and Bo -7, to calculate the inter2electronic repul2
sion in the |# 0 component o. the
,
! state o. d
2
in an octahedral crystal Leld7
|# 0 = !2,

5"|2
+
2
+
!#,

5"|#
+
#
+

*7 Consider t6o d
2
conLgurations o. an octahedral transition metal comple, a+ in 6hich
the electrons occupy the d
y
and d
K
or3itals 6ith paired spins and 3+ in 6hich the
electrons occupy the d
y
or3ital only7
=se the in.ormation in Bo -72 to calculate the electron2repulsion energy o. these
t6o conLgurations7 Rou should Lnd1
'lectron repulsion .or conLguration a = D
0
+ D
2
+ #?D
*
7
'lectron repulsion .or conLguration 3 = D
0
+ *D
2
+ ,?D
*
7
Note: The 6a/e .unction .or conLguration a is 3est o3tained 3y recognising that it
must 3e the product o. a spin .unction and a space .unction o. the .orm descri3ed in
Section ##757
57 =se the operator V l

s
=
#
V !l
s

+
l s

"
+
V l s

to dra6 up the #0 #0 matri .or

2
+ + K K
the spin or3it coupling in the conLguration d
#
7 Sho6 that the matri has si eigen/alues
o. +V and * o. ,V ,2, as one 6ould epect .or the states
2
<
5,2
and
2
<
,,2
7
?7 Amagine a tetrahedral, transition2metal comple ion, ZC9
*
\
*

, in 6hich the .our 9

ions are arranged around the central metal atom as sho6n in the Lgure1
d
y
!ro3lems .or Chapter - 2#,
N
*
#
2
,
F
With the aid o. this Lgure you should 3e a3le to con/ince yoursel. that the o/erlaps
o. each o. the .our 9

#s A"s 6ith the d
y
, d
K
and d
yK
A"s o. the metal are e0ual in
magnitude 3ut depend .or their sign upon the sign o. the nearest lo3e o. the d2or3ital7
'0ually, it should 3e clear that the o/erlap o. the d

2 2
A" 6ith each o. the 9

#s
A"s is Kero7 Rou can see that this is also the case .or the d
K
2
A" 6hen you recall that
d
K
2
= !#,

,"!d
K
2
2 2

+
K y
2
"7
Assuming that there is Kero o/erlap o. the 9

#s A"s 6ith each other, dra6 up an
energy matri .or the C9
*
comple li4e the one .or C9
?
in Section -7-7 <iagonalise
the matri 3y re.orming the columns and ro6s using the .ollo6ing com3inations o.
the 9

#s A"s1

y
=
#
!s
#

s
2

s
,
+
s
*
"
K
=
#
!s
#
+
s
2

s
,

s
*
"
2 2

yK
=
#
!s
#

s
2
+
s
,

s
*
"
s
=
#
!s
#
+
s
2
+
s
,
+
s
*
"
2 2
Rou should Lnd t6o sets o. triply degenerate le/els, one pair o. dou3ly degenerate
le/els and one singly degenerate le/el7
Assuming that1
a+ the initial energy o. the L/e d2or3itals is 50 #0
,
cm

#
3+ the initial energy o. the #s or3itals o. the .our 9

ions is

##0

#0
,
cm

#
c+ 6here the o/erlap is positi/e (negati/e+, the interaction energy o. an interacting
d2or3ital 6ith an 9

#s or3ital is !+"#5 #0
,
cm

#
7
sho6 that 6e epect the d2d transition o. a d
#
comple 6ith this structure to 3e .ound
in the region o. #2.5 #0
,
cm

#
7
Chapter %
Spe#tros#op0
%70 The interaction o. radiation 6ith matter . . . . . . . . . . . . . . . . . . . . . . . . 2#?
%7# 'lectromagnetic radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#?
%7#7# The electric Leld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#-
%7#72 The magnetic Leld . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#$
%72 !olarised light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2#$
%727# Linearly polarised light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
%7272 Circularly polarised light . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22#
%7, The electromagnetic spectrum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 222
%7,7# Three .orms o. electromagnetic radiation . . . . . . . . . . . . . . . . . 222
%7* !hotons and their properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22,
%7*7# 8elocity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22,
%7*72 'nergy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22*
%7*7, Cass . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22*
%7*7* Linear momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22*
%7*75 Angular momentum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
%7*7? !arity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
%75 Selection rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
%757# The Bohr I 'instein condition . . . . . . . . . . . . . . . . . . . . . . . . . 22?
%7? The 0uantum mechanics o. transition pro3a3ility . . . . . . . . . . . . . . . . . . 22-
%7- The nature o. the time2independent interaction

$
.
|
V

! y K"
|
$
i

. . . . . . . . 2,,
%7-7# The transition dipole moment . . . . . . . . . . . . . . . . . . . . . . . . . 2,*
%7-72 The relati/e intensities o. =8 I 8AS, A: and ;C:
transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2,%
%7-7, The particle and 6a/e /ie6s o. spectroscopic transitions . . . . . . . 2*2
%7% Spectroscopic time scales . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2*5
%7$ &uantum electrodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2*-
%7#0 Spectroscopic units and notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2*-
%7#07# The energyH.re0uencyH6a/elength ais . . . . . . . . . . . . . . . . . . . 2*%
%7#072 The intensityHa3sor3ance ais . . . . . . . . . . . . . . . . . . . . . . . . . 2*$
%7## The 'instein coe.Lcients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
%7#2 Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . 250
!ro3lems .or Chapter % . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25$
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
2#? Spectroscopy
,1. THE INTERACTI2N 26 RA3IATI2N 4ITH MATTER
Spectroscopy may 3e deLned as the study o. the interaction o. electromagnetic radia2
tion 6ith matter7 Ats application to chemistry, essentially in the second hal. o. the 20th
century, has 3een primarily responsi3le .or the detailed 4no6ledge o. the structure o.
molecules 6hich 6e no6 ha/e7 Chemistry, as 6e 4no6 it today, is inetrica3ly ent6ined
6ith the methods o. molecular spectroscopy and totally dependent upon them7 At is the
purpose o. this chapter to outline the principles o. atomic and molecular spectroscopy
.rom a 0uantum mechanical point o. /ie67 This 6ill help us to understand, in general
terms, ho6 electromagnetic radiation interacts 6ith matter and ho6 in.ormation a3out the
structure o. molecules can 3e o3tained 3y studying that interaction7 The speciLc 3ranches
o. spectroscopy 6hich are o. particular importance to chemistry I electronic, in.rared and
nuclear magnetic resonance I 6ill 3e discussed in the .ollo6ing chapters7 "ur Lrst tas4 is
to set do6n a suita3le description o. electromagnetic radiation7
,1% E5ECTR2MANETIC RA3IATI2N
There 6ere .e6 de/elopments in the science o. optics during the #%th century and, .or
the most part, ;e6tonGs corpuscular /ie6 o. light held s6ay7
#
An the present contet, it
is interesting to note that the generalisation o. ;e6tonian mechanics 3y Lagrange and
Laplace, 6hich 6as also 3elie/ed to 3e applica3le to particles o. light, 6as at least par2
tially responsi3le .or the general conLdence in the corpuscular description o. light at the
end o. that century7 ;e/ertheless, in #%0# Thomas Roung (#--, I #%2$+ re/i/ed the
6a/e theory o. Christian 9uygens (#?2$ I #?$5+ 3ecause he had come to 3elie/e that
colours might 3e associated 6ith /i3rations o. light as notes are associated 6ith
sound /i3ra2 tions7 Later in the century, t6o Drench amateur scientists, Armand DiKeau
(#%#$ I #%$?+ and Jean Doucault (#%#$ I #%?%+, independently impro/ed the accuracy
6ith 6hich the /elocity o. light could 3e measured and Doucault sho6ed that light tra/els
more slo6ly in 6ater than in air7 This result is in agreement 6ith the prediction o. the 6a/e
theory 3ut in contradiction to the corpuscular theory o. light7 An the years #%?* to #%-,,
6hich imme2 diately .ollo6ed DoucaultGs researches, James Cler4 Ca6ell (#%,# I
#%-$+ de/eloped a mathematical theory o. light in the .orm o. .our di..erential e0uations
6hich descri3e light as oscillating electric and magnetic Lelds7 The ne6 theory o.
electromagnetic radiation 6as a triumph7 ;ot only did it sho6 ho6 electricity,
magnetism and light are connected, a .act Lrst demonstrated eperimentally 3y Cichael
Daraday (#-$# I #%?-+ in #%*?, 3ut it made the relationships 0uantitati/e7 An Ca6ellGs
time, electricity 6as measured in one o. t6o units7 At could 3e measured either in terms
o. charge in electrostatic units (e7s7u7+ or in terms o. its magnetic e..ect in electromagnetic
units (e7m7u+7 Ca6ell deri/ed the simple relationship 3et6een these t6o units in 6hich
electricity might 3e measuredP he .ound that1
/alue in e7s7u. = /elocity o. light /alue in e7m7u. !%.#.#"
in agreement 6ith the eperimental disco/ery o. this result 3y >irchho.. in #%5-7
But Ca6ellGs description o. /isi3le light as electromagnetic radiation 6ent much
.urther7 Though 4no6ledge o. the /isi3le spectrum is clearly as old as man himsel.,
only the spectral regions immediately ad@acent to /isi3le light 6ere 4no6n in Ca6ellGs
#0
-
#0
$
, #0
#-
#0
5
#0
-
,

#0
#5
'lectromagnetic radiation 2#-
day7 The near in.rared, 6hich ad@oins the /isi3le on the long26a/elength side, 6as dis2
co/ered 3y Sir William 9erschel (#-,% I #%22+ in #%00 and the ultra/iolet, on the
other side o. the /isi3le, 6as .ound 3y Johann Wilhelm :itter (#--? I #%#0+ in
#%0#7 But Ca6ellGs e0uations predicted that there 6as an inLnite spectrum o.
electromagnetic radiation, @ust 6aiting to 3e disco/ered, outside the then24no6n range7
This prediction 6as 3rilliantly conLrmed .or long 6a/elengths 3y 9einrich :udol.
9ertK (#%5- I #%$*+ and in modern spectroscopy 6e ma4e use o. a spectral range o.
.re0uency (or 6a/e2 length+ 6hich co/ers approimately #2 po6ers o. ten (Ta3le %7#+7
Ca6ellGs e0uations passed through the great uphea/als 6hich o/ertoo4 theoretical
physics at the 3eginning o. the 20th century 0uite unchanged7 They pro/ide us 6ith a
description o. electromagnetic radiation 6hich is /ery /alua3le 6hen 6e 6ish to
consider ho6 that radiation interacts 6ith matter, the process 6hich is the 3asis o.
spectroscopy7 We there.ore no6 eamine this description7
,1%1% T$e ele#tri# Bel/
Amagine (Digure %7#(a++ an electric Leld represented 3y a /ector E
0
6hich is rotating in
the yK2plane 6ith an angular /elocity o. A radians per second7 Dor this /elocity the time,
t

, re0uired 3y the /ector E
0
to eecute one complete re/olution is1
t

= 2(,A !%.#.2"
Ta?le ,1% The regions o. the electromagnetic spectrum
Branch o. spectroscopy ;ominal 3oundary
a
<Hm > Hcm

#
>Hm

#
>Hs

#
F2ray
Auger
#0

##
#0
$
#0
##
,

#0
#$
#0

$
8acuum ultra/iolet #0

-
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 #0

-
=ltra/iolet
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 ,.% #0

-
8isi3le
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 -.% #0

-
;ear in.rared #0

?
#0
*
#0
?
, #0
#*
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 , #0

?
An.rared #0

5
#0
,
#0
5
, #0
#,
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 , #0

5
Dar in.rared #0

*
#0
2
#0
*
, #0
#2
2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 2 , #0

*
Cicro6a/e
2 2 2 2 2 2 2 2 2 2 2 #0

,
#0 #0
,
, #0
##
'lectron paramagnetic resonance
2 2 2 2 2 2 2 2 2 2 2 #0

2
# #0
2
, #0
#0
;uclear magnetic resonance
2 2 2 2 2 2 2 2 2 2 2 #0 #0

,
#0

#
,

#0
-
a
Set .or the range #0

%
to , #0

*
m in :eport ;o7 ? o. the Joint Committee on ;omenclature in Applied
Spectroscopy, Analytical Chemistry, 25, #,*$ (#$52+7
2#% Spectroscopy
E
y
0
E
0
+#70
R
+075
070
075 N
#70
0 = 6t g 0p 0 #p 2p ,p *p 5p
(a+
E
y
= E
0
l
l
+#70
+075
070
075
#70
t = 2Hv
K = (n 2+cHv
t = #Hv
K = (n #+cHv
(3+
t = 0
K = ncHv
6ig;re ,1% Graphs o. E
0
/ersus # (a+ and t (3+
The in/erse o. this time is the .re0uency o. re/olution, >, in s

#
, there.ore1
> = A,2( !%.#.,"
A. the tail o. the /ector is Led, then its head descri3es a circle in the yK2plane and the
angle, # , 3et6een the K2ais and the /ector is gi/en 3y '0uation (%7#7*+1
# = At !%.#.*"
and the component o. E
0
in the y2direction, E
y
, is1
E
y
= E
0
sin!# " = E
0
sin!At " !%.#.5"
Thus, the electric Leld in the y2direction, E
y
, /aries 6ith time as a sine .unction and
oscillates as illustrated in Digure %7#(a+7
An Ca6ellGs description, this oscillating electric Leld propagates through space in a
direction, usually chosen to 3e K, at $0

to the oscillation direction, 6ith the /elocity o.
light, c7 There.ore, a particular Leld /ector, E
y
(0+ generated at time t = 0, mo/es a6ay
.rom the light source at /elocity c7 An the time, t

= #,>, re0uired 3y the rotating /ector E
0
to complete one cycle, the propagating E
y
/ector 6ill ha/e mo/ed along the K2direction
to a position K = ct

= c,> and a.ter n cycles 6hen # = 2n( , E
y
6ill ha/e reached K
= nc,>7 There.ore, eliminating n, # = 2( K>,c7 Thus, the 6a/e reproduces itsel. e/ery
inter/al o. c,> along the K2direction (Digure %7#(3++ and this repeat distance is 4no6n as
the 6a/elength, <, so that1
and
< = c,> or c = <> !%.#.?"
E
y
= E
0
sin!2( K>,c" = E
0
sin!AK,c" !%.#.-"
The dependence o. E
y
upon time ('0uation (%7#75++ and distance ('0uation (%7#7-++
may 3e com3ined to gi/e1
E
y
= E
0
sinZA!t K,c"\ !%.#.%"
6here the t6o parts o. the argument o. the sine .unction are com3ined 6ith the negati/e
sign 3ecause (Digure %7#(3++ i. 6e mo/e along the 6a/e in the positi/e K2direction 6e
are going 3ac46ards in time7 A. this idea presents a pro3lem, consider the light arri/ing
on the earth today .rom a distant star7 The light 6hich 6e no6 see is a record o. e/ents
that too4 place on the star at the time that the light le.t it, many years ago7 But i. 6e
could @ourney to6ards the star, i7e7 in the negati/e K2direction, 6e 6ould see e/er more
recent light until, upon arri/ing at the starGs sur.ace, 6e 6ould see e/ents as they are
currently happening7 The re/erse is true i. 6e mo/e a6ay .rom the star in the direction
o. propagation o. the light7
,1%1& T$e magneti# Bel/
Apart .rom the oscillating electric Leld discussed a3o/e, Ca6ellGs description o. light
also includes a magnetic Leld, $, 6hich oscillates in phase 6ith the electric Leld 3ut
is al6ays directed at $0

to it, i7e7 along in Digure %7#7 Thus, the .ull description is
one o. an electric and magnetic Leld oscillating in phase and orientated at right angles
to each other and to the propagation direction7 These oscillating Lelds, 6hich propagate
through space (/acuum+ 6ith a speed o. 2.$$-$25

#0
%
ms

#
, constitute 6hat 6e call
light in the region 6here 6e can detect it 6ith our eyes and, in general, electromagnetic
(e2m+ radiation7 At is characterised particularly 3y its 6a/elength and .re0uency, 6hich
are related 3y '0uation (%7#7?+7 An much o. the .ollo6ing 6e use the 6ord QlightG rather
than Qelectromagnetic radiationG on account o. its 3re/ity, 3ut the latter is al6ays implied7
,1& !25ARISE3 5IHT
The electric and magnetic Lelds o. a light 3eam oscillate in directions perpendicular to the
direction o. propagation o. the light7 Thus, i. 6e choose K as the direction o. propagation,
E and $ must lie in the y2plane7 (Clearly, 6e could choose any direction .or the direction
o. propagation, 3ut unless it is stated other6ise 6e 6ill al6ays choose K7+ The /ectors
E and $ are .re0uently said to /i3rate, rather than oscillate, in the y2plane7 Light .rom
the usual sources, e7g7 the sun, incandescent metals, electrical discharges has electric and
magnetic /ectors /i3rating in e/ery direction in the y2plane (Digure %72(a++7 But 3y using
optical de/ices 4no6n as polarisers, it is possi3le to o3tain light 6hich /i3rates in only one
direction (Digure %72(3++7 Such light is said to 3e linearly or plane polarised in the direction
in 6hich the E /ector /i3rates7 !olarised light is /ery important in spectroscopy 3ecause
the direction o. polarisation o. the light can ha/e a decisi/e e..ect upon 6hether or not
the light is a3sor3ed 3y a particular sample7 An this connection it is use.ul to distinguish
t6o 4inds o. polarised lightP linearly and circ1larly polarised7 An 6hat .ollo6s 6e shall
mention only the E /ectorP 3ut the $ /ector is al6ays present .ollo6ing eactly the same
pattern o. 3eha/iour as the E /ector, 3ut al6ays at right2angles to it7 Both E and $ are
important, 3ut usually in di..erent .orms o. spectroscopy7
R
E
$
F
=npolarised light
(E /ectors only+
(a+
!lane polarised light
(E and $ /ectors+
(3+
6ig;re ,1& =npolarised light (a+ and linearly (plane+ polarised light (3+
,1&1% 5inearl0 polarise/ lig$t
The electric /ector o. a polarised light 3eam propagating along K may 3e resol/ed onto
any t6o mutually perpendicular directions in the y2plane7 At is o. particular interest in
connection 6ith the relationship 3et6een linearly and circularly polarised light to resol/e
the E /ector onto t6o such aes each o. 6hich lies at *5

to E (Digure %7,+7 We then
Lnd that the t6o components o. the E /ector, E

and E
y
say, .orm t6o 3eams o. linearly
polarised light 6ith mutually perpendicular planes o. polarisation 6hich /i3rate in phase
and ha/e e0ual amplitudeP i7e7 E

=
E
y
=
E ,

27 Thus, a 3eam o. linearly polarised light

can al6ays 3e descri3ed in terms o. t6o 3eams o. linearly polarised light 6ith mutually
perpendicular planes o. polarisation, e0ual E
0
/alues and /i3rating in phase7
E
y
= EH2
E
*5
E

= EH2
6ig;re ,1' :esolution o. plane polarised light into and y components
,1&1& Cir#;larl0 polarise/ lig$t
Light propagating through some crystalline materials, e7g7 gypsum, mica and 0uartK, tra/2
els at di..erent /elocities depending upon the direction in 6hich it is polarised7 By passing
plane polarised light through a plate o. such a material, 4no6n as a 0uarter26a/e plate, it
is possi3le to create a situation 6here3y t6o perpendicular and e0ual E /ectors /i3rate $0

out o. phase so that one is at a maimum 6hen the other is a minimum, and /ice2/ersa,
though only at one speciLc 6a/elength7 The resultant is an E /ector 6hich descri3es
a circle and i. 6e also thin4 o. the propagation o. the light 6a/e along K, then the E
/ector descri3es a spiral, li4e a staircase, and returns to the same orientation e/ery time
the 6a/e ad/ances 3y a 6a/elength (Digure %7*+7 Le.t2 and right2handed spirals can 3e
.ormed 3y suita3le choices o. phase (Digure %75+7 Light ha/ing these properties is 4no6n
as circularly polarised light, LC! and :C! .or the le.t2 and right2handed /ersions respec2
ti/ely7 To ensure that there is no con.usion, 6e must deLne more eactly 6hat 6e mean
3y right2 and le.t2handed spirals7 The con/ention is that i. the head o. the E /ector
mo/es cloc46ise 6hen /ie6ed 3y an o3ser/er loo4ing at the light source then the light is
:C!7 Counter2cloc46ise rotation is LC!7 The physical signiLcance o. these t6o .orms o.
polarised light lies in the angular momentum properties o. the photons 6ith 6hich they
are associated7 This 6ill 3e made clear in Section %7*75 3elo67
!ropagation
and
K direction
0 pH*
0
lH%
pH2
lH*
,pH*
,lH%
p
lH2
5pH*
5lH%
6ig;re ,1( Circularly polarised light I propagation
E
:
= (EH2+(E

cos 2pnt E
y
sin 2pnt+
right2handed
0 = 0 pH* pH2 ,pH*
le.t2handed
E
L
= (EH2+(E

cos 2pnt + E
y
sin 2pnt+
6ig;re ,1) Circularly polarised light I sense o. rotation
+
+

,1' THE E5ECTR2MANETIC S!ECTRUM

There is, in principle, no limit to the 6a/elength and .re0uency o. e2m radiation7 9o6e/er,
as .ar as chemical spectroscopy is concerned, the range o. interest runs .rom < = #0

##
m
(> = , #0
#$
s

#
+ to < = #0 m (> = , #0
-
s

#
+7 This is an etremely large range and
it is di/ided into a num3er o. smaller regions (Ta3le %7#+7 There is, o. course, no sharp
di/ision 3et6een any t6o ranges, 3ut the eperimental techni0ues used .or spectroscopy
in the di..erent regions and the type o. in.ormation o3tained di..er 6idely7 At is there.ore
con/enient to discuss spectroscopy in the di..erent regions o. the e2m spectrum under
di..erent headings, e7g7 ultra/iolet and /isi3le spectroscopy, in.rared spectroscopy etc7, as
6e shall presently see7
,1'1% T$ree "orms o" ele#tromagneti# ra/iation
The e2m radiation generated 3y the rotating electric Leld /ector, E
0
, as descri3ed in
Sections %7# and %72 is called electric di%ole radiation 3ecause it has eactly the same
.orm as the radiation emitted 3y an oscillating dipole composed o. t6o e0ual and opposite
charges, 0
+
and 0

, separated 3y a distance l (Digure %7?(a++ and each /arying 6ith time

according to the e0uation1
0 = 0
=
0
0
cos At
9o6e/er, though this is the most common .orm o. e2m radiation it is not the only one7
T6o other types o. e2m radiation 6ill ma4e occasional appearances in this 3oo47 T6o
identical electric dipoles arranged co2linearly end to end (Digure %7?(3++ 6ith the central
charge and those at the ends /arying in time according to the e0uation1
20

=
0 = 0
0
cos At
emit electric 71adr1%ole radiation7 Dinally, an oscillating electric current Oo6ing in a
loop (Digure %7?(c++ constitutes an oscillating magnetic dipole and emits magnetic di%ole
radiation7
0
+0
+20
0
'lectric
<ipole
0
'lectric h
&uadrupole
(a+ (3+
6ig;re ,1* Three .orms o. electromagnetic radiation
Cagnetic
<ipole
(c+
!hotons and their properties 22,
,1( !H2T2NS AN3 THEIR !R2!ERTIES
Be.ore 6e em3ar4 upon the study o. the interaction o. radiation 6ith matter in particular
regions o. the spectrum 6e must recall (Section 27?+ that, at the end o. the #$th century,
the 6a/e theory o. light 6as .ound to 3e di.Lcult to reconcile 6ith the results o3tained
.rom a study o. the photoelectric e..ectP the e@ection o. electrons .rom a metal sur.ace
6hen that sur.ace is irradiated 6ith /isi3le or ultra/iolet light7 This 6as @ust one o. the
pro3lems pre/alent at that time 6hich, in #$05, led 'instein to propose that processes
6here light is a3sor3ed or emitted 3y a su3stance might 3e 3etter understood in terms o.
light 0uanta or photons o. energy !h>"7 'instein did not himsel. coin the name QphotonGP he
used the term light2energy 0uantum throughout his #$05 paper7 The 6ord photon .or the
corpuscle o. light 6as proposed 3y Gil3ert ;e6ton Le6is (#%-5 I #$*?+ in #$2? and
the suggestion appears to ha/e recei/ed immediate acceptance7 'insteinGs corpuscular
concept o. light 6as success.ully applied 3y Bohr in his #$#, interpretation o. the hydrogen
atom spectrum7 An #$#? it 6as .ully su3stantiated, 6ith respect to the photoelectric e..ect,
3y Cilli4anGs comprehensi/e eperimental studies (Section 27?+, and since that time this
/ie6 o. the energetics o. the interaction o. light 6ith matter has ne/er 3een challenged7 At is
there.ore appropriate that 6e no6 consider some properties o. the photon7
!hotons are the 0uanta o. the electromagnetic Leld7 Li4e other particles, they ha/e
energy, angular momentum and parityP properties 6hich must 3e conser/ed 6hen photons
interact 6ith other 0uantum2mechanical entities such as atoms and molecules7 "ur interest
in these conser/ation re0uirements arises 3ecause they .orm the 3asis o. the spectroscopic
selection rules7 An particular, 6hen a photon is a3sor3ed (emitted+ 3y an atom or molecule
the energy, angular momentum and parity o. the system, photon + atom or molecule, must
3e the same 3e.ore and a.ter the a3sorption (emission+7 This 3ald statement re0uires .urther
elucidation in the case o. the conser/ation o. angular momentum7 An 0uantum mechanics,
6hen t6o angular momenta, @
#
and @
2
, are added together 2@
P
+ # /alues o. the resultant
sum, J, are possi3le, 6here @
P
is the smaller o. @
#
and @
2
(Section *7?7#+7 These /alues
.orm the Cle3sch I Gordan series ('0uation (*7?7#++1
J = @
#
+ @
2
@
#
+ @
2
# @
#
+ @
2
2 . . . |@
#
@
2
|
8alues o. J, @
#
and @
2
6hich satis.y any o. the a3o/e 2@
P
+ # e0uations are said to
satis.y a triangular condition 6hich is 6ritten (@
#
, @
2
, J+ and is not e0ual to Kero only
i.
J is one o. the Cle3sch I Gordan series .ormed .rom @
#
and @
2
7 Thus, i. @
i
, @
.
and @
p
are
the
angular momenta o. the initial state, Lnal state and photon respecti/ely, then these three
angular momenta must satis.y the triangular condition (@
i
, @
p
, @
.
+ i. angular
momentum is to 3e conser/ed in the a3sorptionHemission process7 The .act that 2@
P
+
# di..erent
outcomes can all satis.y the condition .or the conser/ation o. angular momentum seems,
at Lrst sight, a little surprising7 9o6e/er, this is necessary in order to ta4e account o.
3oth a3sorption and emission processes as 6e shall see 6hen 6e consider electric dipole
transitions 3elo67
,1(1% Velo#it0
The /elocity o. the photon is the /elocity o. light, 6hich is e0ual to the product o. the
6a/elength (< in m+ and the .re0uency (> in s

#
+1
c = < > = 2.$$-$25 #0
%
m s

#
!%.*.#"
22* Spectroscopy
The a3o/e Lgure is the /elocity o. light in a /acuum7 An any other medium the /elocity
is less 3y a .actor o. #Hn, 6here n is the re.racti/e inde o. the medium7 Durthermore,
in any medium other than a /acuum the /elocity o. light depends upon its 6a/elength7
The dependence o. /elocity or re.racti/e inde upon 6a/elength is responsi3le .or the
.act that light is dispersed into a spectrum 6hen it passes through a transparent prism7
As a simple illustration o. '0uation (%7*7#+, 6e ta4e one o. a pair o. lines 4no6n as
the sodium < linesP t6o closely spaced atomic spectral lines 6hich are responsi3le .or
the strong yello6 colour o. the sodium Oame or street lamp and 6hich deri/e .rom the
transitions
2
!
,

2
S
#
and
2
!
#

2
S
#
o. the sodium atom (Chapter 5+7 The Lrst o. these
2 2 2 2
lines has <
=
5.%$2

#0

-
m and >
=
5.0%%

#0
#*
s

#
7 At is clear that these data satis.y
'0uation (%7*7#+7
,1(1& Energ0
The energy o. a photon depends upon its .re0uency according to the e0uation proposed
3y 'instein in #$051
E = h> !%.*.2"
h is !lanc4Gs constant, .or 6hich 6e shall use the truncated /alue o. ?.?2? #0

,*
J s
in this section7 Thus, .or the a3o/e <2line photon 6e Lnd1
E = ?.?2? 5.0%% #0

20
= ,.,-# #0

#$
J !%.*.,"
,1(1' Mass
A relationship also deduced 3y 'instein, 3ut in connection 6ith the special theory o.
relati/ity, may 3e used to determine the mass o. a photon1
E = mc
2
or m = E,c
2
!%.*.*"
Dor our particular eample 6e Lnd1
m = ,.,-# #0

#$
,!2.$$% #0
%
"
2
= ,.-5# #0

,?
4g
;ote that, 3ecause the mass o. the photon depends upon its energy, its mass also
depends upon its 6a/elength or .re0uency7 A. 6e also recall that the mass o. a particle
mo/ing 6ith a /elocity, v, compara3le 6ith that o. light is related to its mass 6hen at
rest, m
0
, 3y yet another e0uation due to 'instein1
m
0
= m

# !v,c"
2
!%.*.5"
then 6e see that, 3ecause the photon mo/es 6ith the /elocity o. light, v,c = # and the
rest mass o. the photon is Kero7
,1(1( 5inear moment;m
The linear momentum, %, o. a particle o. mass m mo/ing 6ith /elocity v is gi/en 3y
% = mv and since .or the photon v = c, in a /acuum our <2line photon has a linear
momentum o.1
% = mc = ,.-5# 2.$$% #0

2%
= #.#25 #0

2-
4g m s

#
!%.*.?"
Selection rules 225
ComptonGs interpretation o. the scattering o. F2rays 3y electrons (see Bo %7#+ pro/ides
one o. the most con/incing pieces o. e/idence .or the photon as a discrete particle 6hich
has mass and, hence, linear momentum7
,1(1) Ang;lar moment;m
'periment sho6s that the electric dipole photon has a spin angular momentum charac2
terised 3y a spin 0uantum num3er o. #, i7e7 a total spin angular momentum o.

2h,2(
(Chapter *+7 But, unli4e a particle 6ith a Lnite rest mass, 6hich 6ould ha/e K2components
o. +#, 0 and # in units o. h,2( (Chapter *+, the photon has only t6o components o.
h,2( directed parallel (++ and antiparallel (+ to its direction o. propagation7 These
t6o components o. angular momentum are related to the property o. light 6hich is 4no6n
as polarisation7 As 6e ha/e seen in Section %7272, t6o types o. circularly polarised light
eist7 LC! light has a K component o. angular momentum o. +h,2( and :C! light
has a K component o. angular momentum o. h,2( 7 The photons in a 3eam o. linearly
polarised light are not in states 6hich are eigen.unctions o. the operator .or the K compo2
nent o. angular momentum7 The epectation /alue .or a measurement o. the K component
o. their angular momentum is Kero, since a large num3er o. measurements 6ould record
e0ual num3ers o. photons ha/ing angular momenta o. +h,2( and h,2( 7 An SA units
the angular momentum o. a photon is1
l =

2h,2( =

2 ?.?2? #0

,*
,2( = #.*$# #0

,*
J s !%.*.-"
The /alue o. l has 3een determined eperimentally in a /ery ingenious 6ay 3y Beth7
2
;ote that l is independent o. the 6a/elength or .re0uency o. the photon and is there.ore
the same .or all photons7
,1(1* !arit0
Li4e atomic 6a/e .unctions (Section 57#072+, an odd (u+ or e/en (g+ character may 3e
assigned to photons and, as 6ith atoms, the parity o. the photon depends upon its state7
!arity and angular momentum together lie at the heart o. the stringent conditions 6hich
determine the 6ay in 6hich photons interact 6ith matter7 These conditions are called
selection r1les7
,1) SE5ECTI2N RU5ES
Three com3inations o. photonic angular momentum and parity play a particular role in
the selection rules o. chemical spectroscopy7 'ach corresponds to a particular .orm o.
e2m radiation7
The photons o. electric dipole radiation are o. odd (u+ parity and carry one unit o.
angular momentum7 Dor an allo6ed electric dipole transition, there.ore, the parities o. the
initial and Lnal states must di..er, i7e7 u

g or g

u, and the triangular condition (@
i
,
#, @
.
+ must 3e o3eyed7 Since the total angular momentum 0uantum num3er, @, is al6ays
positi/e, one might nai/ely thin4 that the a3sorption o. a photon must 3e accompanied
3y an increase in the angular momentum o. the a3sor3ing species, and emission 3y a
22? Spectroscopy
decrease7 But the .act that angular momentum is conser/ed i. the resulting @
.
satisLes
any o. the 2@
P
+ # Cle3sch I Gordan relationships remo/es this apparent restriction7 Dor
eample, i. an atom in a ! state (@ = #+ a3sor3s a photon, states ha/ing increased (@ = 2
Z<\+, unchanged (@ = # Z!\+ or decreased (@ = 0 ZS\+ angular momentum may result7 And
in all three cases angular momentum is conser/ed7 9o6e/er, in the case o. the ! !
transition there is no change o. parity, so it 6ould not 3e electric2dipole allo6ed7 'lectric
dipole transitions are responsi3le .or the /ast ma@ority o. the a3sorption (emission+ 3ands
o3ser/ed in the electronic spectra o. atoms and molecules and in all in.rared a3sorption and
emission processes7 They are much stronger (3y a .actor

#0
*
+ than all other transitions
6hich are .or3idden 3y these selection rules7
The photons o. electric 0uadrupole radiation carry t6o units o. angular momentum
and are o. e/en (g+ parity7 The etra angular momentum is usually called or3ital angular
momentum, 3ut the use o. the terms QspinG and Qor3italG in the case o. photons is to a
large etent a matter o. con/enience 3ecause in most cases the t6o cannot 3e separated7
Dor an electric 0uadrupole transition, there.ore, the triangular condition (@
i
, 2, @
.
+
must 3e o3eyed and the parities o. the initial and Lnal states must 3e the same7 The /ery
6ea4
d d (g g+ and . . (u u+ transitions o. gas2phase metal atoms and ions 6ith
open d or . shells are o. this type7
The photons o. magnetic dipole radiation carry one unit o. angular momentum and
are o. e/en (g+ parity7 Dor an allo6ed magnetic dipole transition, there.ore, the triangular
condition (@
i
, #, @
.
+ must 3e o3eyed and the parities o. the initial and Lnal states
must 3e the same7 These transitions are 6ea4 and rarely seen in electronic
spectroscopy and ne/er in the in.raredP 3ut their signiLcance is great 3ecause they are the
transitions 6hich are o3ser/ed in electron and nuclear magnetic resonance
spectroscopies7
The selection rules that deri/e directly .rom the re0uirements o. conser/ation, espe2
cially conser/ation o. energy, angular momentum and parity, impose many restrictions
upon the process o. a3sorption or emission o. a photon 3y a molecule7 The .act that the
selection rules are so restricti/e should not, in general, 3e regarded as a disad/antage7
This selecti/ity is the 3asic cause o. the highly characteristic spectrum o. each chemical
compound 6hich is, in turn, the reason .or the /alue o. spectroscopy as a means o. iden2
ti.ying atoms and molecules7 We shall return to the su3@ect o. selection rules 6ith some
eamples in Section %7-7,7
We might note here that, since energy and mass are related 3y '0uation (%7*7*+, the
conser/ation o. these t6o 0uantities should 3e considered together7 But this .act plays no
discerna3le role in the spectroscopy o. interest to chemists and 6e conLne our attention
here to conser/ation o. energy 6hich .orms the 3asis o. the most .undamental o. all the
selection rules1 the Bohr I 'instein condition7
,1)1% T$e 8o$r I Einstein #on/ition
Strange as it may seem to us today, 'insteinGs concept o. the light particle or photon
recei/ed little attention in the years immediately .ollo6ing its pu3lication in #$057 But in
#$#, the idea played a central role in BohrGs pre20uantum2mechanical theory o. the hydro2
gen atom (Sections 27-7# and 27-72+7 9a/ing 0uantised the or3ital angular momentum, and
hence the energy, o. his planetary electron, Bohr postulated that 6hen an electron changed
or3it it emitted or a3sor3ed the energy di..erence 3et6een the energy o. the initial, E
i
,
The 0uantum mechanics o. transition pro3a3ility 22-
and the Lnal, E
.
, states according to the e0uation1
E = |E
.
E
i
| = h>. !%.5.#"
Thus, i. the energy o. the photon is h>, as 'instein had proposed, '0uation (%757#+
is the e0uation o. energy conser/ation and determines the region o. the e2m spectrum
in 6hich each type o. atomic and molecular process is o3ser/ed spectroscopically7 To
appreciate the conser/ation o. other 0uantities, especially the most important o. them
angular momentum, 6e must eamine the interaction o. e2m radiation and matter in more
detail, and 6e do this in Section %7?7
An addition to the .undamental concepts associated 6ith conser/ation o. mass, energy
and angular momentum noted a3o/e, at least one other general /ie6 o. the selection
rules can 3e discerned7 A. 6e again consider e2m radiation as a 6a/e rather than as a
stream o. photons, 6e may en0uire as to ho6 the radiation actually interacts 6ith a
molecule7 What is the mechanism 3y means o. 6hich an e2m radiation 6a/e can change
the electron distri3ution in a molecule or induce a higher energy mode o. /i3ration in itJ
The QhandsG 6ith 6hich the e2m radiation QgraspsG the molecule are the oscillating electric
and magnetic Lelds7 The electric Leld, .or eample, can interact 6ith a permanent dipole
moment, i. one eists in a moleculeP the magnetic Leld can interact 6ith the magnetic
moment o. an electron, or o. a nucleus i. that nucleus has a magnetic moment7 These are
the concepts 6ith 6hich 6e shall see4 to understand the nature o. spectroscopic selection
rules 6hich apply in the indi/idual spectral regions7 An the net section o. this chapter 6e
set the scene 3y gi/ing a semi2classical description o. the interaction o. e2m radiation 6ith
matter7 An Section %7$ attention 6ill 3e dra6n to a purely 0uantum2mechanical theory o.
the interaction, 71ant1m electrodynamics7
,1* THE QUANTUM MECHANICS 26 TRANSITI2N !R28A8I5ITY
This section 6ill 3e one o. the more mathematical parts o. the 3oo4 and readers 6ho
6ould pre.er to lea/e it aside at present may do so i. they note care.ully the .ollo6ing
points, 6hich 6ill also ser/e as a guide .or those 6ho propose to 6or4 through the
material7
#7 We Lrst set up a 6a/e .unction that descri3es a system 6hich is changing in timeP i7e7
one 6hich is ma4ing a transition .rom an initial state ha/ing a 6a/e .unction
i
and
an energy E
i
to a Lnal state 6ith 6a/e .unction
.
and energy E
.
7
27 We recognise that such a 6a/e .unction has time2dependent and time2independent parts
and 6e .ocus our attention upon the .ormer7
,7 We disco/er that the com3ination o. the time2dependent part o. the 6a/e .unction
and the time2dependency o. the radiation (sin At +, acting o/er a Lnite period o. time,
- , results in a non2Kero interaction only 6hen the Bohr I 'instein condition o.
energy conser/ation is satisLed7 At must 3e emphasised that the Bohr I 'instein
condition is not introduced into the analysisP it arises 0uite naturally7
*7 This time2dependent part o. the pro3lem is common to all 3ranches o. spectroscopy
and the Bohr I 'instein condition there.ore represents a /ery .undamental and
6idely applica3le selection rule7
22% Spectroscopy
57 The time2independent part o. the pro3lem, ho6e/er, /aries 6ith the type o. spec2
troscopy in/ol/ed and does not ta4e the same .orm in all 3ranches o. the su3@ect7
We no6 attempt to ans6er the 0uestions1 9o6 does an electromagnetic 6a/e interact
6ith an atom or molecule and cause it to change its energy state 3y a3sor3ing energy
.rom the radiationJ What is the mechanism o. this process and ho6 does it gi/e rise to
selection rulesJ
With pro3lems such as the a3o/e in mind, 'r6in SchroM dinger .ormulated
t6o 0uantum2mechanical e0uationsP the time2independent and the time2dependent SchroM
dinger e0uations7 We ha/e already discussed and used the Lrst o. these e0uations in
Chapters 2 and ,7 At ta4es the .orm1
9

$
a
=
E
a
$
a
!%.?.#"
in 6hich $
a
is an eigen.unction o. the energy operator, 9

, 6ith eigen/alue E
a
7
9

$
a
are .unctions o. the spatial co2ordinates , y and K only7
The time2dependent e0uation ta4es the .orm1
and
ih
9


=
2(

D
!%.?.2"
Dt
9

is the same as in '0uation (%7?7#+, i is

!#", h is !lanc4Gs constant and the

simplest .orm o. is a product o. the $
a
.rom '0uation (%7?7#+ and a time2dependent
eponential term1

=
$
a
ep!

i2(E
a
t, h" !%.?.,"
We see that it is a .unction o. the three spatial co2ordinates (.rom $
a
+ and o. the time,
t 7 At is con/enient to simpli.y the a3o/e epression .or 3y noting that1
E = h> = hA,2( or A = 2(E, h !%.?.*"
6here A is an angular .re0uency measured in radians per second7
=sing '0uation (%7?7*+, can 3e 6ritten1
= $
a
ep!iA
a
t " !%.?.5"
An this simple .orm is an eigen.unction o. the time2dependent SchroM dinger
e0uation 6ith the eigen/alue E
a
7 But the most general .orm o. is a linear
com3ination o. .unctions o. the .orm1
= c
#
$
#
ep!iA
#
t " + c
2
$
2
ep!iA
2
t " + c
,
$
,
ep!iA
,
t " +
i7e71
=
a
c
a
$
a
ep!iA
a
t " !%.?.?"
6here c
a
are coe.Lcients 6hich tell us ho6 much o. each .unction $
a
ep!iA
a
t " there
is in 7 The energy o. a system descri3ed 3y such a general 6a/e .unction as is not
constant7 At changes 6ith time (Bo %72+, 6hich is @ust 6hat 6e re0uire .or a description
o. a spectroscopic transition7
An a3sorption spectroscopy 6e are normally particularly interested in a transition
3et6een @ust t6o states, an initial state,
i
, and a Lnal state,
.
, 6hich ha/e energies
o. E
i
and E
.
6ith E
i
P E
.
7 Then the 6a/e .unction 6hich descri3es all stages o. the
process
6here3y the system a3sor3s energy and goes .rom
i
to
.
during the time inter/al t = 0
to t = - is1
and

=
c
i
$
i
ep!

iA
i
t "
+
c
.
$
.
ep!

iA
.
t " !%.?.-"
at t = 01 =
i
= $
i
ep!iA
i
t " 6ith precise energy E
i
and c
i
= # c
.
= 0 at t
= - 1 =
.
= $
.
ep!iA
.
t " 6ith precise energy E
.
and c
i
= 0 c
.
= #
We see that the coe.Lcients, c, are also .unctions o. time and 6e shall use the change
in the /alue o. c
.

c
.
to trac4 the progress o. the transition .rom
i
to
.
7 At is clear
that
.or this process to ta4e place there must 3e some property o. the electromagnetic radiation
6hich lin4s the t6o states
i
and
.
7 Let us represent that property 3y an operator, V

,
6hich 6e 6rite is a product o. t6o parts, one a .unction o. the spatial co2ordinates only
and the other a .unction o. the time1
V

= V

!,y,K" V

!t " !%.?.%"
At 6ill also 3e con/enient to deLne the sym3ol 8
. i
as1
8
. i
$
.
|V

!,y,K"|$
i
ep!iA
.
t"|V

!t "| ep!iA
i
t " !%.?.$"
6hich 6ill ha/e a Lnite /alue .or an allo6ed transition7
We say that the e..ect o. the electromagnetic radiation is to pertur3 the systemP the
operator V

represents that pertur3ation7 This is epressed in 0uantum mechanics (see

Appendi *+ 3y 6riting a ne6 9amiltonian operator, 9

, .or the system as a sum o. the
original 9amiltonian, 9
0
, and the pertur3ation1
9

= 9
0
+ V

!%.?.#0"
The SchroM dinger e0uation 6hich descri3es the system under the inOuence o. the
per2 tur3ation is there.ore1
!9

0
+
V

"
=
ih

D
!%.?.##"
2( Dt
A. descri3es our simple t6o2state system ('0uation (%7?7-++ then su3stitution into
'0uation (%7?7##+ gi/es1
c
i
9
o
$
i
ep!iA
i
t" + c
.
9
o
$
.
ep!iA
.
t" + c
i
V

$
i
ep!iA
i
t" + c
.
V

$
.
ep!iA
.
t"
ih

D c
i D$
i =
2( Dt

$
i
ep!

iA
i
t"
+
c
i
Dt

ep!

iA
i
t"
D c
.
D$
. +
Dt

$
.
ep!

iA
.
t"
+
c
.
Dt

ep!

iA
.
t"
(%7?7#2+
;ote that in .orming D ,D t on the right2hand side o. the a3o/e e0uation the .unctions
to 3e di..erentiated ha/e 3een treated as products 3ecause the coe.Lcients, c, are also
.unctions o. time as 6e sa6 a3o/e7
Because o. '0uations (%7?72+ and (%7?7,+, the Lrst t6o terms on the le.t o. '0uation
(%7?7#2+ cancel the second and the .ourth on the right and the e0uation reduces to1
ih

D c
i
D c
.
c
i
V

$
i
ep!

iA
i
t"
+
c
.
V

$
.
ep!

iA
.
t "
=
2(
Dt

$
i
ep!

iA
i
t"
+
Dt

$
.
ep!

iA
.
t"
!%.?.#,"
c
.
A. 6e multiply each term o. '0uation (%7?7#,+, on the le.t, 3y $
.
ep!iA
.
t"| and
integrate o/er all spatial co2ordinates and time 6e ha/e1
c
i
$
.
ep!iA
.
t"|V

|$
i
ep!iA
i
t" + c
.
$
.
ep!iA
.
t"|V

|$
.
ep!iA
.
t"
ih

D c
i
D c
. =
2( Dt

$
.
ep!

iA
.
t"
|
$
i
ep!

iA
i
t"
+
Dt

$
.
ep!

iA
.
t"
|
$
.
ep!

iA
.
t"

!%.?.#*"
An this *ra+;et notation, 6hich 6e ha/e used 3e.ore in Chapter ,, the PR means
integration o/er all the co2ordinates in the operator, i7e7 , y, K and t 7 ;ote that the
eponential term on the le.t2hand side o. each 3rac4et is re0uired 3y 0uantum mechanics
to 3e the comple con@ugate (i +iP Appendi %+ o. $
.
ep!iA
.
t "7 9o6e/er, this
is not 6ritten eplicitly, rather it is im%lied 3y the *ra ( |+7 The Lrst integration on the
right2hand side o. '0uation (%7?7#*+ gi/es Kero 3ecause the .unctions $
i
ep!iA
i
t " and
$
.
ep!iA
.
t " are orthogonal to each other7 The integration o. the second term gi/es one
3ecause $
.
ep!iA
.
t " is normalised7 Simpli.ying the notation using '0uation (%7?7$+ and
rearranging 6e o3tain '0uation (%7?7#*+ in the compact .orm1
D c
.
Dt
=
2(
ih
{
c
i
8
. i
+
c
.
8
..
}
!%.?.#*a"
At the onset o. the pertur3ation c
i
= # and c
.
= 0 so that1
D c
.
Dt
=
2(
8
. i
!%.?.#5"
ih
This e0uation is an epression .or the change o. c
.
6ith time7 By monitoring its /alue
6e can .ollo6 the change in the system 6ith time under the inOuence o. the pertur3ation7
Suppose that the pertur3ation lasts .or a time - 7 The /alue o. c
.
at the end o. that time,
c
.
-
, can 3e .ound 3y e/aluating the integral1
-
-
= D c
.
=
0
-
2(

ih
0
8
. i
Dt !%.?.#?"
A. 6e recall that the deLnition o. 8
. i
('0uation (%7?7$++ in/ol/es integration o/er the
spatial co2ordinates , y and K, then '0uation (%7?7#?+ re0uires integration o/er all spatial
and time /aria3les and it is con/enient to separate the integrations o/er space and time7
This is 6hy 6e ha/e 6ritten 8
. i
as a product o. a space2dependent and a time2dependent
part in '0uation (%7?7$+, 6hich 6e repeat here .or con/enience1
8
. i
$
.
|V

!,y,K"|$
i
ep!iA
.
t"|V

!t "| ep!iA
i
t " !%.?.$"
The Lrst term, the time2independent term, is 0uite speciLc to the type o. spectroscopy
and is not the same, .or eample, .or in.rared and ;C: spectroscopy7 We there.ore lea/e
the time2independent term aside .or the moment and consider it again in Section %7-7
The time2dependent term, on the other hand, is eactly the same in all cases and it 6ill
there.ore 3e considered here in the general discussion7 Com3ining the t6o eponential
.unctions (remem3er that the *ra implies the comple con@ugate o. the .unction 6ritten
inside it+ the integral can 3e 6ritten1
-
0
6here A = A
.
A
i
7
-
epZi!A
.
A
i
"t \V

!t " dt
0
epZi At \V

!t " dt !%.?.#-"
Since ep!i At " = cos! At " + i sin! At " (Bo ,7# and Appendi %+, 6e see that
the eponential .unction is a .unction 6hich oscillates in time and the integral o. such
a .unction 6ill normally contain a large num3er o. e0ual and opposite contri3utions
6hich 6ill sum to Kero (Digure %7-(a++7 We there.ore re0uire that V

!t " should also 3e
an
oscillating .unction 6hich, i. suita3ly chosen, cancels the oscillations o. the eponential
term gi/ing a non2Kero /alue .or the integral7 The electric Leld o. a 3eam o. light seems a
good choice 3ecause it has the re0uired oscillatory character and the presence o. the Leld
6ill change the potential energy o. the charged particles o. 6hich atoms and molecules
are .ormed7 We there.ore in/estigate the .unction1
V

!t " = E
0
sin At = E
0
{ep!iAt " ep!iAt "},2i !%.?.#%"
3ecause it is o. the .orm 6hich 6e ha/e used earlier to descri3e the 6a/es o. electro2
magnetic radiation7 Su3stituting '0uation (%7?7#%+ into '0uation (%7?7#-+ our integral o/er
time 3ecomes1
-
E
0
epZi At \ sin At dt =
0
-
E
0

2i
0
epZi At \ {ep!iAt " ep!iAt "} dt
i
- -
i
E
0

=
2i
i
0
ep{i! A + A"t } dt
0
ep
{
i! A

A"t
}
dt
i
(%7?7#$+
since E
.
R E
i
A
.
R A
i
and A R 07 There.ore, the argument o. the Lrst
eponential term is al6ays large gi/ing a rapidly oscillating .unction 6hich integrates to a
/ery small 0uantity (Digure %7-(a++7 But the argument o. the second eponential can 3e
small and
(a+
(3+
(c+
6 + 6 >> 0
6 6 0
6 6 = 0
t = 0
6ig;re ,1+ The integral in '0uation (%7?7#$+
t = -
2
is, in .act, Kero 6hen A = A7 There.ore, the second term in the integral is slo6ly
/arying in the .re0uency range A A and it can contri3ute to a signiLcant /alue o.
the integral (Digure %7-(3++7 The maimum contri3ution 6ill 3e o3tained 6hen A = A
since the eponential .unction is then ep!0" = # 6hich sho6s no Ouctuation 6ith time,
(Digure %7-(c++7 Thus the maimum interaction o. the molecule 6ith the radiation arises
6hen1
A = A = A
.
A
i
or (using '0uation (%7?7*++ in terms o. .re0uency and energy, 6hen1
2(> = !2(, h" !E
.
E
i
" or E
.
E
i
= h>
We ha/e o3tained the Bohr I 'instein or energy conser/ation rule 6ithout any
mention o. energy conser/ation7 This result may 3e ta4en as conLrmation, i. such is
needed, o. 'insteinGs proposal that the energy o. an electromagnetic 6a/e could 3e
epressed in terms o. photons o. energy h>7 ;ote that the argument 6ould ha/e 3een
made in eactly the same 6ay, and 6ith eactly the same result, had 6e 3een
considering stimulated emission .or 6hich E
.
P E
i
A
.
P A
i
and A P 07 Then it 6ould
ha/e 3een the Lrst term o. '0uation (%7?7#$+ 6hich 6as the important one7
;o6 6e can complete our analysis 3y carrying out the integration, 6hich is 0uite
simple7 ;eglecting the Lrst term on the right in '0uation (%7?7#$+ 6e ha/e1
-
E
0

E
0

ep
{
i! A

A"t
}

-

2i
0
ep
{
i! A

A"t
}
dt
=
2i

i! A A"
0
E
0
Zep{i! A A"- } #\ =
2! A

A"
We ha/e e/aluated the integral in '0uation (%7?7#?+ to o3tain c
.
-
, the /alue at t = - o.
the 6a/e .unction coe.Lcient c
.
deLned in '0uation (%7?7-+7 Since in 0uantum mechanics,
pro3a3ility is determined 3y the product o. the 6a/e .unction 6ith its comple con@ugate,
the time2dependent part o. the transition pro3a3ility, W !t ", is proportional to the
product o. this result and its comple con@ugate1
W !t " =
E
0
Zep{i! A A"- } #\
2! A

A"

E
2
E
0
Zep{i! A A"- } #\
2! A A"
0
Zep{0} + # ep{i! A A"- } ep{i! A A"- }\ =
*! A

A"
2
E
2 2 2 #
0
Z2 2 cos{! A A"- }\ =
*! A

A"
2
=
E
0
Zsin
{
2
! A

A"-
}
\
! A

A"
2
This important .unction is sometimes 6ritten in the .orm1
E
2 2 #
W !t " =
0
sin
{
2
! A

A"-
}
*
{
#
! A

A"
}
2
!%.?.20"
W !t " is plotted against ( A A+ .rom ,(, - to +,(, - 6ith E
0
= # and - = 2
in Digure %7%7 At is interesting to note that this .unction 6as Lrst o3tained theoretically
The ;ature o. the Time2Andependent Anteraction

$
.
|
V
j
!,y,K"
|
$
i

2,,
0
2
2
T
r
a
n
s
i
t
i
o
n

p
r
o
3
a
3
i
l
i
t
y
#72
#70
07%
sin
2
Zc (6 6+- \
(6 6+
2
07?
07*
072
070
,p 2p p +p +2p +,p
#0 5 0 5 #0
6 6
6ig;re ,1, Graph o. the .unction o. '0uation (%7?720+
in the early #$,0s, 3ut no eperimental con.ormation o. its peculiar .orm 6as a/aila3le
until #$-2 6hen it 6as o3ser/ed directly in a molecular 3eam eperiment7
,
When the Dunction (%7?720+ is multiplied 3y the s0uared, time2independent, part o. the
interaction | $
.
|V

!,y,K"|$
i
|
2
and the .actor !2(, ih" !2(, ih" .rom '0uation (%7?7#?+,
6e ha/e as our Lnal epression .or the transition pro3a3ility 3et6een the t6o states
i
and
.
1
W !,y,K t " = E
2

*(
2
h
2
| $
.
|V

!,y,K"|$
i
|
2

sin
2
{
#
! A A"- }
*
{
#
! A

A"
}
!%.?.2#"
2
The time2independent .unction is the origin o. all spectroscopic selection rules, apart
.rom the Born I 'instein condition, and conse0uently it is responsi3le .or much o. the
detail in the spectroscopic in.ormation 6e o3tain .rom molecules7 An the net section 6e
eamine its particular .orm .or three ma@or 3ranches o. chemical spectroscopy I electronic,
in.rared and nuclear magnetic resonance7
,1+ THE NATURE 26 THE TIME9IN3E!EN3ENT
L
INTERACTI2N $
"
k*
)
!x< 0< M"k$
i

To proceed .urther 6ith our in/estigation o. the interaction o. radiation 6ith matter, 6e
must consider the eplicit .orm 6hich the time2independent part o. the interaction, char2
acterised 3y the operator V

!,y,K", ta4es in the case o. the indi/idual spectroscopies7

Though all 3ranches o. spectroscopy ha/e made important contri3utions to chemical
4no6ledge, electronic (ultra/iolet2/isi3le, =8 I 8AS+, in.rared (A:+ and nuclear
magnetic resonance (;C:+ spectroscopy ha/e played 3y .ar the greatest role in this
contet7 Dur2 thermore, these three 3ranches o. the su3@ect are used much more
etensi/ely e/ery day in e/ery chemical research la3oratory and accordingly 6e here
conLne our attention to these three only7
]
Comment on notation1 An this section 6e need to distinguish 3et6een 6a/e .unctions 6hich relate to di..erent aspects o. a
molecular energy stateP in particular 6e 6ish to distinguish 3et6een electronic and /i3rational 6a/e .unctions7 To ma4e this
possi3le 6e no6 6rite i and . as superscripts lea/ing the su3script position /acant .or later use7
total
total
total
|
"

|
$
= G
G
elec
G
An the case o. =8 I 8AS and A: spectroscopy it is the electric Celd, E, o. the
elec2 tromagnetic radiation 6hich interacts 6ith a changing electric dipole moment, ", in
the molecule and through this interaction causes the electronic or /i3rational state (or 3oth+
o. the molecule to change .rom an initial state $
i
to a Cnal state $
.
7 An ;C:
spectroscopy a magnetic nucleus 6ith magnetic moment, T, changes its orientation 6ith
respect to the applied, static magnetic Leld, B
0
, 3ecause o. its interaction 6ith the
magnetic Celd, B
#
, o. the electromagnetic radiation7 The .orm o. these t6o types o.
interaction is /ery similar1
=8 I 8AS and A:1 electric dipole interaction energy
=
E

"
f
$
.
|E "

|$
i
= E $
.
|"

|$
i
!%.-.#"
;C:1 magnetic dipole interaction energy = B
#
T
$
.
|B
#
T |$
i
= B
#
$
.
|T |$
i
!%.-.2"
These are simply the classical e0uations .or the dipole2Leld interaction energy7 The
QdotG indicates the scalar product o. t6o /ectors 6hich is deLned 3y the e0uation1
A 8 = A

B

+ A
y
B
y
+ A
K
B
K
so that1
E $
.
|"

|$
i
= E

$
.
|5


|$
i
+ E
y
$
.
|5

y
|$
i
+ E
K
$
.
|5

K
|$
i

We see that in order .or there to 3e an interaction 3et6een the electric (magnetic+ Leld
o. the radiation there must 3e a matri element o. the electric (magnetic+ dipole moment
operator in the same direction7 At is this 6hich gi/es spectroscopy 6ith polarised light the
a3ility to pro/ide in.ormation a3out directions 6ithin a molecule7
To calculate the intensity o. a spectral line, 6e must e/aluate the a3o/e matri elements
o.
"

and T .or the spectroscopies in 0uestion7 An the case o. =8 I 8AS and A:

spectroscopy
6e re0uire the electric dipole moment,

$
.
|
"

|
$
i

, associated 6ith the transition and in
the case o. ;C: spectroscopy the corresponding magnetic moment7 We Lrst consider the
=8 I 8AS and A: case7
,1+1% T$e transition /ipole moment
An Appendi $ 6e sho6 that the transition dipole moment, "
i.
, .or a transition .rom an
initial state, $
i
, to a Lnal state, $
.
, is gi/en 3y the e0uation1
"
i.
= $
.
i
total
.
elec
.
/i3
|"

|G
i i
/i3
!%.-.,"
"
i.
is the transitory dipole moment generated 6hen the molecule changes its state
and, in a 6a/e23ased /ie6 o. the interaction o. radiation and matter, it is the QhandleG 3y
means o. 6hich the oscillating electric Leld o. the radiation is a3le to couple 6ith the
molecule7
An deri/ing '0uation (%7-7,+ the Born I "ppenheimer approimation (Section ?7,+
has 3een used to epress the total 6a/e .unction as a product o. an electronic and a
/i3rational .unction1
$
total
!,F"
=
G
elec
!,F"

G
/i3
!F" !%.-.*"
f
;ote that this epression .or the interaction assumes that the 6a/elength o. the radiation is much greater than the dimensions
o. the atom or molecule7 Dor e/eryday chemical spectroscopy this assumption is /ery 6ell @ustiLed7
/i3
| G
elec
| G
/i3 /i3
elec
elec
elec
and G
4
4
4
/i3 /i3


4
elec
= G
/i3
= G
6here the presence o. 3oth electronic (+ and nuclear (F+ co2ordinates .ollo6ing G
elec
reminds us o. the .act that the electronic 6a/e .unction depends upon the positions o.
the nuclei as 6ell as upon those o. the electrons7 Dor a discussion 6hich includes the
rotation o. the molecule see Section #0757 ZAn '0uation (%7-7,+ the (F+ and (,F+ ha/e
3een dropped to simpli.y the notation7\
'0uation (%7-7,+ may 3e 6ritten in the .orm1
"
i.
= G
.
.
elec
|"

| G
i i
/i3
= G
.
|"
F
!e
.
e
i
"| G
i
!%.-.5"
in 6hich "
F
(e
.
e
i
+ is the result o. e/aluating the integral G
.
|"

| G
i
o/er the elec2
tronic co2ordinates .or a particular nuclear conLguration represented 3y F7 The presence
o. the sym3ols F, e
.
and e
i
in "
F
(e
.
e
i
+ again reminds us that the result o. the integra2
tion depends upon the t6o electronic 6a/e .unctions in/ol/ed, G
. i
elec
, and the
particular nuclear co2ordinates chosen, F7
But 6e must allo6 .or the dependence o. "
i.
upon the nuclear conLguration and
there.ore to proceed .urther 6e epress "
F
(e
.
e
i
+ as a sum o. t6o terms1
,;?
"
F
!e
.
e
i
"
=
"
0
!e
.
e
i
"
+

&
;
"

!e
.
e
i
" !%.-.?"
4=#
The Lrst term is the /alue o. "
F
(e
.
e
i
+ at the e0uili3rium nuclear conLguration7 An
the second term, "

!e
.
e
i
" D "
0
!e
.
e
i
",D &
4
, the deri/ati/e o. "
F
(e
.
e
i
+ 6ith respect to
&
4
at
the e0uili3rium conLguration7 &
4
is the 4
th
normal co2ordinate7 The motion o. the atoms
o. a molecule along a normal co2ordinate is a /i3ration 6hich is an eigen.unction o. the
/i3rational 9amiltonian o. the molecule (see Section #07-7#+7
Thus, &
4
"

(e
.
e
i
+ is the change in the /alue o. "
F
(e
.
e
i
+ 6hen the nuclear
conLguration di..ers .rom its e0uili3rium /alue 3y a displacement along the normal
co2ordinate &
4
7
The actual /alue o. that displacement, G
.
|&
4
| G
i
, 6ill enter the calculation 6hen
the integration o/er the /i3rational 6a/e .unction is per.ormed7 The 3asic assumption
o. this epansion is that the Lrst term is /ery much larger than the second 6hich, in
turn, is /ery much larger than any .urther terms, e7g7 &
@
&
4
"

"

(e
.
e
i
+ or &
4
2
"

4
(e
.
e
i
+7
@ 4
An Section %7-72 6e shall Lnd that this assumption is 6ell @ustiLed7 '0uation (%7-75+ can
no6 3e re6ritten in the .orm1

,N

?
"
i.
=
G
.
|
"
0
!e
.
e
i
"
|
G
i
+
G
.


& "

!e
.
e
i
"

G
i
/i3
/i3
/i3

4 4

;=#
/i3
=
G
.
|
G
i
,;?

"
0
!e
.
e
i
"
+


G
.
|
&
|
G
i

"

!e
.
e
i
" (%7-7-+
/i3 /i3
4=#
/i3 4 /i3 4
We can ta4e "
0
(e
.
e
i
+ and "

(e
.
e
i
+ outside the integration o/er the /i3rational
.unctions implied 3y 3ecause they are 3oth constantsP though they do, o. course,
ha/e units7
'0uation (%7-7-+ is a /ery general epression 6hich applies to any molecule, and 6e can
recognise in it the .ollo6ing three important special cases7
Case /: G
.
i
elec
3ut G
. i
/i3
An this case there is a change o. /i3rational state 3ut no change o. electronic state, i7e7 6e
ha/e an in.rared transition7 The Lrst term on the right in '0uation (%7-7-+ is Kero 3ecause
the t6o di..erent /i3rational 6a/e .unctions 3elong to the same electronic state and are
/i3 /i3
/i3
= G
@
@ 4
@
@
@
@
elec
= G
/i3
= G
or G
= G
/i3
= G
/i3
| G
elec
= G
there.ore orthogonal7 Thus, the transition dipole moment is gi/en 3y the second term7
The /i3rational states, G
.
and G
i
, can 3e 6ritten as products o. normal /i3rational
modes (Section #07-+ 3ut 3ecause G
. i
/i3
the t6o products 6ill not 3e identical7 Let
us eamine the possi3ility that a particular /i3rational mode, &
@
say, can lose or gain
0uanta to go .rom G
i
(&

+ in G
i
to G
.
(&

+ in G
.
6hile the num3ers o. 0uanta in all
@ /i3 @ /i3
other /i3rational modes remain unchanged7 The second term in '0uation (%7-7-+ is then1
,;?
"
i.
=


G
.
|
&
|
G
i

"

!e
i
e
i
"
4=#
,;?
/i3 4 /i3 4
=
4=#
G
.
!&
#
"G
.
!&
2
" . . . G
.
!&

" . . . G
.
!&
,;?
"
|
&
4
|
G
i
!&
#
"G
i
!&
2
" . . . G
i
!&

" . . . G
i
!&
,;?
" "

!e
i
e
i
"
=
G
.
!&
#
"
|
G
i
!&
#
"

. . .

G
.
!&

"
|
&
|
G
i
!&

"

. . .

G
.
!& "
|
G
i
!& "

"

!e
i
e
i
"
@ @ @ ,;? ,;

? @
=
G
.
!&

"
|
&
|
G
i
!&

"

"

!e
i
e
i
" (%7-7%+
@ @ @ @
The sum o/er 4 reduces to a single term in the penultimate line o. '0uation (%7-7%+
since it is only 6hen 4
=
@ that 6e do not ha/e the integral

G
.
!&

"
|
G
i
!&

@
"

6hich is
Kero 3ecause 6e ha/e assumed that the same mode, &
@
, has di..erent 0uantum num3ers in
G
.
(&

+ and G
i
(&

@
+7 The simpliLcation in the last line is a conse0uence o. the .act that all
the normal /i3rational modes o. the same electronic state are orthogonal and normalised1
G!&
m
"|G!&
n
" = )
mn
!%.-.$"
The result, '0uation (%7-7%+, sho6s that i. an in.rared transition in the normal mode
&
@
is to 3e allo6ed there must 3e a change o. dipole moment associated 6ith that /i3ra2
tion, i7e7 "

!e
i
e
i
" = 07 The in.rared selection rule is em3odied in the multiplying .actor

G
.
!&

"
|
&
|
G
i
!&

@
"

, 6hich is e/aluated and discussed in Section #0757 At 6ill 3e su.L2
@ @
cient here i. 6e say that it is Kero unless the /i3rational 0uantum num3ers o. the 6a/e
.unctions G
.
!&

" and G
i
!&

@
" di..er 3y #7
Case 2: G
.
i
elec
and "
0
!e
.
e
i
" = 0P G
. i
/i3
.
/i3
i
/i3
This is the case o. an allo6ed electronic transition Z"
0
!e
.
e
i
" = 0\, 6hich may 3e accom2
panied 3y a simultaneous change o. /i3rational state, G
. i
/i3
, or 3y no change,
G
. i
/i3
=
G
/i3
7 Both terms in '0uation (%7-7-+ contri3ute to the transition dipole moment
3ut, .or the reasons gi/en a3o/e, the second term is neglected in comparison 6ith the
Lrst term 6hich is /ery much larger7 Thus, the transition dipole moment is gi/en 3y1
"
i.
= G
.
i
/i3
"
0
!e
.
e
i
" !%.-.#0"
We see that the transition dipole moment .or the /i3ronic (vi*ronic = product o. /i3ra2
tional and electronic states+ transition as a 6hole is determined 3y the electronic transition
dipole moment calculated at the e0uili3rium internuclear distance multiplied 3y the o/er2
lap o. the /i3rational 6a/e .unctions o. the initial and Lnal states7 The t6o /i3rational
.unctions are not orthogonal 3ecause G
. i
elec
7 This result 6as Lrst deri/ed 0uantum2
mechanically 3y 'd6ard =hler Condon (#$02 I #$-*+, 3ut James Dranc4 (#%%2 I #$?*+
had
o3tained it earlier using classical theory7 Accordingly, it is 4no6n as the Dranc4 I Condon
elec
= G
/i3
= G or G = G

4
4
elec
and G
elec
elec
elec
G
elec elec
4
principle7 With its aid e/en 0ualitati/e analysis o. the .orm o. the /i3rational structure o.
an electronic a3sorption 3and can gi/e us /alua3le in.ormation a3out the relati/e shapes
o. the ground and ecited state potential energy cur/es7 This is illustrated in Bo %7,7
The concept is also help.ul in descri3ing the /i3rational structure o. .or3idden electronic
transitions 6hich are allo6ed 3ecause o. molecular /i3rations, as 6e shall see 6hen 6e
consider Case ,7
Case 6: G
.
i
elec
and "
0
!e
.
e
i
" = 0P G
. i
/i3
.
/i3
i
/i3
This is the case o. a .or3idden electronic transition Z"
0
!e
.
e
i
"
=
0\, 6hich may 3e 6ea4ly
o3ser/ed 3ecause o. the presence o. the second term in '0uation (%7-7-+ 6hich deter2
mines 6hether transitions ha/ing "
0
!e
.
e
i
" = 0 occur as a result o. molecular /i3ra2
tions7 The /i3rational states may 3e epanded in terms o. the normal co2ordinates as
in '0uation (%7-7%+ gi/ing1
,;?
"
i.
=


G
.
|
&
|
G
i

"

!e
.
e
i
"
,;?
4=#
/i3 4 /i3 4
=
4=#

G
.
!&
#
"
|
G
i
!&
#
"

. . .

G
.
!&
4
"
|
&
4
|
G
i
!&
4
"

. . .

G
.
!&
,;
?
"
|
G
i
!&
,;?
" "

!e
.
e
i
"
!%.-.##"
since the t6o sets o. normal modes 3elong to t6o di..erent electronic states

G
.
!&
n
"
|
G
i
!&
n
"
=
#7 But such integrals are also unli4ely to 3e Kero, unless the
t6o electronic potential energy cur/es are /ery di..erent7 ;e/ertheless, the /i3rational
contri3ution to the intensity o. the .or3idden electronic spectral 3and can 3e e/aluated,
though this is not normally done using '0uation (%7-7##+7 The /alue o.
"

is re0uired
and the usual method employs pertur3ation theory (Appendi *+ to calculate the degree
to 6hich the /i3rations, 3y changing the shape o. the molecule, mi G
. i
elec
6ith
other electronic states7 An most cases o. practical interest G
i
is the ground state, 6hich
does not mi signiLcantly 6ith other states since they are so much higher in energy7
The miing is there.ore conLned to the miing o. G
.
6ith near3y ecited states7 The
result o. the miing is that the transition is no longer purely G
i .
elec
3ecause there
are some states among those ne6ly mied into G
.
to 6hich transitions .rom G
i
are
allo6ed7 An this 6ay the Q.or3iddenG transition ac0uires some intensity, 6hich it is said
to ha/e Q3orro6edG or QstolenG .rom one or more allo6ed transitions7
A. the potential energy cur/es o. the t6o electronic states are 0uite similar in .orm and
di..er only in energy, 6hich may 6ell 3e the case .or the ecitation o. one electron in a
large molecule, then the /i3rational eigen.unctions o. the t6o states 6ill 3e similar also7
Then, to a good approimation,

G
.
!&
n
"
|
G
i
!&
n
"
=
# and the ma@or contri3utions to the
transition dipole moment .rom each allo6ing /i3ration 6ill 3e o. the .orm1
G
.
!&
4
"|&
4
|G
i
!&
4
" "

!e
.
e
i
"
An Section #075 it is sho6n that the integral G
.
!&
4
"|&
4
|G
i
!&
4
" is Kero unless the
/i3rational 0uantum num3ers associated 6ith G
.
(&
4
+ and G
i
(&
4
+ di..er 3y #7 There.ore,
6here the electronic energy sur.aces o. the ground and ecited electronic states are similar,
6e anticipate that the /i3rational Lne structure o. a .or3idden electronic transition 6ill
correspond predominantly to changes o. # in the /i3rational 0uantum num3ers o. the
allo6ing /i3rations7 The allo6ing /i3rations are e..ecti/e 3ecause they change the shape
o. the moleculeP lo6ering its symmetry7 At is common to Lnd that the Lrst pea4 due to
an allo6ing /i3ration is .ollo6ed 3y a series o. pea4s in 6hich the allo6ing /i3ration
and an increasing num3er o. 0uanta o. a totally symmetric /i3ration are simultaneously
ecited7 Such a series o. 3ands is 4no6n as a %rogression7
Three .urther remar4s should 3e made 3e.ore 6e lea/e the long and complicated su3@ect
o. transition dipole moments7
#7 '0uation (%7?7#2+ sho6s that the intensity o. a transition 3et6een t6o states is pro2
portional to the s71are o. the transition dipole moment 3et6een them or, in the e/ent
that the transition dipole moment is a comple 0uantity, the product o. the transition
dipole moment and its comple con@ugate7
27 A similar analysis can 3e made 6ith respect to transitions stimulated 3y the magnetic
Leld o. the light, and 6e shall use this 6hen 6e come to consider an ;C: transition7
,7 An the case o. the #s 2p transition o. the hydrogen atom .or eample, though the
0uantum mechanical epression is 0uite clear, it is di.Lcult not to as4 ho6 the process
o. interaction 3et6een the light 6a/e and the spherically symmetrical atom Qgets
startedG7 Where is the dipole 6hich pro/ides the Lrst means o. interaction .or the e2m
6a/eJ An ans6er 6e may note that, since the nucleus and the electron are particles,
the atom is only spherically symmetrical 6hen the positions o. the nucleus and the
electron are a/eraged o/er some Lnite period o. timeP at any instant in time the atom
is a dipole7 A .urther eamination o. the conse0uences o. the time2dependency o. the
hydrogen2atom 6a/e .unctions can 3e .ound in Bo %727
An alternati/e, Qmore classicalG /ie6 o. the pro3lem is the .ollo6ing7 When light
passes through a transparent medium it does interact 6ith the medium e/en though it
is not a3sor3edP 6e 4no6, .or eample, that its /elocity is changed7 9o6e/er, 6hen
the .re0uency o. the light .ulLls the Born I 'instein condition, the pre/iously
limited response o. the electrons is much magniLed and a condition o. resonance is
esta3lished 6here3y electrons can a3sor3 the light energy and change their energy
states7 An terms o. the old analogy, a column o. soldiers marching o/er a 3ridge 6ill
certainly cause the 3ridge to sha4e 3ut 6ill do nothing more i. they are not all in
step7 9o6e/er, i. they are in step and the .re0uency o. their step matches a natural
/i3rational .re0uency o. the 3ridge, the 3ridge may oscillate much more /iolently
than is sa.e7 At 6as a phenomenon o. this type, caused 3y normal pedestrians
rather than soldiers, 6hich necessitated structural modiLcations to the Cillennium
Bridge o/er the :i/er Thames in London7 At appears that there 6as a remar4a3le t6o2
6ay process in 6hich the oscillations o. the 3ridge caused 3y the crossing
pedestrians induced in those same people a synchronised stepping .re0uency 6hich
increased the oscillation o. the 3ridge still .urther7
,1+1& T$e relatiAe intensities o" UV I VIS< IR an/ NMR transitions
Armed 6ith the a3o/e results 6e can proceed to eamine the simplest eample o. an
electronic transition1 the #s 2p transition o. the hydrogen atom7 A. 6e select as our
Lnal state the $
2pK
then the transition moment 6hich 6e re0uire is1
" = e $
2pK
|r|$
#s
= e $
2pK
||$
#s
+ e $
2pK
|y|$
#s
+ e $
2pK
|K|$
#s
!%.-.#2"
!
,
/i3 /i3
G
/i3
*
2
and e/aluation o. the three integrals sho6s that only the last gi/es a /alue that is not
Kero7 A. 6e choose $
2p
or $
2py
as our 2p or3ital then the matri elements containing the
operators and y respecti/ely 3ecome the non2Kero 0uantities in '0uation (%7-7#2+7 All
three contri3utions to " are e0ual since the three aes are e0ui/alent7 We shall e/aluate
the last term, "
K
, 3y ta4ing epressions .or the t6o hydrogen 6a/e .unctions (in atomic
units, Appendi #+ .rom Appendi 5 and replacing K 3y r cos # in order to ha/e all our
0uantities in polar co2ordinates7 :ecalling (Appendi -+ that the /olume element in polar
co2ordinates is r
2
sin # dr d# d$, 6e ha/e1
e



(

2(

r ep

r

cos #

r cos #

ep!

r"r
2
sin # dr d# d$
5
N
=
* 2( 0 0
e

0
2

,r

(

2(
=
2( 0
r
*
ep
2
dr cos
2
# sin # d# d$
0 0
(
e

=
2 0
r
*
ep

,r

dr
2
0
cos
2
# sin # d#
e

r
*
ep

,r

dr =
e 2*

= 0.-**$,? au
=
, 2 0
2
, 2
2
"
5
Thus, "
2
=
0.55*$ and "
2
=
,

"
2
=
#.??*% atomic units7 Con/erting .rom atomic
K K
to SA units 6e Lnd that a dipole moment o. 07-**$,? au = ?.,#5% #0

,0
C m so that the
2p transition dipole moment o. hydrogen is ,$.%%$ #0

?0
C
2
m
2
,
6hich agrees eactly 6ith the eperimental /alue7 This is a /ery satis.ying result in that
it conLrms that the 0uantum mechanical method o. calculating transition pro3a3ilities is
correct7 But 6e should not 3e lulled into a .alse sense o. security7 =ni0uely in the case o.
one2electron atoms, 6e ha/e etremely accurate alge3raic 6a/e .unctions at our disposal
.or calculations o. this type7 As soon as 6e mo/e to multi2electron atoms, and a fortiori
to molecules, the interelectronic repulsion drastically reduces the 0uality o. the a/aila3le
6a/e .unctions (see Chapter 5+ and agreement 6ith eperiment deteriorates rapidly7 Dor
a small molecule such as ethene agreement to 6ithin a .actor o. t6o or three is o.ten as
much as 6e can hope .or7
9o6e/er, our purpose here is not to o3tain accurate theoretical intensities 3ut rather
to ha/e some insight into their relati/e /alues in the =8 I 8AS, A: and ;C:
spectral regions7 There.ore, 6e do not consider possi3le reasons .or discrepancies
.urther 3ut go
on to consider a typical A: transition, the .undamental v
=
0 to v
=
# transition o. the
hydrogen chloride (9Cl+ molecule7
We ha/e to e/aluate the 'pression (%7-7%+, 6hich is a product o. G
.
|r|G
i
(r is the
only normal co2ordinate o. a diatomic molecule+ and the rate o. change o. the molecular
dipole moment 6ith 3ond length, "

(e

e+, at the e0uili3rium 3ond length, r
e
7 =sing data
.rom Bo #072 6e Lnd1
.
/i3
|r|G
i
#
=
!h,%(
2
T>"
2 =
-.5$ pm.
A. 6e assume that the charge distri3ution does not change 6ith 3ond length .or small
amplitude /i3rations a3out r
e
, then the change in dipole moment 6ith 3ond length depends
only upon the change o. 3ond length, and the rate o. change o. dipole moment 6ith
2
2
3ond length may 3e o3tained 3y di/iding the .ormer (,.?- #0

,0
C m+ 3y the latter
(#2-75 pm+1
6hence1
"

D "
0
,D : = ,.?- #0

,0
,#2-.5 #0

#2
= 2.%% #0

20
C
" = -.5$ 2.%% #0

,2
= 2.#$ #0

,#
C m "
2
= *.-% #0

?2
C
2
m
2
The 3est eperimental estimate o. " is 2.#% #0

,#
C m gi/ing a much closer agree2
ment 3et6een eperiment and our theoretical /alue than 6e ha/e any right to epectU
;ote that the /alue o. the s0uare o. the transition dipole moment, and hence the
intensity, .or a typical strong electronic transition is some .our orders o. magnitude
greater than that o. a strong in.rared transition7 This @ustiLes the assumption underly2
ing '0uation (%7-7#0+ and raises the 0uestion as to 6hy it should 3e so7 The essential
reason is that in an electronic spectral transition the transition dipole moment in/ol/es
the electrons directly, and they each carry a large charge7 An in.rared spectroscopy the
transition dipole moment depends upon a change o. dipole moment, 6hich depends upon
the differences in the distri3ution o. electronic and nuclear charge in the molecule7 The
di..erence in the intensities o. =8 I 8AS and A: 3ands has an important
eperimental conse0uence7 An.rared a3sorption spectra can .re0uently 3e measured on
samples o. pure su3stance 6hereas =8 I 8AS eperiments almost al6ays re0uire dilution
o. the sample in a suita3le sol/ent or inert matri7
Dor the ;C: case 6e shall again ta4e a simple eample and consider the magnetic
resonance o. a proton, 6hich can ta4e up t6o orientations to an applied, static magnetic
Leld7 A. 6e assume the con/entional eperimental set2up 6ith the static magnetic Leld, B
0
,
orientated along the K2direction and the oscillating radio .re0uency Leld, /
#
, along the
2direction, then the orientation o. lo6er energy has &
:
= +
#
and the higher energy ori2
entation has &
:
=
#
so that .or a3sorption o. radiation 6e must e/aluate (see Chapter $
.or the relation T

= N h` :

"1
/
#

$
.
|
T


|
$
i

/
#

m
:
= |
T


|
m
:
= +
# #
2 2
=
/
#

#
|
N h
`
:

| +
#
=
/
#
N h
`

#
|
:

| +
#
=
/
#
N
#
h
`
(%7-7#,+
2 2 2 2 2
"n inserting the /alue o. the magnetogyric ratio o. the proton (N = 2?.5-2 #0
-
rad
T

#
s

#
+ 6e Lnd that the interaction is /
#

#*.#0?

#0

2-
rad T

#
J7
At this point comparison 6ith A: and =8 I 8AS eperiments 3ecomes rather tenuous
3ecause, .rom the eperimental point o. /ie6, the intensity o. an ;C: signal is go/erned
much more 3y the populations o. the upper and lo6er le/els connected 3y the transition
than 3y any other .actor7 An Section $7? it is sho6n that in a sample o. protons in a Leld
o. .our Tesla at ,00 >, i. there are #0
?
spins in the lo6er energy state then there 6ill
3e only 2% less in the upper stateU There.ore, application o. radiation at the resonance
.re0uency soon e0ualises the populations in the t6o states and no signal is o3ser/ed since
the num3er o. up6ard (a3sor3ing+ transitions is e0ualled 3y the num3er o. do6n6ard
(emitting+7
Durthermore, there is another important di..erence 3et6een the techni0ues o. A: and
=8 I 8AS spectroscopies on the one hand and ;C: on the other7 As .ar as the most
3asic eperiments are concerned, and those are the only ones 6hich 6e can consider here,
in the A: and =8 I 8AS regions the phenomenon measured is the intensity o. a light 3eam
3e.ore
it enters a sample and a.ter it emerges .rom the sampleP i7e7 the 0uantity o. light a3sor3ed
is measured, usually as the a3sor3ance, A7 An the 3asic ;C: eperiment ho6e/er, the
magnetisation induced in the sample 3y the B
#
Leld is measured7
There.ore, it is not possi3le to ma4e a comparison 6ith eperiment 6hich stands on the
same .ooting as the a3o/e eamples ta4en .rom in.rared and electronic spectroscopy7 But
it is possi3le to o3tain a purely theoretical measure o. the relati/e sensiti/ity o. the three
spectroscopies 3y comparing the magnitudes o. the transition dipole matri elements and
the magnetic and electric Lelds o. the radiation 6ith 6hich they couple7
With regard to the latter, 6e ha/e 6ritten the pertur3ing Leld, V

(t +, in '0uation (%7?7#%+
as1
V

!t " = E
0
sin At !%.?.#%"
A. V

(t + represents the electric Leld, E(t + in 8 m

#
, o. the radiation then 6e
ha/e1
E !t " = E
0
sin At
and the magnetic Leld o. the same light 3eam, B(t + in T (Tesla+, is gi/en 3y1
B !t " = !E
0
,c" sin At = B
0
sin At
6here c is the /elocity o. light7
=sing these results and the pre/iously determined transition dipole matri elements, 6e
can dra6 up Ta3le %72, 6hich sho6s the relati/e theoretical intensities .or a light 3eam
ha/ing an electric Leld amplitude, E
0
, o. #70 8 m

#
and the corresponding magnetic Leld
/alue o. ,.,, #0

$
T7 ZDor a #00 W Llament tungsten lamp inside a spherical en/elope
o. ?0 mm diameter (i7e7 a domestic #00 W lamp+ the /alue o. E
0
at the en/elope is
approimately 2 #0

,
8 m

#
7\ The intensity, : , or a3sor3ance, A, is proportional to
the s0uare o. the interaction energy gi/en in units o. J
2
in the last ro6 o. Ta3le %72 (the
units o. : and A are not themsel/es J
2
P see Section %7#072+7 An so .ar as the energy o.
interaction can 3e regarded as a measure o. the relati/e a3sor3ance, 6e see .rom these
data that the primary cause o. the lo6 sensiti/ity o. ;C: spectroscopy lies not in the
/alue o. the transition dipole matri element 6hich, .or protons at least, is mar4edly
larger than the corresponding 0uantities in our A: and =8 I 8AS eamples7 The
pro3lem
lies 6ith the lo6 /alue o. B(t + compared 6ith E(t + and is eacer3ated 3y the
population pro3lem 6hich plays e..ecti/ely no role in =8 I 8AS or A: spectroscopy and
has not 3een included in our deli3erations a3o/e7
Ta?le ,1& Theoretical relati/e intensitiesHa3sor3ances o. electronic, in.rared and proton ;C:
transitions (Calculated .or a transition dipole moment in one Cartesian direction only+
'lectronic An.rared !roton ;C:
9 atom #s

2( 9Cl
v
=
0

v
=
# m
:
= +
2

m
:
=
2
# #
$
.
|T|$
i
= $
.
|m|$
i
= $
.
|T|$
i
=
?,.2 #0

,#
C m 2#.$ #0

,2
C m #*.# #0

2-
J T

#
E!t " = #.0 8 m

#
E!t " = #.0 8 m

#
/!t " = ,.,, #0

$
T
A or A ,.$$ #0

5%
J
2
A or A *.-% #0

?2
J
2
A or A 2.20 #0

?$
J
2
5%%7$$ nm
#? $5?7#%, c
070
5%
,1+1' T$e parti#le an/ waAe Aiews o" spe#tros#opi# transitions
The particle and 6a/e descriptions o. electromagnetic radiation play a role 6here/er
the su3@ect is discussed7 An spectroscopy too, 6e tend to ta4e the corpuscular or 6a/e
approach depending upon 6hich seems to 3e most help.ul in the interpretation o. a
particular o3ser/ation7 An the case o. =8 I 8AS radiation the choice o. description
seems o3/ious7 At is a photon 6hich is detected 3y a spot on a photographic plate or 3y an
electron e@ected .rom a metal sur.ace7 The 6a/es appear to 3e essential to the
interpretation o. inter.erence phenomena7 At the long26a/elength end o. the spectrum
6e spea4 almost eclusi/ely o. 6a/es and it is di.Lcult to en/isage a discussion o.
radio aerials in terms o. photons7 But the angular momentum changes in ;C: and
'!: spectroscopy seem to demand a photonic interpretation7 An this section these
points are illustrated 6ith a discussion o. some selected eamples o. spectroscopic
transitions sho6ing ho6 they are used to o3tain .urther in.ormation a3out the
emittingHa3sor3ing species7 We assume that energy is conser/ed in all cases and it 6ill
not 3e discussed .urther7
As an eample, dra6n .rom atomic electronic spectroscopy, o. an electric dipole tran2
sition, 6e ta4e the transitions .rom the
2
S
#
2
to
2
!
#
2
and
2
!
,
2
states o. sodium7 These
are the transitions 6hich gi/e rise to the .amous <2lines7 An energy le/el diagram is
sho6n in Digure %7$ in 6hich the di..erent 5
Q
le/els are spaced out as they 6ould 3e
i. the atom 6ere placed in a strong magnetic Leld, the Neeman e..ect (Section 57#0+7
2
!
,H2
2
!
#H2
#? $-,7,-$ cm
#
m
#
<2lines split 3y a magnetic .ield
5
Q
+,H2
+#H2
#H2
,H2
+#H2
#H2
$75$ nm
2
S
#H2
:C!
LC!
5
Q
= # 5
Q
= +#
+#H2
#H2
6ig;re ,1- The transitions
2
S
#
to
2
!
#
and
2
!
,
o. sodiumP the < lines
2 2 2
2
#
p
# #
;ote that the diagram is not dra6n to scaleP the spacing 3et6een the 5
Q
le/els is /ery
small (P0.# cm

#
+ compared 6ith the separation 3et6een
2
!
#
and
2
!
,
(#- cm

#
+ and
2 2
the ecitation energy
2
S
#
2
to
2
!
#
2
(

#? $5? cm

#
+7 The le/els 3et6een 6hich transitions
are allo6ed are connected 6ith arro6s7 The total angular momentum o. the system is
conser/ed .or all si allo6ed transitions since # +
#
#,2 (
2
!
#
+ or ,H2 (
2
!
,
+7 An order
2 2
that the K2component o. the angular momentum 3e also conser/ed the three transitions
on the le.t o. the diagram can only ta4e place 6hen an :C! photon is a3sor3ed 6hile
the three on the right re0uire an LC! photon7 To ecite these transitions 6e re0uire light
propagating parallel to the magnetic Leld7 The .our transitions in 6hich 5
Q
is unchanged
re0uire a photon 6hich has no K2component o. angular momentum, i7e7 a photon linearly
polarised in the y2plane7 These ecitations re0uire light propagating at right2angles to
the Leld7 !arity is conser/ed7 The parity o. the S state is +# and that o. the photon
#7 There.ore the parity o. their com3ination is !+#" !#" = #, 6hich is the correct
parity .or a ! state7
As an eample o. the conser/ation o. angular momentum in an electric 0uadrupole
transition 6e ta4e a line o3ser/ed at *,?., nm in the emission spectra o. certain cosmic
ne3ulae7 This and other similar lines puKKled spectroscopists .or many years 3ut it is
no6 4no6n to 3e due to the
#
S
0

#
<
2
emission o. "
2
+
atoms7 Since this is an S <
transition, it 6ould appear that a photon ha/ing t6o units o. angular momentum must 3e
in/ol/ed so that the triangular condition is (@
i
, 2, @
.
+ (Section %7*+7 9o6e/er, 6hen 6e
epress the states in terms o. the atomic or3itals in/ol/ed 6e Lnd that the transition is
due to an electron @umping .rom one 2p or3ital to another7 But (#, 2, #+ is also 0uite
accepta3le as .ar as the conser/ation o. angular momentum is concerned and 6e note
.urther that since the parity o. the product o. t6o 2p or3itals is g the photon must also 3e
g, 6hich rules out an electric dipole photon 3ut not an electric 0uadrupole photon7 Core
detailed study re/eals that at the or3ital le/el the transition is p
+
p

#
or p so
+
that the emission does not change the total angular momentum o. the atom 3ut changes
its K2component 3y 2h` , 6hich only a photon carrying at least t6o units o. angular
momentum can do7
The /alue o. the 6a/e23ased concept o. the direction o. linear polarisation can 3e
illustrated 6ith an eample dra6n .rom the electronic spectroscopy o. moleculesP e7g7
ethene (C
2
9
*
+7 The ethene molecule sho6s a 3and in the region o. #?0 nm that is due
to a transition .rom the ( 3onding to (

anti3onding or3ital (Section -7#+7 The 9uM c4el
or3itals (Section #27#+ are1
(
=

!
#
"
{
$
#
+
$
2
}
and (

=

!
#
"
{
$
#

$
2
}
!%.-.#*"
2 2
6here the $
#
and $
2
are the 2pK atomic or3itals o. the t6o car3on atoms7 There.ore,
neglecting the /i3rational .actor, the transition dipole moment is "
0
(e
.
e
i
+
('0uation (%7-7#0++, and is gi/en 3y1
# # #
C
!( (

"
=
(

|
er
|
(
=
2

!$
#

$
2
"
|
er
|
!$
#
+
$
2
"
=
2

$
#
|
er
|
$
#

2

$
2
|
er
|
$
2

!%.-.#5"
since the or3ital o/erlap contri3utions cancel7 The electron density $
#
|$
#
is centred at
car3on nucleus # and $
2
|$
2
at nucleus 2 so the only contri3ution to C
(

(

is o3tained
.rom the component o. r 6hich lies along the C
=
C 3ond7 There.ore the transition dipole
moment lies along the C
=
C 3ond7 This 3eing the case, it is easy to see that i. 6e had a
sample o. ethene in 6hich all the molecules 6ere orientated in the same direction then
only light polarised, i7e7 6ith its electric Leld /i3rating, in that direction 6ould 3e capa3le
o. interacting 6ith the molecules and hence o. 3eing a3sor3ed7 The orientated sample
6ould 3e completely transparent to light polarised at right angles to the C
=
C 3ond7
The last eample leads us into a consideration o. the selection rules in in.rared spec2
troscopy 6hich ha/e much in common 6ith it7 Consider the C
=
" stretching /i3rations o.
car3on dioide7 There are t6o such /i3rationsP the symmetric stretching 6here 3oth C
=
"
3onds gro6 longer and shorter at the same time and the asymmetric stretching 6here one
gro6s longer as the other gro6s shorter, and /ice /ersa7 The corresponding transitions
occur at #,,0 cm

#
and 2,*$ cm

#
respecti/ely 3ut only the latter is o3ser/ed in
the in.rared7 The reason is, o. course, that the change o. the t6o C
=
" 3ond dipoles
as the 3onds change in length cancel each other eactly in the case o. the symmetric
stretching, so that there is no change o. dipole moment .or the molecule as a 6hole and
hence no means .or it to couple 6ith the oscillating electric Leld o. the light, no matter in
6hat direction it is polarised7 An the case o. the asymmetric stretching there is a change
in dipole moment and in.rared radiation can 3e a3sor3ed, pro/ided that it is polarised
along the "
=
C
=
" ais o. the molecule7 This lin4 3et6een the direction o. polarisation
and molecular geometry is etremely /alua3le in the study o. orientated molecules, e7g7
crystals and stretched polymers, 3y A: and =8 I 8AS
methods7
When the sensiti/ity o. Dourier2trans.orm in.rared spectroscopy made it possi3le to
measure monolayers o. molecules adsor3ed on metal sur.aces, etension o. the a3o/e ideas
led to the metal+s1rface selection r1le .rom 6hich the orientations o. molecules adsor3ed on
the metal sur.ace could 3e determined7 When a molecule a3sor3ed on a metal sur.ace
/i3rates the /alence electrons in the metal are su.Lciently .ree (Section #272+ to .ollo6 the
oscillating dipole, and they do so in such a 6ay as to produce an image o. the dipole (Digure
%7#0+7 Thus a /i3ration producing an oscillating dipole parallel to the metal sur.ace
generates an image dipole in the metal sur.ace 6hich cancels it out (Digure %7#0(a++ so that
there is no interaction 6ith radiation7 A. the molecule generates a changing dipole
perpendicular to the sur.ace then the image dipole rein.orces the molecular dipole (Digure
%7#0(3++ and a3sorption o. in.rared radiation is possi3le7 Thus, 6hen a particular
/i3ration o. a sur.ace2a3sor3ed species is
a 3
Cetal
6ig;re ,1%. The in.rared sur.ace selection rule
Spectroscopic time scales 2*5
identiLed, usually 3y its 6a/e num3er, then the oscillating dipole moment generated must
3e perpendicular to the sur.ace and this ena3les conclusions to 3e dra6n concerning the
orientation o. the adsor3ed molecule on the sur.ace7
Conser/ation o. linear momentum plays no role in the interpretation o. in.rared spectra,
though angular momentum can 3e important in some specialised cases (Section #07%72+7
But parity conser/ation is /ery signiLcant7 The v = 0 le/el o. the harmonic oscillator
is e/en 6hile the v = # le/el is odd and the parity o. the higher le/els is determined
similarly 3y the oddHe/en character o. v7 Thus, the o/erall parity, photon plus molecule,
is conser/ed .or transitions 3et6een ad@acent le/els7
Since magnetism is so intimately related to angular momentum in 0uantum mechanics
(Section #272+ 6e may say that ;C: is all a3out angular momentum7 An the .undamental
;C: transition o. a proton 6e ha/e 6ith a :C! photon1
# # #
9!:
=
#
m
: = +
"
+
!hoton !l
=
# m
l =
#"

9 !:
=
m
: =
".
2 2 2 2
;ote that although the K2component o. the angular momentum is conser/ed this does
not, at Lrst sight, appear to 3e the case .or the total angular momentum .or 6hich 6e ha/e
# #
2
+
#

2
7 But 6e must remem3er that the la6 .or the addition o. angular momentum
in 0uantum mechanics (Section ,7?7#+ is1
Q
#
+ Q
2
= Q
#
+ Q
2
Q
#
+ Q
2
# Q
#
+ Q
2
2 . . . |Q
#
Q
2
|
so that Lnal total angular momentum 0uantum num3ers o.
,
(#
+
#
+ or
#
!#

#
" are in
2 2 2 2
accord 6ith the re0uirement .or the conser/ation o. angular momentum7
,1, S!ECTR2SC2!IC TIME SCA5ES
There is a .urther aspect o. the .undamentals o. spectroscopic transitions that is o. impor2
tance in applications o. spectroscopy to systems 6hich are changing 6ith time7 As .ast as
they are, the processes 6here3y an atom or molecule changes its energy state as a con2
se0uence o. a3sor3ing (or emitting+ radiation are not instantaneous7 At .ollo6s, there.ore,
that i. a molecule changes its structure apprecia3ly during the time in 6hich a photon is
a3sor3ed 6e ha/e to as4 ho6 the spectrum is a..ected 3y this other process7 To 3e precise,
let us consider the e0uili3rium 3et6een the 4eto (A+ and enol (AA+ .orms o. 2,*2pentane
dione (acetyl acetone+1
A AA
9
9
Ce
C
Ce
C C
9
Ce
C
Ce
C C
"
"
"
"
9
A. the proton ;C:, A: and =8 I 8AS spectra o. each o. the t6o species in/ol/ed in
the a3o/e e0uili3rium are measured all sho6 clear di..erences on account o. the
considera3le change in the structure7 But under suita3le conditions, e7g7 in acid
a0ueous solution, there is a rapid echange and, intuiti/ely, 6e en/isage t6o etreme
possi3ilities7 A. the echange is /ery slo6 compared 6ith the time ta4en .or the
particular spectroscopic process 6hich 6e are using then 6e epect to see the spectrum
o. a miture o. A and AA
2*? Spectroscopy
in proportions reOecting the particular position o. the e0uili3rium7 We could measure the
e0uili3rium constant in this 6ay7 "n the other hand, i. the echange is /ery much .aster
than the spectroscopic transition then 6e epect the spectrum to appear li4e the spectrum
o. one su3stance o. a structure intermediate 3et6een A and AAP i7e7 the C
=
" stretching
.re0uencies in the A: 6ould lie some6here 3et6een that epected .or a .ree RC
=
"
group and the lo6er .re0uency o. the hydrogen23onded species, CI" 9 "IC7
Where
the rate o. echange and the spectroscopic transition are o. compara3le magnitude the
situation is more complicated7 An .a/oura3le circumstances, 6here the rate o. echange
can 3e controlled (e7g7 3y changing the temperature, p9 etc7+, the spectra o. an echanging
system can 3e measured at the t6o etremes and in the comple intermediate region7 ;C:
eperiments o. this type ha/e 3een 6idely reported7
"ur purpose here is to attempt to ans6er the important 0uestion, Q9o6 .ast is a spec2
troscopic transitionG J or to 3e more eplicit, Q9o6 long, .or eample, does it ta4e .or an
electron to a3sor3 a photon and @ump .rom the #s to the 2p atomic or3ital o. a hydro2
gen atomG J There appears to 3e no precise 6ay o. ans6ering this 0uestion, 3ut a use.ul
estimate o. the re0uired Lgures may 3e made using the time2energy uncertainty principle
(Section *7#0+ in the .ollo6ing manner7 When a molecule or atom is ma4ing a transition
.rom an initial to a Lnal energy state ha/ing energies E
i
and E
.
, respecti/ely, then its
energy is uncertain to the etent E
.

E
i
=
E
=
h>7 ;o6, according to 9eisen3erg1
E t h,2( h> t h,2( t 0.#?,>
6here t represents the lo6er limit o. the time ta4en to complete the spectroscopic
transition7 At is con/enient to epress the t in terms o. the .re0uency o. the transition,
>7 The times .or electronic, /i3rational and ;C: transitions are listed in Ta3le %7, .or
the speciLc eamples 6e ha/e used throughout this chapter to pro/ide representati/e
numerical data .or the three 3ranches o. spectroscopy7
Dor an A: transition, 6here 6e ha/e a simple classical concept o. a /i3rating molecule,
6e might also argue as .ollo6s7 At seems intuiti/ely reasona3le to assume that 6e could not
o3ser/e that the 9Cl molecule had changed its /i3rational state unless 6e studied it o/er
a period o. at least one complete /i3ration, i7e7 .or #,>

#.#

#0

#*
s7 This is approi2
mately si times longer than our earlier estimate o. t 7 We get the same result i. 6e ma4e
an estimate o. the ;C: time scale in terms o. the Larmor .re0uency ('0uation ($7*7#++,
6hich is %5.#5 #0
?
9K .or protons in a magnetic Leld o. 2 T7 An the case o. the =8 I 8AS
region, 6e might ta4e the time re0uired .or an electron to complete a cycle o. the lo6est
Bohr or3it 6hich is #.52

#0

#?
sP again a some6hat longer time than the /alue o. t
min
deduced .rom the uncertainty principle7 But 6e 4no6 that 0uantum mechanics tells us 6e
cannot /ie6 electrons or3iting a nucleus in the same 6ay as 6e regard planets circling
the sun7 This should 3e a 6arning to us that 6e are treading on /ery insecure ground and
Ta?le ,1' 'stimates o. the minimum time ta4en, t
min
, to complete a spectroscopic transition in
the =8 I 8AS, A: and ;C: regions o. the spectrum
=8 I 8AS A: !roton
;C:
9 atom #s

2p 9Cl
v
=
0

v
=
# m
:
= +
2

m
:
=
2
# #
< = #2#.? nm > = 2$%$-* m# / = 2 Tesla
>
=
2*.?-

#0
#*
9K >
=
%$.?,

#0
#2
9K >
=
%5.#5

#0
?
9K
t
min

?.*

#0

#-
s t
min

#.%

#0

#5
s t
min

#.$

#0

$
s
Spectroscopic units and notation 2*-
are pushing the limits o. our classical /ie6 o. the 6orld too .ar into those regions 6here
6e 4no6 that classical mechanics must 3e replaced 3y 0uantum mechanics7
Be that as it may, these crude theoretical estimates o. spectroscopic time scales sug2
gest clearly that as the processes 6hich 6e 6ish to study 3ecome .aster 6e must mo/e
to higher spectral energies i. 6e 6ish to use spectroscopy as our tool7 This Lnding is
3orne out in the la3oratory 6here ;C: spectroscopy is .re0uently used to study the
comparati/ely slo6 isomerisation processes in 6hich atoms mo/e, 6hereas the /ery .ast
processes 6hich in/ol/e solely electron trans.er must 3e studied in the =8 I 8AS
spectral
region7 An eample o. the .ormer is the study o. the 2,*2pentane dione 4eto enol
e0uili3rium mentioned pre/iously7 The latter might 3e illustrated 3y the in/estigations
o. the photo2synthetic processes in/ol/ed 6hen the chlorophyll o. green plants a3sor3s
sunlight 6here e/ents on the .emto2second (#0

#5
s+ time scale are 3eing studied7 8ery
recently a study o. the photoelectron ionisation o. neon in 6hich the authors claim to 3e
a3le to distinguish e/ents separated in time 3y #0

#?
s has 3een reported7
*
Central to these
eperiments is the generation o. pulses o. light in the etreme ultra/iolet (< # #0

%
m+ lasting only 250 #0

#%
s7
,1- QUANTUM E5ECTR23YNAMICS
)
At 6as clear in the discussion o. spectroscopic time scales that 6e ha/e 3een descri3ing
a theory 6hich is a miture o. classical and 0uantum mechanical concepts7 Throughout
our discussion o. the interaction o. radiation 6ith matter (Section %7?+ 6e ha/e treated
the atoms and molecules as ha/ing 0uantised energy le/els, 3ut in our calculations o.
intensities 6e descri3ed the electromagnetic radiation in terms o. electric and magnetic
Lelds, i7e7 a classical /ie6point7 A consistent theory must 0uantise 3oth the energy le/els
o. the atoms and molecules and the Lelds7 The Lrst step in this direction 6as made
3y 'instein in #$05 6hen he suggested that the interactions 3et6een electromagnetic
radiation and matter 4no6n at that time might 3e 3etter eplained in terms o. light 0uanta
than in terms o. oscillating electric and magnetic Lelds7 The light 0uanta, 6hich 6e no6
call photons, are the 0uanta o. the electromagnetic Leld7 A systematic attac4 upon the
pro3lem o. a complete 0uantum description o. the interaction o. radiation 6ith matter
6as 3egun 3y <irac 0uite early in the history o. 0uantum mechanics7
By the #$-0s a sophisticated and detailed theory 6as a/aila3le7 The modern .orm o.
this theory is 4no6n as 0uantum electrodynamics (&'<+ and it has pro/ed capa3le o.
pro/iding etremely accurate /alues o. crucial 0uantities in the theory o. spectroscopy7
Andeed, though spectroscopic measurements are among the most accurate in the 6hole o.
science, the theories used to analyse them are in many cases e0ual to the challenge o.
interpreting these elegant data 0uantitati/ely7 &'< is especially important in the interpre2
tation o. eperiments in/ol/ing the adsorption andHor emission o. se/eral photons 6ithin
a /ery short time inter/al 6hich are o. gro6ing importance in chemistry7 9o6e/er, this
is not the place to pursue this topic .urther7
,1%. S!ECTR2SC2!IC UNITS AN3 N2TATI2N
The most .re0uently used spectroscopic units and notation are the su3@ects o. the penul2
timate section o. this chapter7 Spectroscopists ha/e 3een some6hat reluctant to adopt SA
units in their entirety and non2SA usage is .re0uently .ound, e/en in modern pu3lications
2*% Spectroscopy
(this 3oo4 includedU+7 ;aturally, it also occurs in earlier 6or4 and it seems appropriate
here to summarise the more commonly used units and notation7 At is help.ul to di/ide
this section into t6o parts and to discuss the 0uantities appearing on the t6o aes o. a
spectrum under di..erent headings7
,1%.1% T$e energ0N"re@;en#0NwaAelengt$ axis
This is normally the horiKontal ais o. the spectrum and the 0uantities 6hich may 3e
sho6n on it are listed in Ta3le %7*7 They relate directly to the position o. the a3sorption
or emission 3and in the electromagnetic spectrum, 6hich implies an energy di..erence
gi/en 3y the Bohr I 'instein condition, E = h>7 An SA units this energy 6ould 3e gi/en
in Joules, 3ut spectroscopists ha/e traditionally used other units, some not e/en strictly
energy units, in 6hich to report E7 The electron /olt (e8+, 6hich is the 4inetic energy
ac0uired 3y an electron 6hen it is accelerated in an electric Leld o. one /olt, is a true
energy unit and is 6idely used in electronic and photoelectron spectroscopy (Chapter ##+7
The 6a/e num3er, >, is not an energy unit 3ut it is directly proportional to energy
(E = hc> +7 An.rared and :aman spectra are almost al6ays discussed in terms o. 6a/e
num3ers7 An ;C: spectroscopy, the spin2spin coupling energy is al6ays epressed as a
.re0uency, i7e7 in 9K, 3ut .or 3oth technical and data2trans.era3ility reasons, the position
o. a resonance is in/aria3ly reported in terms o. its position 6ith respect to the resonance
o. a standard7 (Dor more in.ormation see Chapter $7+
The relati/e num3er o. molecules, ;
a
and ;
3
, in t6o energy le/els separated 3y an
energy di..erence o. E
a3
!= E
a
E
3
" is determined 3y BoltKmannGs la6 as1
;
a
,;
3
= ep! E
a3
, ;- " !%.#0.#"
This relationship plays an etremely important role in spectroscopies, nota3ly ;C:,
6here E
a3
is /ery small so that ;
a
;
3
7 The units o. ; are energy T

#
and an a3solute
temperature o. # > can 3e seen as e0ui/alent to an energy o. ;', 6here ' is the energy
unit in 6hich ; is measured7 This pro/ides a 6ay o. relating energy to the a3solute scale
o. temperature, 6hich is /ery use.ul .or discussing spectroscopic phenomena that depend
upon temperature, such as the population o. energy le/els7
Where the energies o. single molecules are to 3e related to practical chemical 0uantities,
the energy per mole in 4J mol

#
is the appropriate SA unit7
Ta?le ,1( Some 0uantities 6hich may 3e .ound on the energyH.re0uencyH6a/elength ais o. a
spectrumP sym3ols and units
&uantity Sym3ol <eLnition SA unit "ther units or sym3ols
Wa/elength < m nm,
A
l
(A
l
ngstrom+ = #0

#0
m
Dre0uency > > = c,< 9K s

#
P cycles per second
Angular .re0uency A A = 2(> s

#
rad s

# a
Wa/e num3er in /acuum > > = >,c
o
= #,n<
c
m

#
cm

#
= #0

2
m

# *
Wa/e num3er in a medium ' ' = #,< m

#
cm

#
= #0

2
m

# *
Chemical shi.t ) see Chapter $ parts per million (ppm+
a
rad s

#
= radians per second (the radian is dimensionless+7
*
The 4ilo4ayser (4>+ has 3een proposed as the unit .or #000 cm

#
, 3ut this suggestion has not 3een 6idely
adopted7
c
n
=
re.racti/e inde7
Ta?le ,1) 'nergy2con/ersion .actors
Wa/e
num3er
> (cm

#
+
Dre0uency
> (C9K+
'nergy
E!J

#0

#%
"
'nergy
E(e8+
Colar
energy
E
m
(4J mol

#
+
Temperature
- (>+
> 1 # cm

#
# 2.$$-$25
#0
*
#.$%?**-
#0

5
*.55?,,5
#0

?
##.$?2??
#0

,
#7*,%-?$
> 1 # C9K ,.,,5?*
#0

5
# ?.?2?0-?
#0

#0
*.#,5??$
#0

$
,.$$0,#,
#0

-
*.-$$22
#0

5
E1 #atto J 50,*#7# #.50$#%$
#0
$
E1 # e8 %0?575* 2.*#-$%%
#0
%
# ?72*#50? ?0272#,- -.2*2$2
#0
*
07#?02#-- # 2?257500 ,.#5--,
#0
5
E
m
1 # 4J mol

#
%,75$,5 2.50?0?$
#0
?
#.??05*0
#0

,
#.0,?*2-
#0

2
# #2072-2
- 1 # > 07?$50,$ 2.0%,?-

#0
*
#.,%0?5%

#0

5
%.?#-,%

#0

5
%.,#*5# #

#0

,
Ta3le %75 gi/es the con/ersion .actors 3et6een the /arious QenergyG units mentioned
a3o/e7 The in/erted commas around the 6ord energy ser/e as a Lnal reminder that some
o. these units are not energy units and, .or eample, # e8 may 3e thought o. as e0ui/alent
to, *1t not e71al to, %0?575* cm

#
7
,1%.1& T$e intensit0Na?sor?an#e axis
The second ais o. the spectrum is the one 6hich records @ust ho6 much radiation has
3een a3sor3ed or emitted7 This ais is especially important 6hen a spectroscopic mea2
surement is 3eing used in 0uantitati/e analysis7 Such procedures are almost al6ays 3ased
upon relati/e, rather than a3solute, measurements since only in this 6ay is the re0uired
accuracy o3taina3le7 A. the pro3lem is to determine the concentration o. copper in a sam2
ple o. 6ine,
]
then the spectroscopic instrument used, an atomic a3sorption spectrometer
in this eample, 6ould Lrst 3e cali3rated using standard copper solutions and the cop2
per concentration in the un4no6n sample determined 3y comparison 6ith the cali3ration
graph7 The measurement o. the 0uantity o. light a3sor3ed or emitted is recorded as a
change in the output signal o. the detector and a3solute measurement o. the intensity o.
the radiation is not re0uired7
An =8 I 8AS and A: spectroscopy the most common measure o. the 0uantity o.
radiation a3sor3ed is the a3sor3ance, A
<
, 6hich is deLned 3y the e0uation1
A
<
= log
#0
!A
o
,A
tr
"
<
!%.#0.2"
6here A
o
is the intensity o. the radiation .alling upon the sample and A
tr
is the inten2
sity o. the transmitted radiation at a particular 6a/elength, <7 The /alue o. A
<
in
'0uation (%7#072+ is calculated directly 3y modern spectrometers and the determination
o. the a3sor3ance is a particularly important aspect o. 0uantitati/e analysis in the ultra2
/iolet, /isi3le and in.rared regions o. the spectrum7 A
<
is related to the concentration o.
light2a3sor3ing su3stance, C, 3y the Beer I Lam3ert I Bouguer la6 (Bo %7*+1
A
<
= '
<
CL !%.#0.,"
]
There is Cu
2
+
in 6ine 3ecause a .ungal in.ection o. the /ines is treated 3y spraying them 6ith an a0ueous suspension o.
lime and copper sul.ate 4no6n as /ordea1x mixt1re7
6here L is the path length o. the radiation through the sample and '
<
is the molar
decadic a3sorption coe.Lcient, 6hich has a characteristic /alue .or e/ery compound at
e/ery 6a/elength, <, and is directly related to the pro3a3ility that a photon o. that 6a/e2
length stri4ing the molecule 6ill 3e a3sor3ed7 The 6ord QdecadicG arises 3ecause A is
deLned in terms o. logarithms to 3ase #0 rather than to 3ase e in '0uation (%7#072+7
,1%% THE EINSTEIN C2E66ICIENTS
Dinally, mention should 3e made o. three parameters characterising transition pro3a3ilities
deduced 3y 'instein in #$#- using purely thermodynamic reasoning7 They are the 'instein
coe.Lcients o. induced emission (B
m

n
+, a3sorption (B
n

m
+ and spontaneous emission
(A
mn
+7 'insteinGs argument and the relationships 3et6een these parameters are descri3ed
in Bo %757
,1%& 8I85I2RA!HY AN3 6URTHER REA3IN
#7 S7D7 Cason, A 8istory of the Sciences, Collier Boo4s, ;e6 Ror4, #$?2P Chapters ,- and ,%7
27 :7A7 Beth, Phys. Rev., (,, *-# (#$,5+P )., ##5 (#$,?+7
,7 T7:7 <y4e, G7:7 Tomase/ich, W7 >lemperer and W7 Dalconer, Q. Chem. Phys., )+, 22-- (#$-2+7
*7 :7 >ien3erger et al7, Nat1re, (&+, %#- (200*+7
57 <7!7 Craig and T7 Thirunamachandran, 5olec1lar 31ant1m Electrodynamics, Academic !ress,
;e6 Ror4, #$%*, <o/er !u3lications Anc7, ;e6 Ror4, #$$%7
82D ,1% T$e Compton e""e#t
An #$2, Arthur 9olly Compton (#%$2 I #$?2+ o3ser/ed that 6hen F2rays are
scat2 tered 3y electrons the 6a/elength o. the scattered rays is slightly longer than
that o. the incident raysP i7e7 the radiation has lost energy7 This o3ser/ation could not 3e
eplained 3y a 6a/e theory o. light and Compton suggested the .ollo6ing interpreta2
tion, 6hich pro/ides one o. the most con/incing pieces o. e/idence .or the photon as
a discrete particle that has mass and, there.ore, linear momentum7 Consider a photon
6ith .re0uency >
i
mo/ing in the 2direction7 At stri4es a stationary electron o. mass
m
o
and is scattered at an angle o. $ to its original path and its .re0uency is reduced
to >
.
7 The collision causes the electron to mo/e o.. 6ith /elocity v and momentum
& v at an angle o. G to the 2ais, Digure B%7#7#7
photon hn
.
photon hn
i
.
F
y
electron m
6ig;re 8,1%1% Collision o. a photon 6ith a stationary electron7
Boes .or Chapter % 25#
Compton analysed the pro3lem using the re0uirements that energy and linear
momentum 3e conser/ed7 9e epressed the energy o. the electron in terms o. 'in2
steinGs e0uation E = mc
2
, and o3tained the momentum o. the photon 3y com3ining
the t6o e0uations .or its energy, i7e7 E = h> = mc
2
% = mc = h>,c7 The rest mass
o. the electron, m
o
, is related to its mass 6hen in motion, m, 3y '0uation (%7*75+1
#
m
o
=
m
{
#

!v,c"
2
} 2
or m
2
!c
2

v
2
"
=
m
o
2
c
2
(B%7#7#+
There.ore, 3e.ore the impact1
!hoton1 E = h>
i
% = h>
i
,c
'lectron1 '
=
m
o
c
2
%
=
0
and a.ter the impact1
!hoton1 E = h>
.
% = h>
.
,c
'lectron1 '
=
mc
2
%
=
mv
The conser/ation o. momentum re0uires that along 1
h>
i
,c = !h>
.
,c" cos $ + mv cos G mvc cos G = h>
i
h>
.
cos $ (B%7#72+
and perpendicular to 1
!h>
.
,c" sin $ = mv sin G mvc sin G = h>
.
sin $ (B%7#7,+
The conser/ation o. energy re0uires that1
h>
i
+ m
o
c
2
= h>
.
+ mc
2
mc
2
= h!>
i
>
.
" + m
o
c
2
(B%7#7*+
S0uaring 3oth sides o. '0uations (B%7#72+ and (B%7#7,+ and adding gi/es1
mv
2
c
2
= h
2
>
i
+ h
2
>
.
2h
2
>
i
>
.
cos $ = h
2
!>
i
+ >
.
2>
i
>
.
cos $" (B%7#75+
S0uaring 3oth sides o. '0uation (B%7#7*+ gi/es1
m
2
c
*
= h
2
!>
i
>
.
"
2
+ m
o
2
c
*
+ 2h!>
i
>
.
"m
o
c
2
= h
2
!>
i
+ >
.
2>
i
>
.
" + m
o
2
c
*
+ 2h!>
i
>
.
"m
o
c
2
(B%7#7?+
Su3tracting '0uation (B%7#7?+ .rom '0uation (B%7#75+ 6e ha/e1
mc
2
!v
2
c
2
" = 2h
2
>
i
>
.
!cos $ #" m
o
2
c
*
2h!>
i
>
.
"m
o
c
2
and using '0uation (B%7#7#+1
h>
i
>
.
!# cos $" = !>
i
>
.
"m
o
c
2
Since <> = c, this result may 3e 6ritten1
# cos $ = m
o
c
2
!>
i
>
.
", h>
i
>
.
= {m
o
c
2
, h}{!#,>
.
" !#,>
i
"} = {m
o
c, h}{<
.
<
i
}
This e0uation is in eact agreement 6ith ComptonGs o3ser/ations7 The manner
o. its deri/ation sho6s that the photon may 3e considered to 3e a particle 6ith
momentum h>,c7 The .actor h,m
o
c, 6hich has the units o. length, is 4no6n as the
Compton 6a/elength and has the numerical /alue 2.*2

#0

#2
m7

82D ,1& T$e transition /ipole moment in t$e $0/rogen atom
:eaders 6ill ha/e noted that '0uation (%7-7%+ re0uires that there is a change o.
dipole moment associated 6ith the /i3ration i. the transition moment o. an in.rared
transition is to 3e non2Kero, 6hereas no such condition attaches to the epression
('0uation (%7-7#0++ .or an electronic transition dipole moment7 And i., as an eample,
6e consider the strongly allo6ed #s 2p transition o. the hydrogen atom, it is di.L2
cult to en/isage ho6 the dipole, 6hich is to interact 6ith the electric Leld o. the light,
arises7 Whereas a classical /ie6point is 0uite satis.actory .or /i3rational spectroscopy,
and also .or ;C: 6here 6e ha/e a precessing magnet 6hich can interact 6ith an
oscillating magnetic Leld (Chapter $+, the case o. an electronic transition demands
a 0uantum2mechanical analysis7 We can, ho6e/er, ma4e the 6hole process more
plausi3le 3y considering the time2dependent initial, #s, and Lnal, 2p, 6a/e .unctions7
According to '0uation (%7?7,+, the t6o time2dependent 6a/e .unctions ha/e the
.orms1

#s
= $
#s
ep!i2(E
#s
t, h" and
2p
= $
2p
ep!i2(E
2p
t, h"
'ach o. the states is an eigenstate o. the atomic 9amiltonian operator and 6e may
also .orm a state 6hich is a superposition o. the t6o1

sum
=
#s
+
2p
= $
#s
ep!i2(E
#s
t, h" + $
2p
ep!i2(E
2p
t, h"
Compare '0uation (%7?7?+7 The a3o/e epression .or
sum
may 3e 6ritten1

sum
= ep!i2(E
#s
t, h"{$
#s
+ $
2p
ep!i2( ZE
2p
E
#s
\t, h"}
;ote that
sum
is not an energy eigenstate7 At t = 0, the pro3a3ility o. Lnding the
hydrogen electron at any point in space is gi/en 3y the product1
sum

sum
= {$
#s
+ $
2p
}
2
We no6 eamine ho6
sum
changes 6ith time7
When a time t
=
h,2!E
2p

E
#s
" has elapsed the 6a/e .unction can 3e 6ritten1

sum
= ep!i2(E
#s
t, h"{$
#s
+ $
2p
ep!i( "} = ep!i2(E
#s
t, h"{$
#s
$
2p
}
3ecause ep!i( " = # (see Bo *7,+7 We might also ha/e su3stituted the Lrst t in
the a3o/e e0uation, 3ut this is unnecessary since that part o. the epression reduces
to # 6hen 6e carry out our net step7
The pro3a3ility o. Lnding the hydrogen electron at any point in space is no61
sum

sum
= ep!+i2(E
#s
t, h" ep!i2(E
#s
t, h"{$
#s
$
2p
}
2
= {$
#s
$
2p
}
2
A.ter a .urther period o. time e0ual to h,2!E
2p
E
#s
"
sum
6ill ha/e returned
to its /alue at t = 0 and the oscillation 3et6een $
#s
+ $
2p
and $
#s
$
2p
continues
indeLnitely7
Because o. the di..ering phases o. the t6o lo3es o. the 2p .unction, the centre
o. the electronic charge distri3ution mo/es .rom one side o. the nucleus to the other
(Digure B%727#+, thus creating an incipient oscillating dipole 6hich is al6ays ready
#s
2p
#s + 2p #s 2p
6ig;re 8,1&1% The time2dependence o. the #sH2p electron distri3ution7
and a3le to interact 6ith light o. the correct .re0uency, should such light .all on the
atom7 Andeed, the .re0uency o. the oscillation is !E
2p
E
#s
", h 6hich is eactly the
.re0uency o. the #s 2p transition, 3ut 6e must 3e care.ul not to dra6 un6arranted
conclusions .rom this .act7 We are in danger o. straying into the 0uantum2mechanical
6orld armed only 6ith classical2mechanical concepts7
82D ,1' T$e 6ran#> I Con/on prin#iple
The data in Ta3le %7* sho6 that the time re0uired .or an /i3rational transition is o. the
order o. #00 times that re0uired .or an electronic transition7 Already in #$25, James
Dranc4 (#%%2 I #$?*+ had reasoned that 3ecause the masses o. nuclei 6ere so
much greater than that o. electrons the .ormer 6ould mo/e much more slo6ly and that
they might 3e considered to 3e essentially stationary during the period re0uired .or an
elec2 tronic transition7 The same concept underlies the Born I "ppenheimer
approimation (Section ?7,+7 A. 6e thin4 in terms o. the potential2energy cur/es .or the
ground and ecited states o. a diatomic molecule (Digure B%7,7#+, then an
electronic transition 3et6een these states 6ith no motion o. the nuclei during that time
implies a transition 6ith no change o. internuclear distance, i7e7 a /ertical transition7
An #$2$ 'd6ard =hler Condon (#$02 I #$-*+ analysed the pro3lem 6ith the
ne6 0uantum mechanics7 9e deri/ed '0uation (%7-7#0+, .ollo6ing essentially the
method descri3ed in Section %7-7#, Case 2, and came to the same conclusion as Dranc47
But 3y introducing the concept o. the o/erlap o. the /i3rational .unctions o. the ground
and ecited electronic states, Condon made it possi3le, in .a/oura3le cases, to calculate
the relati/e intensities o. /i3rational Lne structure and pro/ided a method o.
determining the change o. shape 6hich ta4es place 6hen a molecule is electronically
ecited7 This sort o. in.ormation is o. great /alue in the study o. molecules in their
electronically ecited states7
And e/en 6hen a 0uantitati/e calculation is not possi3le, 6e can dra6 conclu2
sions a3out the ground and ecited state potential energy cur/es .rom the appearance
o. the /i3rational structure7 Digure #07? sho6s that, as 6e mo/e to higher 0uan2
tum num3ers, the lo3es o. harmonic /i3rational .unctions 3ecome disproportionately
'
n
e
r
g
y
n
,
2
#
0
0
Anternuclear distance
6ig;re 8,1'1% The Dranc4 I Condon principle 6ith r
e
(ground state+ r
e
(ecited
state+
larger at the turning points o. the /i3ration and this is more mar4ed in the case
o. anharmonic /i3rations7 Thus, the maimum o/erlap occurs 6here the upper state
potential energy cur/e lies /ertically a3o/e the e0uili3rium internuclear conLguration
o. the ground state 3ecause, at room temperature, almost all molecules 6ill 3e in
their /i3rational ground state7 When the e0uili3rium 3ond length o. the upper state is
similar to that o. the lo6er state 6e ha/e the situation depicted in Digure B%7,7#7 The
/i3ronic transition, 6hich has the maimum o/erlap, is the 0 0 transition and so
the Lrst 3and is the most intense and as 6e go to higher energies the intensity .alls o..
6ith increasing v

, the /i3rational 0uantum num3er o. the upper state7 The resulting
spectrum is sho6n diagrammatically to the le.t o. the potential energy cur/es7 The
#

+
!r
e
= #*$7#0 pm"
#
!r
e
= #5*7?? pm" transition o. !;, 6hich is .ound in the
region o. *0 000 cm

#
, is o. this type7 The relati/e intensities o. the Lrst .our 0 v

/i3ronic 3ands .all in the se0uence 20, ,, 2, 07
When, as is usually the case, the upper electronic state is more 6ea4ly 3ound than
the ground state, the e0uili3rium 3ond length o. the upper state increases and the
particular /i3ronic transition 6hich has the maimum o/erlap 6ith the v

= 0 le/el
o. the ground state changes mo/es to higher /alues o. v

7 ;o6 the /i3ronic 3and o.
maimum intensity has 3ands o. decreasing intensity to6ards 3oth higher and lo6er
/alues o. v

, i7e7 to6ard 3oth higher and lo6er energies (Digure B%7,72+7 The
#

+
!r
e
=
##27%# pm"

#
!r
e
=
#2,75# pm" 3and o. C", .ound at a3out ?5 000 cm

#
, .alls
into this category7
'
n
e
r
g
y
'
n
e
r
g
y
c
o
n
t
i
n
u
u
m
n
*
,
2
#
0
0
Anternuclear distance
6ig;re 8,1'1& The Dranc4 I Condon principle 6ith r
e
(ground state+ P r
e
(ecited state+
n
,
2
#
0
0
Anternuclear distance
6ig;re 8,1'1' The Dranc4 I Condon principle 6hen a /ertical transition enters the continuum
,

At is 0uite common .or the upper state potential energy cur/e to 3e so .ar displaced
to longer 3ond length andHor so shallo6 that maimum /i3rational o/erlap occurs at
an energy a3o/e the dissociation energy o. the molecule, so that a3sorption o. the
corresponding photon results in decomposition o. the molecule into its constituent
atoms7 When this is the case the spacing o. the /i3ronic 3ands decreases until it
is unresol/a3le and the intensity o. the spectrum reaches a maimum some6here
in the continuum (Digure B%7,7,+7 The .amous Schumann2:unge 3ands o. oygen,
g
!r
e
=
#207-* pm"

,

u

!r
e
=
#?0 pm", pro/ide an eample o. this 3eha/iour7
The 0 0 3and is .ound at *$ %02 cm

#
and the con/ergence limit at 5? %50 cm

#
at 6hich energy the oygen molecule dissociates into one ground2state atom "(
,
!+
and one ecited atom "(
#
<+7 At is little 6onder that ecitation processes such as this
lead to etensi/e photochemistryU
9erK3erg
#
should 3e consulted .or .urther details and eamples o. the Dranc4 I
Condon principle7
RE6ERENCE
#7 G7 9erK3erg, S%ectra of Eiatomic 5olec1les, <7 8an ;ostrand Anc7, ;e6 Ror4, #$507
82D ,1( T$e 8eer I 5am?ert I 8o;g;er 5aw
a
An this 3o 6e interpret theoretically the la6s o. light a3sorption disco/ered eperi2
mentally 3y Beer, Lam3ert and Bouguer during the #$th century7
Suppose (Digure B%7*7#(a++ that a 3eam o. light tra/erses a path o. L m in a
solution o. an a3sor3ing solute, concentration C mol dm

,
, in a transparent sol/ent
contained in a transparent cell or cu/ette7 Let the intensity o. the light o. .re0uency
> 3e A
0
!>" on entering the solution and A(>+ on lea/ing it7 We do not need to speci.y
the units o. the intensity since 6e shall Lnd that our result depends upon an intensity
ratio7
As the light ma4es its 6ay through the solution each succeeding layer o. the
solution is su3@ect to a diminished intensity o. light since some o. the light has
already 3een a3sor3ed 3y the preceding layers7 There.ore, in order to calculate the
total intensity loss, 6e consider (Digure B%7*7#(3++ an inLnitely thin layer o. thic4ness
dl and # m
2
cross section at right angles to the direction o. propagation o. the light7
Let the cross2sectional area o. the a3sor3ing molecules 3e a m
2
per molecule, the
intensity o. the light entering the thin layer o. the solution i, the amount o. light
A
0
(n) A(n)
C
L
#
i dl
#
(a+ (3+
6ig;re 8,1(1% The passage o. a light 3eam through an a3sor3ing solution7
=
a3sor3ed in the layer di and the pro3a3ility that a photon .alling upon a molecule
is a3sor3ed 07 Then the num3er o. molecules per m
,
is #0
,
CN
A
6here N
A
is the
A/ogadro constant7 There.ore, the cross2sectional area o. the molecules in the layer is
#0
,
aCN
A
dl7 Since the pro3a3ility o. each photon 3eing a3sor3ed is 0, the .raction
o. light a3sor3ed in the layer is #0
,
0aCN
A
dl1
di = #0
,
0aCN
A
idl or di = ' Cidl 6here '
= #0
,
0aN
A
The di has a negati/e sign 3ecause i gets smaller as l increases7
Antegrating o/er the intensity .rom A
0
to A and path length .rom 0 to L 6e ha/e1
A L

di


i
=
'

C
A
0
0
dl log
e

A0

A
= '

CL
or, con/erting to logarithms to 3ase #01

A
0

log
#0
A
=
0.*,*,'

CL

'CL
The 0uantity log
#0
(A
0
HA+ is called the a3sor3ance, AP it has no dimensions or units7 '
is the molar decadic a3sorption coe.Lcient, its units are m
2
mol

#
, i7e7 cross2sectional
area per mole, 6hich eplains 6hy ' is sometimes spo4en o. as a cross section in
some 3ranches o. science and technology, though rarely in chemistry7
*
A. 6e set
the cross2sectional area o. a molecule to #0

#$
m
2
then .or 0 = #.0 6e ha/e the
maimum possi3le /alue o. ' o. 2.5 #0
-
7 The minimum /alue is, o. course, Kero7
The 0uantity T, 4no6n as the percentage transmission, is also used as a measure o.
the light a3sorption1
The e0uation1

A

T
A
0
#00 Y
or 3etter
c
1
A = 'CL
A
<
= '
<
CL
sho6s that A is proportional to path length (the Bouguer I Lam3ert la6+ and also
to concentration (the Beer la6+7 All 0uantitati/e applications o. spectroscopy are 3ased
upon BeerGs la6 and its practical signiLcance cannot 3e o/erestimated7
#otes:
a Terminology o. the type used here (a3sor3ance, a3sor3ance coe.Lcient, path length+
is uni/ersal in =8 I 8AS spectroscopy, /ery much less common in A:
spectroscopy and ne/er used in ;C: spectroscopy7
* An older literature the a*sor%tion coe.Lcient is almost al6ays called the extinction
coe.Lcient and has units o. cm
2
mol

#
7 The a*sor*ance is .re0uently called the
o%tical density7
c At must 3e remem3ered that A and ' are .unctions o. the 6a/elength or .re0uency
o. the light7 This is the 3asic .act responsi3le .or 6hat 6e 4no6 as a spectrum7
82D ,1) T$e Einstein #oe"B#ients
Although no 0uantum mechanics is in/ol/ed, any account o. the a3sorption and
emission o. radiation 6ould 3e incomplete 6ithout a mention o. the coe.Lcients
6hich 'instein introduced, on the 3asis o. thermodynamic arguments, in #$#-7
There are three distinct 6ays in 6hich an atom or molecule can undergo a transition
3et6een t6o 0uantised energy states, m and n, ha/ing energies E
m
and E
n
7 All three
are o. interest to the chemical spectroscopist7 A. 6e assume that E
m
R E
n
, then the
transition .rom n to m 6ill 3e accompanied 3y the a3sorption o. a photon o. .re0uency
>
mn
gi/en 3y the Bohr I 'instein relationship1
>
mn
= !E
m
E
n
", h (B%757#+
Similarly, the transition .rom m to n 6ill result in the emission o. a photon o.
.re0uency >
mn
7 'instein proposed that the pro3a3ility o. the transition .rom n to m,
!
nm
, is proportional to =!>
mn
", the energy density o. the radiation at the .re0uency
>
mn
, and gi/en 3y the e0uation1
!
n

m
= B
n

m
=!>
mn
" (B%7572+
The constant o. proportionality, B
n

m
, is called the Einstein coefCcient of a*sor%+
tion7 Dor the transition .rom the higher to the lo6er energy state 'instein postulated
that there 6ere t6o processes to 3e considered7 Dirstly, the system could simply emit
a photon spontaneously and drop to the lo6er state .or no eternal reason7 Secondly,
the transition .rom m to n could 3e induced 3y a photon in @ust the same 6ay as the
transition .rom n to m is induced7 The total pro3a3ility o. the transition .rom m to n
is there.ore the sum o. t6o processes and1
!
m

n
= A
m

n
+ B
m

n
=!>
mn
" (B%757,+
6here A
m

n
is 'insteinGs coe.Lcient o. spontaneous emission and B
m

n
is 'insteinGs
coe.Lcient o. induced emission7 The process o. spontaneous emission is eactly the
same as the spontaneous emission o. a N 2ray 3y a radioacti/e nucleus7 A. 6e no6
consider a large num3er o. systems at e0uili3rium 6ith radiation at a temperature, - ,
then the energy density o. the radiation is gi/en according to !lanc4 (Section 275+ 3y
the e0uation1
=!>
mn
" = %( h!>
mn
"
,
,!c
,
Zep{h>, ;- } #\" (B%757*+
6here ; is the BoltKmann constant7 A. the num3er o. systems in state m is ;
m
and
the num3er in state n is ;
n
, then the num3er o. systems ma4ing the transition .rom
state n to state m in unit time is1
;
n
B
n

m
=!>
mn
" (B%7575+
!ro3lems .or Chapter % ,
mn mn
a 3 a
3

/i3
and the num3er mo/ing in the re/erse direction is1
;
m
{A
m

n
+ B
m

n
=!>
mn
"} (B%757?+ At
e0uili3rium these t6o num3ers must 3e e0ual and 6e ha/e1
;
n
,;
m
= {A
mn
+ B
mn
=!>
mn
"},B
nm
=!>
mn
" (B%757-+
But according to BoltKmann the ratio ;
n
H;
m
is gi/en 3y the e0uation1
;
n
,;
m
= ep{!E
m
E
n
", ;- } = ep{h>
mn
, ;- } (B%757%+
'0uating the t6o epressions .or ;
n
H;
m
6e Lnd the .ollo6ing epression .or
=!>
mn
"1
=!>
mn
" = A
m

n
,!B
n

m
ep{h>
mn
, ;- } /
m

n
" (B%757$+ A.
this is to 3e identical 6ith '0uation (B%757*+, the three 'instein coe.Lcients must
3e related as .ollo6s1
and
B
n

m
= B
m

n
(B%757#0+
A
m n
= %( h!> ,c"
,
B (B%757##+
We Lnd that the coe.Lcients o. induced emission and a3sorption are e0ual 6hile
the coe.Lcient o. spontaneous emission di..ers .rom them 3y a .actor o. %( h!>
mn
,c"
,
7
!R285EMS 62R CHA!TER ,
#7 Com3ine t6o plane2polarised 6a/es, E
o
and E
o
$0

out o. phase and 6ith E
o
=
2

E
o
7 What path is traced 3y the head o. the com3ined E2/ectorJ
27 Calculate G
2pK
|C

|G
#s
and G
2p
|C

|G
#s
6here G
#s
and G
2p
are hydrogen2atom
or3itals (Appendi 5+
,7 =sing the data .or
#
9I
,5
Cl in Bo #072 and the /i3rational 6a/e .unctions in Bo
#07,, sho6 that1
.
/i3
|r|
i
=
h
%(
2
T\
= -.5$ pm
9int1 A. .(+ is a .unction o. e/en po6ers o. only then1

+
.(+ d = 2

+
.(+ d
0
Rou 6ill also Lnd the .ollo6ing integral use.ul, it holds .or a R 0 and all integer
/alues o. n R #7 {nU = n !n #" !n 2" . . . #P 0U = #}

+

n
e

a
d =
nU
a
n
+
#
0
2
#
;
*7 Sho6 that the 6a/e .unction ('0uation (%7?75++1
= $
a
ep!iAt "
is an eigen.unction o. SchroM dingerGs time2dependent e0uation ('0uation (%7?72++,
3ut that the 6a/e .unction ('0uation (%7?7?++1
=
a
c
a
$
a
ep!iAat"
is not7
57 The energies, '
m
, and 6a/e .unctions,
m
, o. the 9uM c4el ( 2electron molecular
or3itals o. linear con@ugated polyenes may 3e 6ritten in closed alge3raic .orm1

m
'
m
= L + 2 cos
+ #
K
m
=

2

;
+
#
r
sin

rm(
$
r
; + #
6here ; is the num3er o. con@ugated car3on atoms and r = # 2 . . . ; num3ers the
atoms7 The deLnitions o. L and K are gi/en in Section #27# 3ut this 4no6ledge is not
re0uired .or this pro3lem7
The highest occupied C" has m =
#
; and the lo6est unoccupied C" has m =
2
; + #7 The ( (

transition .rom the lo6er to the higher o. these t6o C"s is

responsi3le .or the strong, long26a/elength a3sorption 3and 6hich characterises these
compounds and increases mar4edly in intensity as the chain gets longer7 Sho6 that the
intensities predicted using the a3o/e C"s also increase in the series ; = * ? %7
A suggested method .or this calculation is the .ollo6ing1
(a+ Consider a polyene to 3e a Kig2Kag chain o. atoms 6ith a uni.orm 3ond length o.
#*0 pm and all CICIC angles #20

7 <eLne an ais as the line passing through

the centre points o. all the 3onds 6ith = 0 in the centre o. the molecule7
(3+ Calculate the transition density at each car3on atom assuming, in accord 6ith the
9uM c4el theory, that there is no o/erlap 3et6een the A"s on di..erent car3on
atoms7 Cultiply the transition density 3y the co2ordinate o. that atom7
(c+ Sum the results .or each atom to o3tain the component (in e pm+ o. the transition
dipole moment .or molecules ha/ing ; = *, ? and %7
(Ta4ing account o. symmetry 6ill considera3ly reduce your 6or4U+
The results .or ; = * are ta3ulated 3elo6 as a guide7
r = # 2 , *
Transition density = +0.,?2 e 0.#,% e +0.#,% e 0.,?2 e
co2ordinate = #%#7% pm ?07? pm +?07? pm +#%#7% pm
Transition dipole moment = ?5.%# e pm +%.,? e pm +%.,? e pm ?5.%# e pm
Sum
=
##*.$ e pm The intensity is proportional to (sum+
2
=
#,202 e
2
pm
2
Chapter $
N;#lear Magneti# Resonan#e
Spe#tros#op0
$70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?#
$7# The magnetic properties o. atomic nuclei . . . . . . . . . . . . . . . . . . . . . . . . 2?2
$72 The .re0uency region o. ;C: spectroscopy . . . . . . . . . . . . . . . . . . . . . . 2?*
$7, The ;C: selection rule . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?*
$7* The chemical shi.t . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?-
$7*7# The delta ()+ scale . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2?%
$7*72 The shielding constant, ' (sigma+ . . . . . . . . . . . . . . . . . . . . . . . . 2-0
$75 ;uclear spin I spin coupling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-0
$7? The energy le/els o. a nuclear spin system . . . . . . . . . . . . . . . . . . . . . . 2-,
$7?7# Dirst order spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-*
$7?72 Second order spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-5
$7- The intensities o. ;C: spectral lines . . . . . . . . . . . . . . . . . . . . . . . . . . 2-?
$7% &uantum mechanics and ;C: spectroscopy . . . . . . . . . . . . . . . . . . . . . 2--
$7$ Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-%
!ro3lems .or Chapter $ . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2%-
-1. INTR23UCTI2N
An Chapter * 6e sa6 that electrons and many nuclei ha/e an intrinsic angular momentum
6hich 6e call spin angular momentum7 This angular momentum is in/aria3ly associated
6ith a magnetic moment as Wol.gang !auli, originator o. the !auli eclusion principle,
proposed in #$2*7 !auliGs suggestion 6as conLrmed in #$,$ 6hen the deOection o.
atomic 3eams 3y magnetic Lelds 6as detected7 ;uclear magnetic resonance in 3ul4 matter
6as Lrst reported in #$*?7 The presence o. the magnetic moments associated 6ith the
spin o. electrons and nuclei causes these particles to interact 6ith each other and 6ith
applied magnetic Lelds and these interactions are /ery important in se/eral 3ranches o.
spectroscopy7 An nuclear magnetic resonance and electron spin or paramagnetic resonance
spectroscopies the interactions o. the nuclei and the electrons 6ith applied magnetic Lelds
are studied7 The 0uantum mechanics 6hich underlies the t6o .orms o. spectroscopy is
/ery similar, though they are o.ten discussed in /ery di..erent language7 Some important
.ormulae are collected together in Ta3le $7# and descri3ed in more detail 3elo67
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
? ;uclear Cagnetic :esonance Spectroscopy
Ta?le -1% The Cagnetic !roperties o. the 'lectron and the !roton
'lectron !roton
Spin angular momentum
in units o. hH2(
characterised 3y the
h` h,2( = #.05*5$2 #0
,*
Js
0uantum num3ers s and m
s
: and m
:
The magnetic moment in Bohr magnetons, T
B
nuclear magnetons, T
;
T = g
e

Zs!s + #"\ T = +g
9

Z: !: + #"\
6here T
B
= eh,*(m
e
T
;
= eh,*(5
= $.2-* #0
2*
J T
#
= 5.05# #0
2-
J T
#
and the g .actors are
An J T
#
Alternati/ely
g
e
= 2.002,#$
T = g
e
T
B

Zs!s + #"\
T = +N
e
!h,2("

Zs!s + #"\
g
9
= 5.5%5?$#
T = +g
9
T
;

Z: !: + #"\
T = +N
9
!h,2("

Z: !: + #"\
6here N is the
magnetogyric ratio N
e
= g
e
T
B
,!h,2("
= #.-?0 #0
##
rad T
#
s
#
N
9
= g
9
T
;
,!h,2("
= +2?.-52 #0
-
rad T
#
s
#
Similarly T
K
= +N
e
hm
s
,2( T
K
= +N
9
hm
:
,2(
Since E = T_B = T
K
/
K
.or a magnetic Leld aligned along the K ais1
E = +g
e
T
B
m
s
/ E = g
9
T
;
m
:
/
and
#
E!+
#
" = g
e
T
B
/ g
9
T
;
/
2 2
The data .or the proton also ser/e as an eample .or all nuclei7 But it must 3e noted that the /alues o. the
nuclear gGs and N Gs are di..erent .or e/ery nucleus, i7e7 .or e/ery isotope7
-1% THE MANETIC !R2!ERTIES 26 AT2MIC NUC5EI
The spin and magnetic properties o. all sta3le nuclei are no6 6ell documented7 There
are three use.ul rules 6hich can 3e used to predict the spin angular momenta o. nuclei7
#7 ;uclei 6ith an odd mass num3er ha/e a hal.2integral spin 0uantum num3er, .or
eample1
#
9, : =
#
P
2,
;a, : =
,
P
2-
Al, : =
5
7
2 2 2
27 ;uclei 6ith an e/en mass num3er and an e/en charge num3er ha/e Kero spin, .or
eample1
#2
C,
#?
",
,2
S7
,7 ;uclei 6ith an e/en mass num3er and an odd charge num3er ha/e an integral spin
0uantum num3er, .or eample1
2
9, : = #P
#0
B, : = ,P
#*
;, : = #7
The spin angular momentum, P , o. a nucleus is determined 3y the 0uantum num3er
: according to '0uation ($7#7#+1
P =

Z: !: + #"\h,2(
!$.#.#"
and its magnetic moment, T, is gi/en 3y the e0uation1
T = g
;
T
;

Z: !: + #"\ = 2( g
;
T
;
P, h
!$.#.2"
2
2
'
n
e
r
g
y

(
/
m
)
<
i
r
e
c
t
i
o
n

o
.


N

a
n
d

/
The Cagnetic !roperties o. Atomic ;uclei 2?,
T
;
= eh,*(5 is the nuclear magneton 6hich has the /alue 5.050$5 #0
2-
J T
#
and relates the spin angular momentum to the magnetic Leld produced7 (e is the elementary
charge, h !lanc4Gs constant and 5 the mass o. the proton7+ g
;
is the nuclear g .actor,
a 0uantity 6hich, at the present state o. our 4no6ledge, can only 3e determined 3y
eperiment and may 3e either positi/e or negati/e7 A negati/e /alue indicates that the
magnetic moment and the angular momentum /ectors point in opposite directions7 At is
con/enient to epress T in terms o. a 0uantity N
;
, the magnetogyric ratio, rather than
g
;
, 6here1
and there.ore1
N
;
= g
;
T
;
2(, h !$.#.,"
T = N
;
P !$.#.*"
The magnetogyric ratio is a .actor 6hich con/erts the angular momentum in units o.
hH2( into magnetic moment in units o. J T
#
, hence its name7 Thus, the nuclear magnetic
moment is related to the nuclear spin 0uantum num3er, : , 3y the e0uation1
T = g
;
T
;

Z: !: + #"\ = N
;

Z: !: + #"\h,2(
($7#75+ As 6e 4no6 .rom Chapter *, .or a spin 0uantum num3er : there are 2: + #
possi3le orientations o. the spin angular momentum in space, each characterised 3y
a di..er2
ent /alue o. the 0uantum num3er m
:
, 6hich ta4es all integer or hal.2integer /alues
.rom : to +: 7 Conse0uently, 2: + # orientations o. the nuclear magnet are also pos2
si3le and the component o. the magnetic moment in the K direction, in analogy to
'0uations ($7#7*+ and ($7#75+, is (Bo #272+1
T
K
= N
;
P
K
= N
;
m
:
h,2( !$.#.?"
An general, this 6ill 3e o. no o3/ious conse0uence, 3ut in the presence o. a magnetic
Leld each orientation 6ill ha/e a di..erent energy, as illustrated in Digure $7# .or : =
,
, e7g7 the
2,
;a nucleus7 The energy, E, o. a magnet, T, placed in a magnetic Leld
o.
strength / is (Bo #272+1
E = T/ cos # !$.#.-"
+(,H5+
m
:
,H2
+(#H#5+
#H2 0
(#H#5+
+#H2
(,H5+
+,H2
6ig;re -1% The energy le/els o. the .our 5
:
components o. an : =
,
nucleus in a magnetic Leld
% ;uclear Cagnetic :esonance Spectroscopy
#0
2-
>(C9K+ #0
2-
>(C9K+ #0
2-
>(C9K+
# 2%72# *275% 07-0* -7#0 #07-# 27%00 ##7*, #-725 #7-,-
* ##27$ #-07, 07#-? 2%7,% *27%, 07-00 *57-, ?$702 07*,*
% 2257- ,*07? 070%% 5?7-? %57?- 07,50 $#7*? #,%70 072#-
2
2
#
6here # is the angle 3et6een the ais o. the magnet T and the direction o. / (Digure $7#+7
A. 6e orientate the Leld along the K2direction then '0uation ($7#7-+ can 3e 6ritten1
E = T
K
/ = N
;
/m
:
h,2(
!$.#.%"
Thus, i. a molecule containing atoms 6hich ha/e nuclear magnetic moments is placed
in a magnetic Leld each o. the 2: + # su32le/els 6ill ha/e a di..erent energy and, i. the
molecule is irradiated 6ith e2m radiation o. a suita3le .re0uency, transitions 3et6een these
energy le/els may 3e induced7 Such transitions are 4no6n as nuclear magnetic resonance
(;C:+ and the process .orms the 3asis o. ;C: spectroscopy7
-1& THE 6REQUENCY REI2N 26 NMR S!ECTR2SC2!Y
The conser/ation o. energy, as epressed in the Bohr I 'instein condition (Section
%757#+ determines the region o. the e2m spectrum in 6hich ;C: spectra 6ill 3e o3ser/ed7
The condition re0uires that the energy di..erence 3et6een the t6o states shall 3e e0ual to
the energy, h>, o. the photon 6hich is a3sor3ed 6hen it stimulates the transition7 Ta3le
$72
# #
sho6s the energy gap 3et6een the t6o m
:
le/els, m
:
= +
2
and m
:
=
2
, .or
three
nuclei ha/ing : =
#
and three magnetic Lelds7 We see that the energy separation, e/en
at high magnetic Lelds, is /ery small7 The corresponding 6a/elengths and .re0uencies
are those 6hich 6e associate 6ith tele/ision and radio transmission7 Although 6e may
say that ;C: is o3ser/ed in the region o. the e2m spectrum 3et6een #0 and #000 C9K,
this is a /ery 6ide range o. .re0uencies and 6ithin it each nucleus is conLned to 0uite
a narro6 3and, 6ell separated .rom the resonances o. other nuclei7 Though a modern
;C: instrument can 3e readily ad@usted to measure the spectra o. a num3er o. di..erent
nuclei, e7g7
#
9,
#,
C,
#$
D,
,#
! . . . in chemical applications only the range o.
resonance .re0uencies o. one particular nuclear species is co/ered in any one
eperiment7
-1' THE NMR SE5ECTI2N RU5E
The .act that the energy di..erence 3et6een the t6o energy le/els ha/ing m
:
=
#
and
+
2
satisLes the Bohr I 'instein condition is not in itsel. su.Lcient to ensure that
transitions 3et6een the t6o le/els can 3e o3ser/ed 6hen the sample is irradiated 6ith e2
m radiation
o. the a3o/e .re0uencies7 There must 3e a mechanism 6here3y the photon or e2m 6a/e
can interact 6ith the nucleus and cause it to change its energy 3y a3sor3ing the photon7
The mechanism is the interaction 3et6een the oscillating magnetic Leld o. the radiation
# #
Ta?le -1& The energy gap 3et6een the nuclear spin le/els 6ith m
:
= +
2
and m
:
=
2
.or
three .re0uently2studied nuclei at three /alues o. the applied magnetic Leld (The corresponding
.re0uencies and 6a/elengths are also gi/en+
/ (T+ E(J+
#
9 <(m+ E(J+
#,
C
<(m+ E(J+
,#
!
<(m+
$ ;uclear Cagnetic :esonance Spectroscopy
The ;C: Selection :ule 2?5
and the magnetic moment o. the nucleus7 To understand ho6 this happens Lrst recall
(Chapter *+ that, e/en 6hen m
:
= : , the magnetic moment o. the nucleus does not
lie eactly along the K2direction7
;o6, suppose that 6e place a 3ar magnet, in the .orm o. a rod and mounted at its centre
on a .rictionless 3earing, in a magnetic Leld7 A. 6e displace the magnet .rom alignment
6ith the Leld there is a tor0ue 6hich tries to return the magnet to the aligned orientation7
A. 6e release the magnet it 6ill realign itsel. 6ith the Leld, 3ut it 6ill o/ershoot the
position o. minimum energy and then oscillate a3out it7 Since the 3earing is .rictionless,
this oscillation 6ill continue indeLnitely (Digure $72(a++7 Suppose .urther that the magnet
is spinning a3out its ais so that there is angular momentum directed along that ais7
The tor0ue 6hich see4s to realign the magnet 6ith the magnetic Leld is no6 opposed 3y
the re0uirement that the angular momentum and its direction in space 3e conser/ed7 The
result o. these t6o conOicting demands is that the magnet precesses a3out the direction o.
the Leld li4e a gyroscope or top in the gra/itational Leld o. the earth7 That is, the magnet
rotates a3out the Leld in such a 6ay that its north and south poles descri3e circles around
the direction o. the Leld as illustrated in Digure $72(3+7 This is eactly the same as the
motion o. a top 6hen the ais o. the top slo6ly circles around the /ertical line dra6n
through the point at 6hich the top is in contact 6ith the ground7 This motion o. nuclei
in a magnetic Leld is 4no6n as Larmor %recession and its .re0uency, f , the
Larmor .re0uency, is gi/en 3y1
f = N
;
/,2( !$.,.#"
in 6hich the magnetogyric ratio is again in/ol/ed7
The precession o. T a3out the K2ais (Digure $7,+ produces a rotating magnetic Leld in
the y2plane and this pro/ides the QhandleG 3y means o. 6hich the e2m radiation is a3le
to distur3 the precessional motion o. the nucleus7 A. the precessing nucleus is irradiated
6ith circularly polarised radiation then, i. the .re0uency o. the radiation is /ery di..erent
.rom the Larmor .re0uency, there 6ill 3e no e..ect7 But i. the .re0uency o. the radiation
is e0ual to the Larmor .re0uency then the rotating magnetic moment and the rotating
magnetic Leld o. the radiation 6ill remain in phase 6ith each other and the e..ect is to tip
Dield direction
Dield direction
;
;
;
;
magnet not
spinning magnet
spinning
S
S S S
magnet oscillates
magnet precesses
(a+ (3+
6ig;re -1& The dynamic 3eha/iour o. a 3ar magnet mounted on a .rictionless 3earing and placed
in a magnetic Leld
#0 ;uclear Cagnetic :esonance Spectroscopy
2
N
B
0
m
B
#
6ig;re -1' Larmor precession
# #
the nucleus o/er .rom the m
:
= +
2
into the m
:
=
2
orientation7 But energy also
has
to 3e conser/ed and 6e there.ore ha/e t6o criteria 6hich the .re0uency o. the radiation
must satis.y1
#7 The .re0uency o. the radiation must 3e e0ual to the Larmor .re0uency, i7e7 it must
satis.y '0uation ($7,7#+, so that > = f = N
;
/,2( 7
27 The .re0uency o. the radiation must satis.y the Bohr I 'instein condition1
h> = E > = N
;
/h!
#

#
",2h( = N
;
/,2(
($7,72+
2 2
# #
Thus, the energy re0uired .or the transition 3et6een the t6o le/els m
:
= +
2
and
2
does indeed imply radiation o. the same .re0uency as the Larmor precession and the t6o
re0uirements are satisLed 3y the same radiation7 The same analysis applies .or nuclei
6ith /alues o. m
:
other than
#
and, clearly, the criterion that the radiation shall
ha/e the re0uired energy and the Larmor .re0uency is al6ays met 3y a transition
3et6een any pair o. le/els 6hose m
:
/alues di..er 3y #, 3ut not .or any other transition7
The ;C: selection rule is there.ore1
m
:
= #
!$.,.,"
;ote that the selection rule is eactly the same .or the a3sorption o. a photon and an
increase in energy as .or the emission o. a photon and a decrease in energy7 The .act that
3oth processes are e0ually pro3a3le is /ery important in ;C: spectroscopy and 6e shall
return to it later7
;aturally, 0uantum mechanics also pro/ides a more precise description o. the process
6here3y interaction 6ith an electromagnetic 6a/e changes the energy o. a nucleus in a
magnetic Leld7 :ecall (Section %7?+ that the lin4 3et6een the initial and Lnal states o.
a spectroscopic transition 3rought a3out 3y e2m radiation can 3e 6ritten as the product
o. a time2dependent and a time2independent part7 '/aluation o. the time2dependent part
2
2
2
2
The Chemical Shi.t ##
results in the Bohr I 'instein or energy conser/ation condition, 6hich is the same in
all 3ranches o. spectroscopy7 The time2independent part, in the case o. ;C:, ta4es the
.orm (see Bo $7# .or .urther @ustiLcation+1
!N /
#
"
2
|
Lnal
|:

|
initial
|
2
!$.,.*"
6here /
#
is the magnetic Leld o. the applied radiation that oscillates in the 2direction
and :

is the operator .or the 2component o. the nuclear spin7 ;ote that in ;C: it is
the
oscillating magnetic Leld o. the radiation 6hich interacts 6ith the nucleusP in almost all
other spectroscopies it is the electric Leld7 But this ma4es no di..erence in the e/aluation
o. the time2dependent part o. the interaction since the electric and magnetic Lelds o. the
radiation oscillate in phase and are descri3ed 3y eactly the same cosine or sine .unctions7
Since there are only t6o spin states .or a nucleus ha/ing : =
#
, the operation o. :

on
one o. them must gi/e the otherP in .act, in units o. h,2( (Bo $7#+1
:

|+
#
=
#
!:

+ :

"|+
#
=
#
|
#

!$.,.5a"
and
2 2
+
2 2 2
:

|
#
=
#
!:

+ :

"|
#
=
#
| +
#

!$.,.53"
2 2
+
2 2 2
(;ote that these are not eigen.unction2eigen/alue e0uationsP the .unction, |
#
, on
either side o. the e0uality sign is not the same7+ There.ore, the interaction o. an e2m
6a/e 6ith its magnetic Leld /i3rating in the 2direction con/erts states .rom m
:
=
#
to m
:
= +
#
, and /ice /ersa, 6ith e0ual .acilityP i7e7 3oth processes are e0ually
pro3a3le7
Though the case does not arise here 6e might also note that :

lin4s any t6o spin states
6hose m
:
/alues di..er 3y #, e7g7 +
#
is lin4ed to
#
and +
,
P +# is lin4ed to 0 and +27
2 2 2
-1( THE CHEMICA5 SHI6T
'amination o. the e0uations a3o/e sho6s that the .re0uency at 6hich a nucleus resonates
depends only upon its magnetogyric ratio and the magnetic Leld in 6hich it is placed7 A.
this 6ere the 6hole story ;C: spectroscopy 6ould 3e o. little interest to chemists7 But in
January #$50 the editor o. the Physical Revie0 recei/ed t6o letters re0uesting pu3lication
o. eciting and surprising ne6 o3ser/ations7 W7C7 <ic4inson 6rote1 QCost unepectedly,
it has 3een .ound that .or
#$
D the /alue o. the applied magnetic Leld .or nuclear magnetic
resonance at a Led radio .re0uency depends on the chemical compound containing the
Ouorine nucleus7G W7G7 !roctor and D7C7 Ru reported that1 QAn the course o. measurements
on
#*
; 6e made the surprising o3ser/ation that its .re0uency o. resonance, in li0uid
samples, depended strongly upon the chemical compound in 6hich it 6as contained7G
These o3ser/ations, so clearly unepected, 6ere the trigger .or an eplosi/e gro6th o.
;C: spectroscopy 6hich has completely changed the 6ay in 6hich much o. chemistry
is practised and sho6s no sign o. diminishing a.ter more than 50 years7
Dollo6ing the introduction o. the Dourier2trans.orm method and the de/elopment o.
;C: into argua3ly the most important spectroscopic techni0ue .or chemical applications,
ne6 imaging techni0ues ha/e made it a /ital ad@unct to medicine7 !ictures o. the li/ing
human 3rain and other /ital organs are no6 routinely o3tained in all ma@or hospitals
6here the techni0ue is 4no6n as ;C: tomography7 Those 6ho 3elie/e that the only
research 6orth pursuing is research 6ith an o3/ious application @ust around the corner
S
i
g
n
a
l

h
e
i
g
h
t

(
a
r
3
i
t
r
a
r
y

u
n
i
t
s
+
T
C
S

(
s
t
a
n
d
a
r
d
+
should study the history o. ;C: care.ully7 The ad/ances in imaging, in particular, arose
.rom eperiments in 6hich magnetic nuclei 6ere made to dance a @ig to an intricate
se0uence o. pulses o. radiation7 Who could ha/e dreamed that this esoteric pursuit o.
4no6ledge 6ould lead, 6ithin a3out 20 years, to detailed pictures o. the li/ing, 6or4ing
human 3rainJ
:eturning to chemistry, the cause o. the /ariation in resonance .re0uency or Leld
6ith chemical composition 6as soon clear to those 6ho o3ser/ed it7 The nuclei 6e meet
in chemistry are al6ays surrounded 3y clouds o. electrons and these electrons ha/e an
important e..ect upon the magnetic Leld eperienced 3y the nuclei7 When an atom is placed
in a magnetic Leld the motion o. its electrons 6ill 3e slightly changed and, according
to LenKGs la6, the change 6ill 3e such as to oppose the applied Leld7 There.ore, all
other things 3eing e0ual, 6hich is usually 3ut not 0uite al6ays the case, the nucleus 6ill
eperience a Leld slightly less than the applied Leld and 6ill resonate at a slightly lo6er
.re0uency than that gi/en 3y '0uation ($7,72+7 This di..erence in resonance .re0uency,
6hich depends upon the electron density in the immediate neigh3ourhood o. the nucleus,
is called the chemical shift7 At has 3een .ound that the resonance .re0uency o. a nucleus
is highly characteristic o. its chemical en/ironment and can there.ore 3e used to identi.y
molecules and particular groupings o. atoms 6ithin molecules7 The ;C: spectrum o. a
solution o. *23romo22,?2dimethylphenol, in 6hich the di..erent resonance .re0uencies o.
the three types o.
#
9 in the molecule can 3e readily seen, is sho6n in Digure $7*7 The
pea4s can e/en 3e assigned to the particular
#
9 types, since their heights are directly
proportional to the num3er o. protons in any particular chemical en/ironment7 The t6o
horiKontal scales in Digure $7* re0uire .urther eplanation and 6e no6 turn to the su3@ect
o. the chemical shi.t scale7
-1(1% T$e /elta F)G s#ale
The most o3/ious chemical shi.t scale might appear to 3e one in 6hich the resonance
.re0uency o. a particular nucleus in a molecule is related to the .re0uency o. that nucleus
Chemical shi.t (d+ (delta+
#0700 %7,, ?7?- 5700 ,7,, #7?- 0700
-
"9
?
9
,
C
C
5
C C
*
C C
9
C
,
Br
2
C9
,
9
#
0
?00 500 *00 ,00 200 #00 0
:esonance .re0uency shi.t .rom TCS (9K+
6ig;re -1( The ;C: spectrum o. *23romo22,?2dimethylphenol
%
5
7
#
5
,
$
*
2


9
+
%
5
7
#
5
2
*
2
%


9
%
5
7
#
5
2
2
$
5


9
2
S
"
*
%
5
7
#
5
#
$
2
?


C
9
C
l
,
%
5
7
#
5
#
?
-
-


9
2
%
5
7
#
5
#
,
-
0


9
2
"
%
5
7
#
5
#
,
0
-


T
C
S
%
5
7
#
5
0
$
*
$


C
9
*
%
5
7
#
5
0
#
$
#

9
A
Dre0uency (C9K+ (.or a magnetic .ield o. 2 T+
,5 ,0 25 20 #5 #0 5 0 5 #0 #5
Chemical shi.t (d+ .rom TCS
6ig;re -1) Typical proton chemical shi.ts ()+ .rom TCS
Ta?le -1' Some
#
9 resonance .re0uencies (>+ at a
Leld o. 2 T and the corresponding shi.ts ()+ .rom
tetramethyl silane (TCS+
9ydrogen nucleus > at 2 T(C9K+ )
Bare proton, 9
+
%57#5,$*2 +,#7**
9ydrogen atom %57#52*2% +#,7#?
9
2
S"
*
%57#522$5 +##7?0
C9Cl
,
%57#5#$2? +-72-
9
2
molecule %57#5#?-- +*7,*
Water /apour %57#5#,-0 +07-*
TCS %57#5#,0- 0700
C9
*
%57#50$*$ *72#
9A %57#50#$# #,7##
in the total a3sence o. all its electrons, i7e7 the 3are nucleus7 Digure $75 and Ta3le $7,
present some
#
9 resonance data in such a .orm .or a magnetic Leld o. 2 T7
9o6e/er, it is /ery di.Lcult to measure the eact magnetic Leld to 6hich a molecule
is eposed7 This is especially so 6hen it is dissol/ed in a sol/ent, contained in a sample
tu3e and surrounded 3y a thermostat to maintain constant temperature7 But this 6ould
3e necessary i. the chemical shi.ts o. the nuclei 6ere to 3e measured as a3solute /alues
against the resonance .re0uency o. the 3are nucleus7 At has there.ore 3ecome uni/ersal
practice to measure the shi.t relati/e to the resonance position o. a standard su3stance that
has one 6ell deLned resonance7 Dor
#
9,
#,
C and
2$
Si tetramethyl silane ZTCS, Si(C9
,
+
*
\ is used and the chemical shi.t scale, 4no6n as the ) scale, is deLned as1
)
a
= #0
?
!>
a
>
TCS
",>
TCS
!$.*.#"
The .actor o. #0
?
is included simply to gi/e readily handled num3ers and the ) /al2
ues o. the chemical shi.t scale are said to 3e in %arts %er million (ppm+7 This .orm o.
chemical shi.t scale has a .urther ad/antage7 Since it is a ratio o. a .re0uency di..erence
and a .re0uency, 3oth o. 6hich are directly proportional to the applied magnetic Leld
('0uation ($7,72++, the ) /alue is independent o. the Leld and measurements made 6ith
di..erent instruments using any com3ination o. Leld and .re0uency can 3e immediately
compared7 Thus, 6hen the chemical shi.ts in an ;C: spectrum are reported in these units
the result is o. permanent /alue, and such data .orm the 3asis o. the ta3les o. chemical
shi.t /alues 6hich are used to identi.y molecules and groupings o. atoms in them7 The )
/alues .or the protons in Digure $75 are gi/en in Ta3le $7,7
T6o important comments may 3e made concerning these data7 An the Lrst instance 6e
note that the range o. resonance .re0uency is /ery small, some ,7% 49K as compared 6ith
the mean resonance .re0uency, 6hich is /ery near to %5 C9K7 Secondly, the resonance
.re0uency depends directly upon the magnetic Leld used7 There.ore, the greater the Leld
the greater is the spacing 3et6een the resonances, i7e7 the resolution o. the spectrometer
is increased and, in order to 3e a3le to study more comple molecules, there has 3een
a continuous dri/e to increase the a/aila3le magnetic Leld7 The highest Lelds currently
a/aila3le in commercial ;C: instruments are in the region o. #0 T7 With the aid o. such
instruments, plus a /ariety o. sophisticated 6ays o. carrying out the eperiment including
the use o. isotopic la3elling 6ith
#5
;,
#,
C and
2
9, the ;C: spectra o. proteins
6ith :C: /alues o. the order o. ,0 I *0 4<a can no6 3e measured and interpreted7
-1(1& T$e s$iel/ing #onstant< ' FsigmaG
An Section $7, 6e sa6 that the .re0uency, >, o. a nuclear magnetic resonance signal in
a Leld /
0
is gi/en 3y '0uation ($7,72+, > = N
;
/
0
,2( 7 We introduce the e..ect o.
the chemical shi.t into this epression 3y deLning a shielding constant, '
a
, .or each
nucleus, a, in a molecule so that the Leld, and hence the resonance .re0uency, is reduced
according to the e0uation1
>
a
= N
;
/
0
!# '
a
",2(
!$.*.2"
6here, in continuing to use N
;
rather than N
a
, it is assumed that only nuclei o. the same
species are in/ol/ed in the spectrum7
By su3stituting '0uation ($7*72+ into '0uation ($7*7#+ 6e o3tain the relation 3et6een
' and ) as1
)
a
= #0
?
!'
TCS
'
a
",!# '
TCS
"
But since the ' /alues o. nuclei important .or chemical ;C: spectroscopy are /ery much
less than #, the .orm1
)
a
= #0
?
!'
TCS
'
a
"
!$.*.,"
is 0uite su.Lcient .or chemical purposes7 ;ote that increasing ) corresponds to decreasing
' and that spectra are plotted 6ith > and ) increasing .rom right to le.t7
-1) NUC5EAR S!IN I S!IN C2U!5IN
An practice, ;C: spectra are normally more comple than the a3o/e discussion might
lead us to epect7 Dor eample, the
#
9 spectrum o. #,#,22trichloroethane, (Digure $7?+
sho6s 5 lines (resonances+, although it contains only three hydrogen atoms7 A clue as to
the assignment o. the lines is gi/en 3y the .act that the sum o. the t6o signals centred
2
S
i
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h
e
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g
h
t

(
a
r
3
i
t
r
a
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y

u
n
i
t
s
+
T
C
S

(
s
t
a
n
d
a
r
d
+
;uclear Spin I Spin Coupling 2-#
Chemical shi.t (d) (delta+
#0700 %7,, ?7?- 5700 ,7,, #7?- 0700
5
* C
3
9Cl
2
C
a
9
2
Cl
,
2
#
0
?00 500 *00 ,00 200 #00 0
Dre0uency shi.t .rom TCS (9K+
6ig;re -1* The ;C: spectrum o. #,#,22trichloroethane
at ,7$5 ppm (2,- 9K+ is t6ice that o. the three signals at 57-- ppm (,*? 9K+7 Since,
in ;C:, the signal height is usually proportional to the num3er o. nuclei in the same
chemical en/ironment, this suggest that the t6o lines at ,7$5 ppm are caused 3y the
protons mar4ed QaG and the three lines at 57-- ppm 3y that mar4ed Q3G7 The cause o.
this splitting o. the resonance lines is the nuclear spin I spin coupling, 6hich arises in
the .ollo6ing manner7
'ach nucleus capa3le o. gi/ing a resonance signal does so 3ecause it has a magnetic
moment 6hich, in the case o. nuclei 6ith : =
#
, can 3e aligned in t6o directions
6ith respect to the direction o. the applied magnetic Leld, /
0
7 The magnetic moment o.
each nucleus is there.ore capa3le o. increasing or decreasing the applied Leld and this
change
can 3e detected 3y other nuclei i. they are su.Lciently close to it7 The process is mutualP
i. QaG .eels the e..ect o. Q3G then Q3G .eels the e..ect o. QaG7 Consider the spectrum o.
#,#,22trichloroethane again7 The protons QaG eperience either an increased or a decreased
magnetic Leld depending upon 6hether the proton Q3G is aligned 6ith the applied Leld
or against it7 There.ore, they eperience t6o Lelds, and resonate at t6o slightly di..erent
.re0uencies7 But this is too simple an eplanation o. the actual mechanism o. spin I
spin coupling and 6e must eamine the phenomenon more closely7
Consider Lrst Digure $7-7 The large open circles represent nuclei and the Llled circles
electrons in a hydrogen molecule7 The arro6s indicate the orientation o. the spin magnetic
moments associated 6ith the .our particles7 "n the le.t2hand side 6e Lnd that the electron
6ig;re -1+ Spin I spin coupling in the hydrogen molecule
#? ;uclear Cagnetic :esonance Spectroscopy
dra6n closest to the nucleus has its magnetic moment in the direction opposite to that
o. the nucleus, i7e7 the t6o particles ha/e orientated their magnetic moments so as to
minimise the energy o. interaction7 This type o. electron nucleus interaction is 4no6n as
Dermi contact interaction a.ter 'nrico Dermi (#$0# I #$5*+ 6ho Lrst suggested it in
#$,0 to eplain e..ects seen in atomic spectroscopy7
At is important to note that it is not the same as the dipole2dipole interaction, 6hich is
.elt 6hen t6o 3ar magnets held in the hands are 3rought close together7 The interaction 6e
are concerned 6ith here arises 3ecause, as small as they are, the nucleus and the electron
are not point charges and this interaction is present 6hen the t6o are in QcontactG7
]
Thus, 3ecause o. the Dermi contact e..ect, the t6o electrons in the 929 3ond are not
eactly e0ually distri3uted in the 3ond7 An the region o. the hydrogen nucleus on the le.t
there is a slight ecess o. the electron 6ith its magnetic moment directed do6n6ards
3ecause the magnetic moment o. the nucleus is directed up6ards7 But since the electron
spins must 3e paired in total this must imply that there is also a slight im3alance at the other
end o. the molecule in the sense that there is an ecess o. the electron 6ith its magnetic
moment directed up6ards in the region o. the right2hand hydrogen nucleus7 The energy
o. the molecule is there.ore slightly lo6er 6hen the right2hand nucleus has its magnetic
moment directed do6n6ards7 Thus, the energy o. the hydrogen molecule is slightly lo6er
6hen the nuclear magnetic moments are opposed (antiparallel+ than it is 6hen they are
parallelP this energy di..erence is the spin I spin coupling energy7 At is etremely
small7
An the case o. the hydrogen molecule its /alue is h 2%0 9K = #.%55 #0
,#
J,
6hich
should 3e compared 6ith the molecular 3inding energy o. -.?05 #0
#$
J, a .actor
o. approimately * #0
#2
U Cost coupling constants are much smaller than this and it
is a
tri3ute to the technology o. the ;C: eperiment that 6e are a3le to measure and ma4e
use o. such tiny energy di..erences7
;ote ho6 the nuclear spin in.ormation is transmitted 3y the electrons7 An molecules that
do not ha/e a Led spatial orientation, e7g7 in a solution, the dipole2dipole interaction o.
the nuclear spins eists, 3ut 6e do not see it 3ecause the constantly changing orientation
o. the molecule 6ith respect to the applied magnetic Leld a/erages the dipolar coupling
to Kero7 The spin I spin coupling 6hich 6e measure is the electron+mediated
coupling7 At should 3e noted that t6o other mechanisms, the s%in+di%olar and or*ital
terms, also contri3ute to the electron2mediated coupling o3ser/ed in the Ouid phase, 3ut
since these mechanisms ha/e a negligi3le e..ect on proton2proton coupling 6e ignore
them here7
Digure $7% is a similar illustration o. the 9ICICI9 unit o. #,#,22trichloroethane and
in the Lrst 9IC 3ond the situation is 0ualitati/ely eactly the same as that in the 9I9
9 C C 9
6ig;re -1, Spin2spin coupling in a hydrocar3on .ragment
]
The idea that the electron can 3e Qin contact 6ithG or QatG the nucleus is a poor classical description, 3ut the 3est 6e ha/e,
o. a situation 6hich can only 3e properly descri3ed in mathematical terms7 But it does ma4e clear 6hy only s2electrons ha/e
The 'nergy Le/els o. a ;uclear Spin System #-
a Dermi contact interaction 6ith the nucleusP all other atomic or3itals ha/e a node at the nucleus7
2
=
#% ;uclear Cagnetic :esonance Spectroscopy
3ond a3o/e and i. the car3on atom is a
#,
C atom 6ith : =
#
then CI9 coupling is
o3ser/ed7 But the coupling message can 3e transmitted .urther along the molecule7 The
t6o electrons sho6n on either side o. the car3on atom are in/ol/ed in di..erent 3ondsP a
9IC 3ond on the le.t and a CIC 3ond on the right7 Conse0uently, these electrons are not
paired and, according to 9undGs rule (Chapter 5+, their energy is lo6er 6hen their spins,
and there.ore their magnetic moments, are parallel7 This e..ect transmits the electron spin
polarisation into the CIC 3ond and hence to the second car3on atom, 6here the same
mechanism induces a spin polarisation in the CI9 3ond7 Dinally, 6e arri/e at the second
hydrogen nucleus, 6hich .or lo6est energy should ha/e its magnetic moment aligned
antiparallel to that o. the Lrst7 This spin I spin coupling mechanism leads to the
result that .or coupling o/er an odd num3er o. 3onds the more sta3le orientation o. the
nuclear magnetic moments is antiparallel, 6hile .or coupling o/er an e/en num3er o. 3onds
the parallel orientation is the more sta3le7 The .ormer coupling is deCned to 3e
positi/e and the latter negati/eP this alternation o. the sign o. the coupling 6ith the num3er
o. inter/ening 3onds is .re0uently o3ser/ed in ;C: spectroscopy7 9o6e/er, the
magnitude o. the coupling diminishes 0uite rapidly as the num3er o. 3onds increases7
Though the mechanism o. spin I spin coupling 3y electrons is comple, the
0uantum mechanical epression o. the e..ect is /ery simple i. 6e regard the coupling
interaction energy 3et6een t6o nuclei, r and s, as a parameter, the coupling constant
J
rs
, to 3e determined 3y eperiment7 The energy can then 3e 6ritten as J
rs
multiplied 3y
the scalar
product o. I

r
and I

s
, the nuclear spin operators .or the t6o
nuclei1
Anteraction energy = E
J
= J
rs
I

r
I

s
= J
rs
Z:

r
:

s
+ :

ry
:

sy
+ :

rK
:

sK
\
=
J
rs
Z:

rK
:

sK
+
#
r s r
s
!$.5.#"
2
!:

+
:


+ :

:

+
"\
and 6e al6ays di/ide E
J
3y !lanc4Gs constant and 0uote the coupling in 9K, the unit in
6hich it is measured eperimentally7
-1* THE ENERY 5EVE5S 26 A NUC5EAR S!IN SYSTEM
Summarising Sections $7* and $751 the 9amiltonian operator .rom 6hich the energy o. all
the nuclear spins in a molecule can 3e calculated includes the interaction 6ith the applied
Leld, /
0
, allo6ing .or the shielding, ' , and the nuclear spin I spin coupling, J7
=sing
:

K
|: m
:
= m
:
|: m
:
to trans.orm '0uation ($7#7%+ to operator .orm and com3ining
6ith
'0uation ($757#+ 6e 6rite the 9amiltonian, in units o. .re0uency, as1
h
#
9

= !2( "
#

N
r
/
0
!# '
r
" :

rK
+

J
rs
I

r
I

s
or, using '0uation ($7*72+, as1
h
#
9

r

>
r
:

rK
+
r

rPs
rPs
J
rs
I

r
I

s
!$.?.#"
As an eample 6e shall consider the simple case o. t6o protons, QaG and Q3G7 8ery
detailed treatments o. much more comple systems may 3e .ound else6here7
#2
The 'nergy Le/els o. a ;uclear Spin System #$
There are .our possi3le arrangements o. the K components o. the spins o. t6o protons
(al6ays 6ritten in the order a,3+, |+
#
+
#
|+
#

#
|
#
+
#
, and |
#

#
7 These
2 2 2 2 2 2 2 2
are the 3asis .unctions o. the pro3lem and 6e shall .ollo6 the approach, descri3ed in
#
2
2
2
Appendi ,, o. setting up the matri o.
9

in this 3asis and diagonalising it7 The Lrst

term in '0uation ($7?7#+ is the chemical shi.t, 6hich gi/es a contri3ution to the on2
diagonal elements o. our * * matri7 There are no o..2diagonal elements since the
t6o nuclei are not lin4ed in any 6ay 3y :

rK
7 As an illustration o. the operation o. this
Lrst term on a 3asis state 6e ha/e1


>
r
:

rK
|+
#

#
= >
a
:

aK
|+
#

#
>
3
:

3K
|+
#

#
= Z>
a
>
3
\|+
#

#
2 2 2 2
r
2 2 2 2 2
To illustrate the second part o. the operator, the scalar coupling, 6e e/aluate1
J
a3
Z:

aK
:

3K
+
#
a 3 a
3
# # #
a3
# # # # # #
a3
2
!:

:

+
+ :

+
:

"\|+
2

2

= J
Z
2

2
\|+
2

2
+
2
J
|
2
+
2

# # # # # #
=
*
J
a3
|+
2

2
+
2
J
a3
|
2
+
2

The Lrst term gi/es a diagonal, the second an o..2diagonal matri element7 =sing the
.act that the spin 3asis .unctions are orthogonal and normalised the complete matri is
.ound to 3e1
# # # #
# # # #
# # #
|+
2
+
2
|+
2

2
|
2
+
2

|
2

2

#
+
2
+
2
|
2
Z>
a
+ >
3
\ +
*
J
a3
0 0 0
# # # # #
+
2

2
| 0
2
Z>
a
>
3
\

*
J
a3
2
J
a3
0
# # # # #

2
+
2
|
0
2
J
a3
2
Z>
a
>
3
\
*
J
a3
0
# # # #

2

2
| 0 0
0
2
Z>
a
+ >
3
\ +
*
J
a3
The matri is 3loc4ed out (Appendi ,+ and the energies o. the spin .unctions |+
#
+
# # # # #
2
and |
2

2
can 3e 6ritten do6n immediately7 The spin .unctions |+
2

2

and
# #
|
2
+
2
, ho6e/er, are mied 3y the coupling and the degree o. miing depends upon
the separation o. the t6o diagonal elements and the magnitude o. their interaction,
#
J
a3
7
T6o etreme cases can 3e distinguished7
-1*1% 6irst or/er spe#tra
A. the chemical shi.ts o. the t6o protons are /ery di..erent 6e ha/e an AF system7
;o6, the energies o. the states |
#

#
and |+
#
+
#
are as 3e.ore 3ut the t6o
other
2 2 2 2
states, |+
#

#
and |
#
+
#
are not mied e0ually and their energies must 3e
.ound
2 2 2 2
3y diagonalising the 2 2 matri7 An the etreme 6here the di..erence in energy o.
the
on2diagonal elements, |Z>
a
>

\|, is /ery much greater than the o..2diagonal element
6hich lin4s them,
#
J
a
, the eigen.unctions o. the spin system are e..ecti/ely the .our
3asis .unctions and the energy le/els are gi/en 3y the diagonal elements o. the a3o/e
matri7 The ;C: spectra .rom spin systems .or 6hich this is true are 4no6n as Crst order
spectra7 Assuming that >
a
R >

, 6e can dra6 the energy2le/el diagram (Digure $7$+7 The
energies o. the allo6ed transitions, i7e7 those .or 6hich one m
:
/alue changes 6hile the
other remains constant are1
F changes1
E!+
#

#
" E!+
#
+
#
" = >


#
J
a
2 2 2 2 2
E!
#

#
" E!
#
+
#
" = >

+
#
J
a
2 2 2 2 2
'nergy
km
:a
m
:

kc c
'nergy
+cZn
a
+ n

\ + m J
a
kc +c
+cZn
a
n

\ m J
a
k+c c
k+c +c
J
a
J
a
cZn
a
n

\ m J
a
cZn
a
+ n

\ + m J
a
Spectrum
Dre0uency
n

n
a
6ig;re -1- The energy le/els and spectrum o. an AF system (>
a
R >

and Z>
a
>

\ |J
a
|+
A changes1
E!
#
+
#
" E!+
#
+
#
" = >
a

#
J
a
2 2 2 2 2
E!
#

#
" E!+
#

#
" = >
a
+
#
J
a
2 2 2 2 2
We ha/e .our lines o. e0ual intensity e0ually spaced on either side o. >
a
and >

6ith
a separation o. J
a
(Digure $7$+7
-1*1& Se#on/ or/er spe#tra
A. the chemical shi.ts o. the t6o protons are the same, i7e7 they are in identical en/iron2
ments as in the hydrogen molecule, 6e ha/e 6hat ;C: spectroscopists call an A
2
spin
system7 The .unctions |+
#

#
and |
#
+
#
are mied in e0ual proportions and
the
2 2 2 2
.ollo6ing .our spin energy le/els result1
Spin .unction 'nergy
# |+
#
+
#

#
Z>
a
+ >
3
\ +
#
J
a3
2 2 2 *
2 Z|+
#

#
+ |
#
+
#
\,

2 +
#
J
a3
2 2 2 2 *
, |
#

#

#
Z>
a
+ >
3
\ +
#
J
a3
2 2 2 *
* Z|+
#

#
|
#
+
#
\,

2
,
J
a3
2 2 2 2 *
2 2
Dunctions #, 2 and , are the three components o. a triplet state ha/ing : = # and
5
:
= +#, 0 and # respecti/ely7 Dunction * is a singlet 6ith : = 5
:
= 07 ;C:
spectra
in 6hich the eigenstates o.
9

can only 3e descri3ed in terms o. com3inations o. the 3asis

.unctions are 4no6n as second order spectra7 Since ;C: transitions are allo6ed only
3et6een states in 6hich one proton spin is changed .rom +
#
to
#
, or /ice /ersa, 6e
might epect to o3ser/e the .our transitions # 2, # *, 2 , and , *7
9o6e/er, transitions 3et6een states o. di..erent multiplicity are not allo6ed (!ro3lem #+,
so transi2 tions # 2 and 2 , only should occur and since they correspond to the
same energy
di..erence, >
a
, the corresponding spectral lines 6ill appear as one7 This is a general result7
The ;C: spectrum o. a group o. identical protons appears as a single line and although
spin I spin coupling is present its magnitude cannot 3e determined .rom the spectrum7
We epand on this point in Bo $72 and there are more details on ;C: transition
pro3a3ilities in Bo $7# and Section $7-7
The description Qsecond order spectrumG also applies to the intermediate case o. a
smaller di..erence 3et6een the t6o chemical shi.ts 6here there is une0ual miing o. t6o
or more 3asis states7 An the case o. t6o protons une0ual miing produces the AB spectrum
6hich /aries smoothly 3et6een the t6o etremes descri3ed a3o/e7 9arris
#
gi/es a detailed
discussion o. all aspects o. this pro3lem7
-1+ THE INTENSITIES 26 NMR S!ECTRA5 5INES
T6o .actors determine the strength o. an o3ser/ed spectral line in all 3ranches o. spec2
troscopy7 These are the magnitude o. the transition pro3a3ility 3et6een the initial and the
Lnal state and the relati/e populations o. the t6o states7 An normal electronic and in.rared
spectroscopy the population aspect o. the intensity plays no role since the population o.
the state o. lo6er energy al6ays massi/ely eceeds that o. the state o. higher energy7
An ;C: spectroscopy this is not the case since, as 6e ha/e seen, the energy di..erence
3et6een the resonating states is /ery small and, at the start o. the eperiment, the num3er
o. nuclei, ;
L
, in the lo6er2energy state is only slightly larger than that in the upper state,
;
=
7 Dor eample, .or hydrogen nuclei at room temperature in a Leld o. * T 6e ha/e,
using data .rom Ta3le $72 and the BoltKmann distri3ution1
;
=
,;
L
= epZ!##2.$ #0
2-
",!#.,%0?2 #0
2,
,00"\
= epZ0.2-2? #0
*
\ = 0.$$$$-2
So that, i. 6e ha/e one million nuclei in the lo6er state there 6ill 3e almost as many in
the upper state, 2% less to 3e eact7 There.ore, 6hen 6e irradiate our sample 6e rapidly
e0ualise the num3er o. nuclei in the t6o states and then, since the selection rule .or
a transition a3sor3ing a photon and one gi/ing out a photon are eactly the same, the
num3er o. photons a3sor3ed 6ill 3e e0ual to the num3er emitted and no net signal 6ill 3e
o3ser/ed7 This phenomenon is 4no6n as signal saturation and it presents many pro3lems
.or the ;C: spectroscopist7 The opposing relaxation processes, 6here3y the system
returns to the lo6er2energy state also play an important a role in determining the intensity
o. an ;C: signal, (see Section $7%+7 The second .actor 6hich determines the strength o.
an ;C: signal, the transition dipole moment, has 3een outlined in Sections %7-72 and $7,
and is discussed .urther in Bo $7#7
2
2
+
+
&uantum Cechanics and ;C: Spectroscopy 2--
An the case o. a molecule containing a num3er o. ;C:2acti/e nuclei the pro3a3ility
o. the transition |
i
|
.
is proportional to the matri element1
|
.
|

:

r
|
i
|
2
= |
.
|
#

!:

r
+ :

"|
i
|
2
($7-7#+
r r
6here the sum etends o/er all the nuclei, r, in/ol/ed in the initial and Lnal 6a/e
.unctions7 Since the operator :

r
operates only on the spin o. nucleus r, lea/ing the
spins
other nuclei unchanged, it is clear that these must all 3e the same i. the matri element
is to 3e non2Kero7 Thus an ;C: transition 3et6een |+
#
+
#

#
and |
#
+
#
+
#

is
2 2 2 2 2 2
allo6ed through :

,
, 3ut the transition |+
#
+
#

#
|
#
+
#
+
#
is .or3idden7 Dor
2 2 2 2 2 2
the purposes o. calculation it is /ery con/enient to replace :

r
3y
#
!:

r
+ :

"7 !ro3lem
, pro/ides an eample o. the use o. the a3o/e result to determine the relati/e intensities
o. the proton ;C: lines o. a t6o2spin system7
Dinally, it is note6orthy that the relati/e intensities o. a line in a normal ;C: spectrum
is proportional to the num3er o. resonating nuclei responsi3le .or that particular line7
Allo6ance must 3e made .or the splitting o. lines 3y spin I spin coupling7 This
simple proportionality is a great help in the interpretation o. the spectra and in the
0uantitati/e analytical applications o. ;C: spectroscopy7
-1, QUANTUM MECHANICS AN3 NMR S!ECTR2SC2!Y
The applications o. 0uantum mechanics in chemical ;C: spectroscopy .all into three
rather distinct categories1
(a+ The calculation o. the energy le/els o. a nuclear spin system in order to interpret
a spectrum7
(3+ The calculation o. chemical shi.ts and coupling constants .rom molecular 6a/e .unc2
tions7
(c+ The description o. the dynamic processes associated 6ith the Dourier trans.orm ;C:
techni0ue7
An this Chapter 6e ha/e 3een concerned eclusi/ely 6ith topic (a+, the analysis o.
eperimental spectra in terms o. the chemical shi.ts, ' , and coupling constants, J, 6hich
are regarded as parameters7 But 0uantum mechanics also o..ers the possi3ility o. calcu2
lating chemical shi.ts and coupling constants .rom the 6a/e .unctions o. the molecules
concerned and the theoretical epressions re0uired ha/e 3een a/aila3le since the #$50s7
Though the methods are 6ell 4no6n their application has had only limited 0uantitati/e
success and the 3asic reason .or this is not .ar to see47 The energy o. an ;C: transi2
tion corresponds to a .re0uency in the radio6a/e region o. the spectrum and the small
changes in the resonance .re0uency, 6hich are 3rought a3out 3y chemical shi.ts and cou2
pling constants, correspond to e/en smaller energies7 The energies o. the electrons in a
molecule, ho6e/er, correspond to .re0uencies in the /isi3le and ultra2/iolet regions o.
the e2m spectrum some % to #0 orders o. magnitude greater7 There.ore, the calculation
o. ' and J /alues 6hich are o. su.Lcient accuracy to 3e use.ul re0uires etremely good
molecular 6a/e .unctions, much 3etter than those re0uired .or a 0uantitati/e interpreta2
tion o. electronic spectra7 An general, apart .rom in the case o. a .e6 small molecules,
22 ;uclear Cagnetic :esonance Spectroscopy
0
2
2
6e do not ha/e such 6a/e .unctions7 ;e/ertheless, the e..orts 6hich ha/e 3een made
to calculate chemical shi.ts and coupling constants ha/e 3een /alua3le in that they ha/e
re/ealed the ma@or determining .actors and made possi3le a deeper understanding o. the
phenomena7 Space does not permit a .urther eamination o. the calculation o. chemical
shi.ts and coupling constants here 3ut an introduction to the Leld can 3e .ound in 9arris
#
and Cemory7
,
The su3@ects su3sumed under category (c+ are many and comple7 The modern ;C:
eperiment utilises the Dourier2trans.orm (DT+ techni0ue and as such it is a dynamic
eperiment in 6hich the resonating nuclei are su3@ected to an intricate se0uence o. pulses
o. radio2.re0uency radiation 6hich /ary in .re0uency, 3and 6idth, intensity, duration etc7
The result o. this treatment is to produce in the spin system a non2e0uili3rium orientation
o. the nuclear spins so that the sample 3ecomes magnetised in some specially chosen
6ay7 The Lnal step is normally the recording o. the decay o. this induced magnetisa2
tionP the free ind1ction decay7 The response o. the nuclei to the radiation pulses and the
su3se0uent relaation processes are all time2dependent phenomena and /ery ad/anced
0uantum2mechanical calculations are re0uired to analyse them7 An introduction to this
type o. ;C: spectroscopy may 3e .ound in 9arris
#
and in the Lrst edition o. SlichterGs
*
tet7 Dreeman
5
has gi/en a /ery reada3le descripti/e account 6ith almost no mathematics7
The most penetrating description o. the resonance phenomenon remains the classic trea2
tise o. A3ragam
?
3ut, naturally, it does not deal 6ith many aspects o. the modern ;C:
eperiment .or 6hich the latest edition o. Slichter
-
and Goldman
%
can 3e recommended7
-1- 8I85I2RA!HY AN3 6URTHER REA3IN
#7 :7>7 9arris, N1clear 5agnetic Resonance S%ectrosco%y, !itman, London, #$%,7
27 J7A7 !ople, W7G7 Schneider and 97J7 Bernstein, 8igh+Resol1tion N1clear 5agnetic Resonance,
CcGra629ill Boo4 Company, ;e6 Ror4HLondon, #$5$7
,7 J7<7 Cemory, 31ant1m -heory of 5agnetic Resonance Parameters, CcGra629ill Boo4 Com2
pany, ;e6 Ror4HLondon, #$?%7
*7 C7!7 Slichter, Princi%les of 5agnetic Resonance, 9arper & :o6, ;e6 Ror4HLondon, #$?,7
57 :7 Dreeman, 5agnetic Resonance in Chemistry and 5edicine, ".ord =ni/ersity !ress, ".ord,
200,7
?7 A7 A3ragam, -he Princi%les of N1clear 5agnetism, ".ord =ni/ersity !ress, ".ord, #$?#7
-7 C7!7 Slichter, Princi%les of 5agnetic Resonance, ,rd edn, Springer28erlag, ;e6 Ror4, #$%$7
%7 C7 Goldman, 31ant1m Eescri%tion of 8igh+Resol1tion N5R in Li71ids, ".ord =ni/ersity !ress,
".ord, #$%%7
82D -1% T$e NMR sele#tion r;le
To calculate the ;C: transition pro3a3ility, W ! y K t", 6e return to
'0uation (%7?72#+, repeated here .or con/enience, in 6hich the electric Leld, E
0
,
has 3een replaced 3y the magnetic Leld, /
0
, 3ecause it is the magnetic Leld o. the e2m
radiation 6hich interacts 6ith the nuclear spins1
W ! y K t " = /
2

*(
2
h
2
| $
.
|V

! y K"|$
i
|
2

sin
2
{
#
! A A"-
}
*{
#
! A
A"}
2
(%7?72#+
!
2 2
/
0
is gi/en 3y the eperimental conditions and the term in sin
2
is the time2
dependent .actor, 6hich is the same in all 3ranches o. spectroscopy7 We ha/e to
e/aluate the time2independent .actor1
#
2
h`
2
|
$
.
|
V

! y K"
|
$
i
|
An the case o. ;C: spectroscopy the operator V

! y K" ta4es the .orm1
!N h` /
#
"
.
|:

|
i

(B$7#7#+
so that 6e ha/e to calculate1
#
2
2 2 2
h
`
2
!N h
`
/
#
"
|

.
|
:

|

i
|
= !N /
#
" |
.
|:

|
i
|
(B$7#72+
6here /
#
is the magnetic Leld o. the applied radiation 6hich oscillates in the 2
direction and :

is the operator .or the 2component o. the nuclear spin7
'0uation
(B$7#7#+ as the .orm o. the lin4 3et6een the initial and Lnal states is understanda3le
i. 6e Lrst recall ('0uation ($7#7-++ that the energy o. interaction 3et6een a nuclear
magnetic moment and an applied Leld is gi/en 3y the product o. the nuclear moment,
the applied Leld and the cosine o. the angle 3et6een them7 There.ore, i. a Leld is
applied along the 2direction the interaction 6ill 3e determined 3y the 2component
o. the nuclear magnetic moment7 We can epress this interaction 6ith e0uations
li4e ($7#7?+ and ($7#7%+ 3ut 6ith K replaced 3y 7 That :

lin4s nuclear spin
states
ha/ing m
:
+
#
and
#
can 3e readily demonstrated 3y epressing :

in terms the
raising and lo6ering operators o. Chapter *7 We ha/e1
6hich, on addition, gi/e1
:

+
= :

+ i:

y
and
:

=
#
!:

= :

i:

y
(B$7#7,+
+ :

" (B$7#7*+
2
+

The e..ect o. operating on an angular momentum eigen.uction |: m

:
6ith :

+
and
:

is gi/en 3y '0uations (*7-75+ and (*7-7?+1

:

+
|: m
:
= Z: !: + #" m
:
!m
:
+ #"\ h
`
|: m
:
+ # (B$7#75+
:

|: m
:
=
Z: !: + #" m
:
!m
:
#"\ h` |: m
:
#
(B$7#7?+
Anserting the appropriate /alues o. :
#
" and m
:
!
#
", 6e easily Lnd that1
2 2
# # # # # #
6hile
:

+
|
2
+
2
= 0
and
:

+
|
2

2
= |
2
+
2

# # # # # #
so that
:

|
2
+
2
= |
2

2
and
:

|
2

2
= 0
:

|
#
+
#
=
#
|
#

#

and
:

|
#

#
=
#
|
#
+
#
(B$7#7-+
2 2 2 2 2 2 2 2 2 2
;ote that
h
`
has not 3een included in these epressions 3ecause 6e ha/e N , 6hich
is the .actor 6hich con/erts angular momentum in units o.
h` (see Section $7#+7
into magnetic moment
We can no6 e/aluate any matri element in '0uation (B$7#72+1
!N /
#
"
2
|
#

#
|:

|
#
+
#
|
2
= !N /
#
"
2

#
|
#

#
|
#

#
|
2
= !
#
N /
#
"
2
2 2 2 2 * 2 2 2 2 2
ZCore sophisticated analyses o. this pro3lem include a line2shape .unction in the
epression .or the transition pro3a3ility7 This introduces a multiplicati/e .actor o. 2(
and a ) .unction into the a3o/e e0uation, 3ut that need not concern us here7\
We see that the interaction o. an e2m 6a/e 6ith its magnetic Leld /i3rating
# #
in the 2direction con/erts states .rom m
:
= +
2
to m
:
=
2
, or /ice /ersa,
6ith
e0ual .acilityP i7e7 3oth processes are e0ually pro3a3le7 And, 3ecause o. the .orm o.
'0uations (B$7#75+ and (B$7#7?+, :

lin4s any t6o spin states 6hose m
:
/alues
di..er 3y #, e7g7 +
#
is lin4ed to
#
and +
,
and 0 to +# and #7 But note that the
matri
2 2 2
elements .or the t6o possi3le lin4s are not, in general, e0ual7
Thus .ar 6e ha/e .ocused our attention upon a single spin 3ut the spin .unctions
o. interest in ;C: spectroscopy are eigenstates o. sets o. coupled nuclei and 6e
re0uire the transition pro3a3ilities 3et6een such states7 Dirst 6e note that, since the
operator :

r
operates solely on the spin o. nucleus r, the operator re0uired .or a
molecule containing se/eral ;C:2acti/e nuclei is

r
:

r
7 'ach term o. the sum can
lin4 only initial and Lnal eigen.unctions, 6hich di..er in the m
:
/alue o. nucleus r,
6hile the m
:
/alues o. all other nuclei are the same7 Thus +
#
+
#
+
#
|

r
:

r
|
#
+
# # # # #
2 2 2 2
# # #
2
+
2
= 0 3y /irtue o. :

#
3ut +
2
+
2

2
|

r
:

r
|
2
+
2
+
2
= 0
3ecause, .or
eample, +
#
|:

#
|
#
+
#
|+
#

#
|+
#
= 0 on account o. the orthogonality o.
the
2 2 2 2 2 2
spin .unctions o. nucleus ,7
Because o. the many and comple .actors that determine the intensity o. an ;C:
signal, e7g7 relaation rates, intensity o. the eciting radiation, strength o. the static
magnetic Leld, it is /ery rare that anything more than relati/e intensity /alues are
re0uired and .or this it is su.Lcient to calculate only the matri elements |
.
|:

|
i
|
2
7
But the relati/e intensities are /itally important to spectral interpretation, especially
in the case o. second order spectra, and recourse to them is .re0uently made7
As a Lnal comment on the su3@ect o. the ;C: selection rule 6e note that the
# #
transition .rom m
:
= +
2
to m
:
=
2
in/ol/es a decrease o. one (hH2( + unit o.
the
K2component o. the angular momentum7 There.ore, since the K2component o. angular
momentum must 3e conser/ed, 6e re0uire a right circularly polarised photon to e..ect
it7 An an ;C: spectrometer 6e irradiate the sample 6ith linearly rather than circularly
polarised radiation7 This is not essentially di..erent 3ecause linearly polarised radiation
can al6ays 3e regarded as a sum o. le.t and right circularly polarised 3eams (see
Section %72+7 We ha/e ta4en account o. this in the de/elopment a3o/e 3y epressing
:

in terms o. :

+
and
:

7
82D -1& E@;iAalent n;#lei
The resonating nuclei in a molecule can .re0uently 3e di/ided into groups o. e0ui/alent
nuclei7 This simpliLes the analysis o. the ;C: spectrum and ma4es possi3le certain
generalisations a3out the spectrum7 The nuclei must 3e o. the same isotopic species
2
2
2
and, 6hen that condition is satisLed, the su32di/ision o. e0ui/alence into t6o classes
is possi3le7 An 6hat .ollo6s 6e shall consider only protons, though the concept can
3e etended to other nuclei7
A. t6o or more protons ha/e identical electronic en/ironments, as they 6ill ha/e
i. they are interchanged 3y one or more o. the symmetry operations o. the molecule,
then all their properties 6ill 3e the same and, in particular, they are isochrono1s,
i7e7 they all resonate at the same .re0uency7 Such protons are said to 3e chemically
e0ui/alent7 The si protons o. 3enKene and the .our o. methane are eamples7 But
6hen 6e consider their magnetic properties 6e note that each 3enKene proton has
di..erent coupling constants to the protons 6hich are ortho meta and %ara to it in
the molecule 6hile all si 9ICI9 couplings in methane are the same7 The methane
protons are said to 3e magnetically e0ui/alent, 3ut the 3enKene protons are not7
To ma4e the distinction clear, some authors descri3e the methane protons as 3eing
com%letely e0ui/alent7
Drom the theoretical standpoint, the signiLcance o. the e0ui/alence classiLcation is
that, in spectral analysis, a group o. magnetically e0ui/alent protons can 3e considered
as a single com%osite %article7 This also re/eals 6hy the coupling 6ithin a group o.
e0ui/alent nuclei does not result in a splitting o. spectral lines7 The argument goes as
.ollo6s7
A. the spins o. a group o. magnetically e0ui/alent nuclei are coupled, the resulting
total spin angular momenta and K2components can 3e .ound 3y eactly the same
methods as 6e ha/e used else6here in this 3oo4 .or electrons7 A. 6e ta4e the three
protons, 9
a
, 9
3
and 9
c
o. a methyl group as our eample then, @ust as 6ith three
electrons and in accord 6ith the Cle3sch I Gordan rule, the coupled system gi/es rise
to a 0uartet state and t6o dou3lets7 The eigen.unctions o. these states can 3e o3tained
3y applying the lo6ering operator to the 0uartet .unction ha/ing 5
:
=
,
@ust as in
Appendi #0, i7e7 6e e/aluate 3oth sides o. the e0uation1
, , # # # # # #
:

|
2
+
2
=
r
:

r
|
2
+
2
P
2
+
2
P
2
+
2

(The spins o. the three protons on the right2hand side o. the a3o/e e0uation are
6ritten in the order a, 3, c+7 We continue do6n the ladder o. 5
:
/alues until 6e reach
, , #
# # # # #
|
2

2
= |
2

2
P
2

2
P
2

2
.
We Lnd, 0uoting only the m
:
/alues o. the indi/idual spins1
Spin eigen.unction 5
:
'nergy
A 0uartet, : =
,
# # # ,
|+
2
+
2
+
2
+
2
,>,2 + ,J,*
!#,

,"{|+
#
+
#

#
+ |+
#

#
+
#
+ |
#
+
#
+
#
}
+
#
>,2 + ,J,*
2 2 2 2 2 2 2 2 2 2
!#,

,"{|
#

#
+
#
+ |
#
+
#

#
+ |+
#

#

#
}

#
+>,2 + ,J,*
2 2 2
# # #
2 2 2 2 2 2 2
,
|
2

2

2

2
+,>,2 + ,J,*
A dou3let, : =
#
!#,

2"{|+
#

#
+
#
|
#
+
#
+
#
}
+
#
>,2 ,J,*
2 2 2 2 2 2 2
2
2
A
=
Spin eigen.unction 5
:
'nergy
!#,

2"{|
#
+
#

#
|+
#

#

#
}

#
+>,2 ,J,*
2 2 2 2 2 2 2
A second dou3let, : =
#
!#,

?"{2|+
#
+
#

#
|+
#

#
+
#
|
#
+
#
+
#
}
+
#
>,2 ,J,*
2 2 2 2 2 2 2 2 2 2
!#,

?"{2|
#

#
+
#
|
#
+
#

#
|+
#

#

#
}

#
+>,2 ,J,*
2 2 2 2 2 2 2 2 2 2
At is con/enient to include the energies o. the spin eigen.unctions here7 'amples o.
ho6 they may 3e calculated are descri3ed later in the Bo7
A. 6e deLne an operator, 9

A
, .or the total spin o. the group o. the three magnetically
e0ui/alent protons1
9

A
=

I

r

(B$727#+
r
6e can 6rite the 9amiltonian operator ('0uation ($7?7#++1
in the .orm1
h
#
9

>
r
:

rK
+
r

rPs
J
rs
I

r
I

s
($7?7#+
h
#
9

= >9

AK
+ J{I

a
I

3
+ I

3
I

c
+ I

c
I

a
}
6here > is the resonance .re0uency o. the three protons and J is the 9ICI9 coupling
constant7
= >9

AK
+ J{
#
ZI

a
+ I

3
+ I

c
\
2

#
ZI

2
+ I

2
+ I

2
\}
2 2
a 3 c
=
>9
AK
+
J
{
#
9
2

#
Z
,
+
,
+
,
\
}
2

A
2 * * *
= >9

AK
+
#
J{9

2

$
}
2
A
*
This de/elopment can easily 3e generalised7 Dor n nuclei 6ith : =
#
.or eample,
6e ha/e1
h
#
9

= >9

AK
+
#
J{9

2
,n,*}
(B$7272+
2 A
Thus, the energy depends only on the total spin o. the methyl group, 9
A
, and its
K2component, 9
AK
7 And the spin states are eigen.unctions o. these t6o commuting,
#
angular momentum operators 6ith eigen/alues Z9
A
!9
A
+ #"\
2
and 5
A
7 But ;C:
transitions are allo6ed only 3et6een states 6ith the same /alue o. 9
2
7 To see 6hy
this is so 6e use '0uation (B$7#7*+ o. Bo $7# 6here the ;C: transition moment
operator, :

, is epressed as a sum o. the corresponding raising and lo6ering
operators1
:

=
#
!:

+ :

"
2
+

When applied to the eigen.unctions o. the operator 9

A
, these t6o operators
simply mo/e us up or do6n the ladder o. the 5
A
/alues o. a single /alue o. 9
A
, so an
;C: transition can ne/er change the /alue o. 9
A
7 But, though they di..er in energy
in an
applied magnetic Leld, all the 29
A
+ # components o. a state o. total spin 9
A
are
e0ually spaced and all ha/e the same spin I spin coupling energy 6hich there.ore does
not change in such a transition7 Thus, the coupling has no /isi3le e..ect on the ;C:
spectrum7
We shall no6 loo4 a little more closely at the energies in/ol/ed7 At is a use.ul
eercise in 3asic 0uantum2mechanical calculation to determine the energy matri o.
the three methyl protons7 The on2diagonal matri elements can 3e calculated (in
.re0uency units+ using '0uation ($7?7#+, the Lrst term o. 6hich gi/es the contri3ution
o. the chemical shi.t and the second that o. the coupling constants7
As an eample 6e Lrst e/aluate a diagonal element1
# # # # # #
+
2
+
2

2
|
r
The chemical2shi.t term gi/es1
>
r
:

rK
+
rPs
J
rs
I

r
I

s
|+
2
+
2

2

# # # # # #
+
2
+
2

2
|>
a
:

aK
+ >
3
:

3K
+ >
c
:

cK
|+
2
+
2

2

= >
a
+
#
|:

aK
|+
#
+
#
|+
#

#
|
#
>
3
+
#
|+
#
+
#
|:

3K
|+
#

#
|
#
2 2 2 2 2 2 2 2 2 2 2 2
>
c
+
#
|+
#
+
#
|+
#

#
|:

cK
|
#

2 2 2 2 2 2
= >
a
+
#
|+
#
|+
#
+
#
|+
#

#
|
#
>
3
+
#
|+
#
+
#
|+
#
|+
#

#
|
#
2 2 2 2 2 2 2 2 2 2 2 2 2 2
>
c
+
#
|+
#
+
#
|+
#

#
|
#
|
#

2 2 2
#
2 2 2 2
#
=
2
!>
a
+ >
3
>
c
" =
2
>
i. the protons are e0ui/alent7
The coupling term re0uires a little more thought7 We Lrst replace I

r
I

s
6ith the
e0ui/alent epression using the raising and lo6ering operators '0uation ($757#+1
J
rs
I

r

I

s
=
J
rs
Z:

r
:

s
+
:

ry
:

sy
+
:

rK
:

sK
\
=
J
rs
Z:

rK
:

sK
+
#
r s r s
2
!:

+
:


+ :

:

+
"\ ($757#+
The term in '0uation ($757#+ 6hich contains raising and lo6ering operators cannot
gi/e an on2diagonal matri element 3ecause any operation 6ith it changes the spins
o. t6o o. the three nuclei and the spin .unctions are orthogonal7 But the term J
rs
:

rK
:

sK
can gi/e rise to on2diagonal elements 3ecause the spin .unctions are unchanged 3y it
and .or our particular eample 6e Lnd1
# # # # # #
+
2
+
2

2
| rPs
J
rs
:

rK
:

sK
|+
2
+
2

2

# # # # # #
= +
2
+
2

2
|J
a3
:

aK
:

3K
+ J
3c
:

3K
:

cK
+ J
ca
:

cK
:

aK
|+
2
+
2

2

# # # # # #
= +
2
+
2
|J
a3
:

aK
:

3K
|+
2
+
2

2
|
2

# # # # # #
+ +
2

2
|J
3c
:

3K
:

cK
|+
2

2
+
2
|+
2

# # # # # #
+ +
2

2
|J
ca
:

cK
:

aK
|+
2

2
+
2
|+
2

# #
=
*
!J
a3
J
3c
J
ca
" =
*
J
i. the protons are e0ui/alent7
+
2
#
We can Lnd all the other on2diagonal matri elements in the same 6ay7 They are1
Basis state "n2diagonal matri element o.
9

#7 |+
#
+
#
+
#

#
!>
a
>
3
>
c
" +
#
!J
a3
+ J
3c
+
J
ca
"
2 2 2 2 *
27 |+
#
+
#

#

#
!>
a
>
3
+ >
c
" +
#
!J
a3
J
3c
J
ca
"
2 2 2 2 *
,7 |+
#

#
+
#

#
!>
a
+ >
3
>
c
" +
#
!J
a3
J
3c
+ J
ca
"
2 2 2 2 *
*7 |
#
+
#
+
#

#
!>
a
>
3
>
c
" +
#
!J
a3
+ J
3c
J
ca
"
2 2 2 2 *
57 |+
#

#

#

#
!>
a
+ >
3
+ >
c
" +
#
!J
a3
+ J
3c
J
ca
"
2 2 2 2 *
?7 |
#
+
#

#

#
!>
a
>
3
+ >
c
" +
#
!J
a3
J
3c
+ J
ca
"
2 2 2 2 *
-7 |
#

#
+
#

#
!>
a
+ >
3
>
c
" +
#
!J
a3
J
3c
J
ca
"
2 2 2 2 *
%7 |
#

#

#

#
!>
a
+ >
3
+ >
c
" +
#
!J
a3
+ J
3c
+ J
ca
"
2 2 2 2 *
The o..2diagonal matri elements can 3e .ound in a similar manner7 The Lrst term
on the right o. '0uation ($7?7#+ operates on only one nucleus and cannot there.ore lin4
t6o nuclei and contri3ute an o..2diagonal matri element7 9o6e/er, the raising and
lo6ering operators in the coupling term ('0uation ($757#++ can7 Since :

|+
#
=
0,
# # # # #
:

+
|
2
= |+
2
, :

|+
2
= |
2
and :

|
2
= 0 6e ha/e1
#

J
rs
!:
r
:
s # # #
r s
2
rPs
+


+ :

:

+
"|+
2
+
2

2

=
2
{J
a3
!:

a+
:

3
+ :

a
:

3+
" + J
3c
!:

3+
:

c
+ :

3
:

c+
"
# # #
+ J
ca
!:

c+
:

a
+ :

c
:

a+
"}|+
2
+
2

2

# # # # # # # #
=
2
J
3c
|+
2

2
+
2
+
2
J
ca
|
2
+
2
+
2
The 3asis .unctions are orthogonal so this result means that 6e ha/e o..2diagonal
matri elements o. the .orm1
9
,2
=
#
+
#

#
+
#
|J
3c
|+
#
+
#

#
=
#
J
3c
and
2 2 2 2 2 2 2 2
9
*2
=
#

#
+
#
+
#
|J
ca
|+
#
+
#

#
=
#
J
ca
2 2 2 2 2 2 2 2
The other o..2diagonal elements are1
9
?-
=
#

#
+
#

#
|J
3c
|
#

#
+
#
=
#
J
3c

2 2 2 2 2 2 2 2
9
5-
=
#
+
#

#

#
|J
ca
|
#

#
+
#
=
#
J
ca

2 2 2 2 2 2 2 2
9
,*
=
#
+
#

#
+
#
|J
a3
|
#
+
#
+
#
=
#
J
a3
2 2 2 2 2 2 2 2
9
5?
=
#
+
#

#

#
|J
a3
|
#
+
#

#
=
#
J
a3
2 2 2 2 2 2 2 2
#
#
#
T$e eigen";n#tions an/ energies
T6o eigen.unctions and energies can 3e 6ritten do6n immediately1

#
= |+
#
+
#
+
#
'
#
=
#
!>
a
>
3
>
c
" +
#
!J
a3
+ J
3c
+ J
ca
"
2 2 2 2 *

%
= |
#

#

#
'
%
=
#
!>
a
+ >
3
+ >
c
" +
#
!J
a3
+ J
3c
+ J
ca
"
2 2 2 2 *
To o3tain the remaining solutions to our pro3lem 6e must diagonalise t6o ,
, matrices, one o. 6hich is1
# # # # # # # # #
|+
2
+
2

2
|+
2

2
+
2
|
2
+
2
+
2

# # # # # #
+
2
+
2

2
|
2
!>
a
>
3
+ >
c
"
+
*
!J
a3
J
3c

J
ca
"
2
J
3c
2
J
ca
# # # # # #
+
2

2
+
2
|
2
J
3c
2
!>
a
+ >
3
>
c
"
+
*
!J
a3
J
3c
+ J
ca
"
2
J
a3
# # # # # #

2
+
2
+
2
|
2
J
ca
2
J
a3
2
!>
a
>
3
>
c
"
+
*
!J
a3
+ J
3c
J
ca
"
A general solution o. this pro3lem is clearly rather di.Lcult and it illustrates 6ell
ho6 rapidly the compleity o. the analysis o. an ;C: spectrum increases 6ith the
num3er o. spins in the system7 A general solution is possi3le i. certain approimations
are made and analyses along these lines are descri3ed in many tets7 We can 3rieOy
mention t6o7
T$e A8D spe#tr;m
A. the chemical shi.t, i7e7 > /alue, o. one proton, QcG say, is /ery di..erent .rom those o.
protons QaG and Q3G and the di..erence is also much larger than the coupling constants
J
ca
and J
3c
6e ha/e an ABF spin system and the spectrum may 3e regarded as second
order in AB and Lrst order in F (Section $7?+7 An this approimation J
ca
and J
3c
are
regarded as Kero 6here they occur in o..2diagonal matri elements, 3ut not in the
on2diagonal, and the matri a3o/e reduces to a 2 2, 6hich is easy to sol/e, and
a single eigen/alue 3elonging to the spin .unction |+
#
+
#

#
7
2 2 2
T$e A
'
spe#tr;m
A. the three protons are magnetically e0ui/alent the a3o/e matri reduces to1
# # #
# # # # # #
|+
2
+
2

2
|+
2

2
+
2
|
2
+
2
+
2

# # # # # # #
+
2
+
2

2
|
2
>
*
J
2
J
2
J
# # # #
# # #
+
2

2
+
2
|
2
J
2
>
*
J
2
J
# # # #
# # #

2
+
2
+
2
|
2
J
2
J
2
>
*
J
This matri is 0uite simple to diagonalise, 3ut it is much easier to determine the
energies o. the spin eigen.unctions, 6hich ha/e 3een o3tained using the raising and
# # # # # # #

lo6ering operators, 3y the procedure descri3ed 3elo67 Dor eample, the energy o. the
component !#,

2"{|+
#

#
+
#
|
#
+
#
+
#
} o. the Lrst spin dou3let is1
2 2 2 2 2 2
!#,2" { +
#

#
+
#
|
#
+
#
+
#
|}|9

|{| +
#

#
+
#
|
#
+
#
+
#
}
2 2 2 2 2 2 2 2 2 2 2 2
= !#,2"{ +
#

#
+
#
|9

| +
#

#
+
#
+
#
+
#
+
#
|9

|
#
+
#
+
#

2 2
# # #
2 2 2 2
# # # #
2 2 2 2 2 2
# # # # #
+
2

2
+
2
|9

|
2
+
2
+
2

2
+
2
+
2
|9

| +
2

2
+
2
}
= !#,2"{ > J > J J J} = >
,
J
2 * 2 * 2 2 2 *
To calculate the ;C: transition pro3a3ility, !, 3et6een the t6o states o. the Lrst
dou3let a3o/e 6e must e/aluate ('0uation ($7-7#++1


# # # # # # #

# # # # # # #
2
{ +
2

2
+
2
|
2
+
2
+
2
|}

r
and s0uare the result1
:

r
2
{|
2
+
2

2
| +
2

2

2
}

# # # # # # # # # # # # # #
=
2
+
2

2
+
2
|
r
:

r
|
2
+
2

2
+
2

2
+
2
+
2
|

:

r
| +
2

2

2

r
# # # # # # # # # # # # # #

2
+
2

2
+
2
|
r
:

r
|+
2

2

2

2

2
+
2
+
2
|

:

r
|
2
+
2

2

r
# # # # # # #
=
*
{ +
2

2
+
2
|
!:

r+
+ :

r
"|
2
+
2

2

r
+
2
+
2
+
2
|

!:
r
+
:

"
|+
2

2

2

# # #
+ r
r
# # #

# # #
# # #
+
2

2
+
2
|
!:

r+
+ :

r
"| +
2

2

2

r
# # # # # #

2
+
2
+
2
|
!:

r+
+ :

r
"|
2
+
2

2
}
r
"nly the third and .ourth o. the a3o/e .our integrals are non2Kero7 To illustrate
their e/aluation consider the third1
+
2

2
+
2
|

!:
r
+
:
"|+
# # #
+
r
# # #
#
r
2
# #
2 2
# # #
= +
2

2
+
2
|!:

a+
+ :

a
"|+
2

2

2

# # #
# # #
+ +
2

2
+
2
|!:

3+
+ :

3
"|+
2

2

2

# # #
# # #
+ +
2

2
+
2
|!:

c+
+ :

c
"|+
2

2

2

# # # # # #
= +
2
|!:

a+
+ :

a
"|+
2

2
|
2
+
2
|
2

# # #
# # #
+ +
2
|+
2

2
|!:

3+
+ :

3
"|
2
+
2
|
2

# # # # # #
+ +
2
|+
2

2
|
2
+
2
|!:

c+
+ :

c
"|
2

!ro3lems .or Chapter $ ,#
2
2
3
2
3
2
". these three epressions, si terms in total, only the last is non2Kero7 The others
are Kero 3ecause o. the orthogonality o. the spin .unctions7 The term containing :

c+
in the last e/aluates as1
# # # # # #
+
2
|+
2

2
|
2
+
2
|+
2
= #
The .ourth term also contri3utes # so that the total transition pro3a3ility is pro2
portional to {
#
!# #"}
2
=
#
7
* *
!R285EMS 62R CHA!TER -
#7 =se the in.ormation in Bo $7# to sho6 that transitions 3et6een the singlet state o.
t6o identical protons, !#,

2"{|+
#

#
|
#
+
#
}, and the triplet states, |+
# +
2 2 2 2 2
2

,
|
2

2

and !#,

2"
{|+
2

2
+ |
2
+
2
}
, are .or3idden7 That is, sho6 that
# # # # # # #

S
|:

|
T
= 07
27 Sho6 that .or a system o. n nuclei the matri o. the 9amiltonian operator gi/en
in '0uation ($7?7#+ can ha/e o..2diagonal matri elements only 3et6een 3asis states
6hich ha/e the same total K2component o. the nuclear spin, i7e7 ha/e the same /alue
o. m
: #
+ m
: 2
+ m
: ,
+ + m
: n
7
,7 Starting .rom the matri in Section $7? and the general method .or diagonalising a
2 2 matri .rom Appendi ,, sho6 that the energies and 6a/e .unctions o. a
system o. t6o nuclei, QaG and Q3G, each 6ith : =
#
are !J
a3
J to simpli.y the
notation+1
Wa/e .unction 'nergy (as .re0uency+

#
= |+
#
+
#

#
Z>
a
+ >
3
\ +
#
J
2 2 2 *
#

2
= sin A |+
#

#
+ cos A |
#
+
#

#
{Z>
a
>
3
\
2
+ J
2
}
2

#
J
2 2 2 2 2 *
#

,
= + cos A |+
#

#
+ sin A |
#
+
#
+
#
{Z>
a
>
3
\
2
+ J
2
}
2

#
J
2 2 2 2 2 *

*
= |
#

#
+
#
Z>
a
+ >
3
\ +
#
J
2 2 2 *
i
#
Where sin A =
i
2
{
Z>
a
#
>
3
\
2
+ J
2
}
2
+
#
Z>
a

#
#
> \
i
2
i
{Z>
a
>
3
\
2
+ J
2
}
2
#
i
#
and cos A =
i
2
{
Z>
a
#
>
3
\
2
+ J
2
}
2

#
Z>
a

#
> \
i
2
i
{Z>
a
>
3
\
2
+ J
2
}
2
Sho6 that the .our lines o. the AB spectrum ha/e .re0uencies o.
#
(< J+ relati/e
#
,2 ;uclear Cagnetic :esonance Spectroscopy
2
to the mean .re0uency
#
Z>
a
+ >
3
\, 6here < = {Z>
a
>
3
\
2
+ J
2
}
2
7
2
Sho6 that the intensities o. the .our possi3le transitions are proportional to1
Transition Antensity Transition Antensity

#

2
#
!# sin 2A"
*

2
#
!# sin 2A"
* *

#

,
#
!# + sin 2A"
*

,
#
!# + sin 2A"
* *
*7 The nucleus
#*
; has : = # and N = #.$,* #0
-
T
#
s
#
7 The corresponding
data .or
#
9 are : =
#
and N = 2?.-5 #0
-
T
#
s
#
7 =se '0uation ($7?7#+ to
construct the
? ? matri analogous to that in Section $7? .or the nuclear spin energy le/els o. the
molecule ;I9 in a magnetic Leld7 ZRou should Lnd that the matri is 3loc4ed out into
t6o # # and t6o 2 2 matrices 6ith o.. diagonal elements o.

2J7\ J, the
#*
;I
#
9
coupling constant, has not 3een reported .or ;I9, 3ut .rom other measurements o. the
coupling 3et6een directly 3onded ; and 9, e7g7 Z;9
*
\
+
, it is epected to 3e a3out
50 9K7
Assuming that the spectrum is Lrst order, calculate the transition pro3a3ilities and
predict the
#
9 ;C: spectrum o. the molecule7
=sing the /alues o. the magnetogyric ratios and J gi/en a3o/e and a magnetic Leld
.or 6hich protons resonate in the region o. #00 C9K, sho6 that the assumption that
the spectrum is Lrst order is .ully @ustiLed7
Chapter #0
In"rare/ Spe#tros#op0
#070 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2%$
#07# The origin o. the in.rared spectra o. molecules . . . . . . . . . . . . . . . . . . 2$0
#072 Simple harmonic motion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2$0
#07, The 0uantum2mechanical harmonic oscillator . . . . . . . . . . . . . . . . . . . 2$,
#07,7# &uantisation o. the energy . . . . . . . . . . . . . . . . . . . . . . . . . . 2$,
#07,72 Nero2point energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2$*
#07,7, 8i3rational eigen.unctions . . . . . . . . . . . . . . . . . . . . . . . . . . 2$*
#07* :otation o. a diatomic molecule . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2$*
#07*7# 'igen.unctions o. the rigid rotator . . . . . . . . . . . . . . . . . . . . . 2$-
#075 Selection rules .or /i3rational and rotational transitions . . . . . . . . . . . . . 2$-
#0757# A semi2classical /ie6 o. the selection rules . . . . . . . . . . . . . . . ,0#
#07572 An.rared intensities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0#
#07? :eal diatomic molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,02
#07- !olyatomic molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0,
#07-7# ;ormal co2ordinates, normal /i3rations, /i3rational
eigen.unctions and eigen/alues . . . . . . . . . . . . . . . . . . . . . . . ,0,
#07-72 8i3rations o. real polyatomic molecules . . . . . . . . . . . . . . . . . ,05
#07-7, Characteristic group .re0uencies . . . . . . . . . . . . . . . . . . . . . . ,0%
#07-7* Large molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0%
#07% Anharmonicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0$
#07%7# Dermi resonance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,0$
#07%72 8i3rational angular momentum and the Coriolis interaction . . . . . ,##
#07$ The a*+initio calculation o. A: spectra . . . . . . . . . . . . . . . . . . . . . . . . ,#?
#07#0 The special case o. near in.rared spectroscopy . . . . . . . . . . . . . . . . . . . ,#-
#07## Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,#-
!ro3lems .or Chapter #0 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2*
%.1. INTR23UCTI2N
There are numerous 3oo4s dealing, in 6hole or in part, 6ith the theory and practice o.
in.rared (A:+ spectroscopy
#I,
and an authoritati/e account o. the historical de/elopment o.
the su3@ect has recently 3een gi/en 3y Sheppard7
*
BrandGs
5
historical re/ie6 o. dispersi/e
spectroscopy also contains much o. theoretical as 6ell as practical interest7 An 4eeping 6ith
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
,* An.rared Spectroscopy
the title o. the 3oo4, the purpose o. the present chapter is to highlight those aspects o. A:
spectroscopy in 6hich 0uantisation, and hence 0uantum mechanics, plays an important
role7 We shall Lnd that the theory o. A: spectroscopy leans 0uite hea/ily on classical
concepts and classical mechanics7
At is di.Lcult to pin2point the Lrst application o. 6a/e mechanics to the harmonic
oscillator pro3lem, since the theory o. oscillation has 3een inetrica3ly ent6ined 6ith
the classical and 0uantum2mechanical description o. radiation since 3e.ore the turn o.
the 20th century until the present day7 At is clear, ho6e/er, that the Lrst application o.
matri mechanics to the one2dimensional oscillator 6as pu3lished 3y Ca Born, Werner
9eisen3erg and 'rnst !7 Jordan (#$02 I #$%0+ in #$257 The matri mechanics o.
the symmetric rotor 6as Lrst descri3ed 3y <a/id C7 <ennison (#$00 I #$-?+ in #$2?P
the 6a/e mechanics o. the same system 3y DritK :eiche (#%%, I #$?2+ and,
independently, 3y :alph de L7 >ronig (#$0* I + and Asador A7 :a3i (#%$% I #$%%+ in
#$2-7
%.1% THE 2RIIN 26 THE IN6RARE3 S!ECTRA 26 M25ECU5ES
A. 6e ha/e a group o. ; atoms 6hich are not 3onded together then each can mo/e,
independently o. the others, in one o. three directions, i7e7 in the 2, y2 or K2direction,
and the ; atoms are said to possess ,; degrees of freedom7 A. these ; atoms are 3onded
together, then the molecule as a 6hole can mo/e in three directions (translation+ and it can
also rotate a3out aes directed along , y and K7 (A. the molecule is linear it can only rotate
a3out the t6o directions perpendicular to the line o. atoms since a rotation o. the line
itsel. implies no mo/ement o. any o. the atomic masses7+ Thus, a non2linear molecule has
three degrees o. translational .reedom and three degrees o. rotational .reedom and, since
degrees o. .reedom cannot 3e destroyed, the remaining ,; I ? (,; I 5 .or a linear
molecule+ degrees o. .reedom must 3e /i3rational, i7e7 they must 3e mo/ements o. the
atoms 6ith respect to each other in 6hich the position o. the centre o. mass o. the molecule
remains stationary7 The most important /i3rations .rom the point o. /ie6 o. chemical
spectroscopy are those 6hich in/ol/e the changing o. 3ond lengths and angles since
these properties are directly related to molecular structure and the strengths o.
chemical 3onds7 But a molecule o3eys the la6s o. 0uantum mechanics7 There.ore the
energy associated 6ith these /i3rations is 0uantised and 6hen a molecule changes its
/i3rational energy le/els radiation in the in.rared region may 3e emitted or a3sor3ed and
the o3ser/ation o. this process, almost in/aria3ly in a3sorption, is A: spectroscopy7 An
discussing this pro3lem it is help.ul Lrst to consider /i3ration .rom the point o. /ie6 o.
classical mechanics7
%.1& SIM!5E HARM2NIC M2TI2N
A sphere o. mass, m, attached 3y t6o e0ual, mass2less springs to t6o immo/a3le 6alls
is sho6n in Digure #07#7 A. the mass is displaced slightly .rom its position o. rest (the
e0uili3rium position+ on release it 6ill /i3rate a3out the e0uili3rium position and, i. no
energy 6as dissipated in the springs and the surrounding air etc7, this /i3rational motion
6ould continue indeLnitely7 An order to 3e 0uantitati/e, 6e assume that the restoring
force 9, 6hich returns the mass to the e0uili3rium position,
o
, is proportional to its
displacement, , .rom that position, according to the la6 disco/ered 3y :o3ert 9oo4e
2
2
Simple 9armonic Cotion 2$#
m
6ig;re %.1% A /i3rating mass, m
(#?,5 I #-0,+7 The constant o. proportionality, the force constant, is 47 Then, since .orce =
mass acceleration1
9 = 4 = mD
2
,D t
2
!#0.2.#"
The negati/e sign indicates that a displacement in the positi/e 2direction generates
a .orce in the negati/e 2direction, and /ice /ersa7 The solution o. '0uation (#0727#+ is
6ell 4no6n, it is1
#
= F sin!Z4,m\
2
t + $" F sin!A
c
t + $" F sin!2( >
c
t + $" (#07272+
An '0uation (#07272+ >
c
is the classical /i3rational .re0uency, A
c
the corresponding angular
.re0uency, F is the amplitude o. the /i3ration and $ is an angle, 4no6n as the %hase angle,
6hich depends upon 6hat point in the /i3rational cycle 6e choose to call the starting
point7 The su3script ecd ser/es to remind us that >
c
or A
c
is the classical /i3rational
.re0uency, 6hich 6e shall ta4e o/er into the 0uantum2mechanical analysis shortly7 An
terms o. the .undamental properties o. the oscillator, 4 and m, the .re0uency is gi/en 3y
'0uation (#0727,+1
#
>
c
= !
#
( "Z4,m\
2
!#0.2.,"
The restoring .orce is the negati/e deri/ati/e o. the potential energy, V , and there.ore1
4 = 9 = DV ,D DV = 4D
Antegration gi/es1
V =
#
4
2
+ C
so that setting the constant o. integration to Kero, 3ecause 6e are interested only in relati/e
energies, and using '0uation (#0727,+ 6e ha/e1
V = 2(
2
m>
c
2

2
!#0.2.*"
Thus, the graph o. the potential energy against displacement is a para3ola (Digure #072+7
Cotion descri3ed 3y '0uations (#0727#+ to (#0727*+ is 4no6n as simple harmonic motion
and our mo/ing mass is a harmonic oscillator7
We can etend the a3o/e model to something /ery much li4e a diatomic molecule i. 6e
en/isage t6o masses, m
#
and m
2
connected 3y a spring o. .orce constant 4 (Digure #07,+7
An this dum323ell model o. a diatomic molecule the t6o masses mo/e, in phase, a6ay
.rom and to6ards each other 6hile the centre o. mass o. the system remains Led7 An
order to treat the t6o masses as one 6e introduce the concept o. reduced mass, T, 6hich
is deLned 3y '0uation (#07275+1
T = m
#
m
2
,!m
#
+ m
2
" !#0.2.5"
,? An.rared Spectroscopy
V

#
0
2
0

(
J
+
5
V = c ;
2
*
; g 5#? ; m
#
,
2
#
0
20 #0 0 #0 20
<isplacement (pm+
6ig;re %.1& 'nergy /ersus internuclear distance .or a simple harmonic oscillator
R
r
#
r
2
m
#
m
2
Center
o. mass
6ig;re %.1' The dum323ell model o. a diatomic molecule
=sing the reduced mass 6e o3tain (see Bo #07#+ e0uations eactly analogous to
'0uations (#0727#+ to (#0727*+ a3o/e 6here, in each case, m is replaced 3y T7 F and
are replaced 3y : and R r
e
respecti/ely, 6here r
e
is the distance 3et6een the centres o.
the t6o masses at e0uili3rium and R is the distance at any other time7 : is the amplitude
o. the oscillation in the sense that the maimum /alue o. R is r
e
+ : and the minimum
/alue is r
e
:7 Thus, '0uation (#07272+ is replaced 3y1
R r
e
= : sin!A
c
t + $" : sin!2( >
c
t + $"
(#0727?+ The change o. the 3ond length o/er the /i3rational cycle is illustrated in
Digure #07*
in a grossly eaggerated .orm7 The rate o. change o. R is v
R
, 6here1
v
R
= D :,D t = :A
c
cos!A
c
t + $"
!#0.2.-"
and oscillates 3et6een the /alues o. Kero and the maimum o. :A
c
as the total energy
changes .rom purely potential to purely 4inetic t6ice during each cycle7 "nly one
2
# 2 2 2 2 2
2
B
o
n
d

l
e
n
g
t
h
The &uantum2Cechanical 9armonic "scillator 2$,
%
-
r
e
+ R
?
5
*
r
e
,
2
#
0
time
r
e
R
6ig;re %.1( The change o. 3ond length 6ith time .or a /i3rating diatomic molecule
/i3rational .re0uency1
A
c
= 2( >
c
=

!4,T" !#0.2.%"
is possi3le 3ut the energy associated 6ith it can 3e changed 3y changing the amplitude
and any energy is possi3le, including Kero1 no displacement, masses at rest7
%.1' THE QUANTUM9MECHANICA5 HARM2NIC 2SCI55AT2R
The classical energy o. the dum323ell model o. a diatomic molecule is (Bo #07#+1
E = V + - =
#
4!R r
e
"
2
+ !Tv
R
"
2
,2T !#0.,.#"
Trans.orming to 0uantum2mechanical operators in the usual 6ay (Chapter ,+, the
9amiltonian operator, 9

, is gi/en 3y '0uation (#07,72+1
9

=
2
4!R r
e
" !h ,%( T"D ,D R !#0.,.2"
and the SchroM dinger e0uation, 9

= E
, is1
9

=
#
4!R r
e
"
2
!h
2
,%(
2
T"D
2
,D R
2
= E
(#07,7,+ As it turns out, this is a tedious e0uation to sol/e, 3ut the method o. solution is
descri3ed
in detail 3y !auling and Wilson
?
and in many other tets7 We shall content oursel/es 6ith
eamining the solutions o. the e0uation, i7e7 the eigen/alues and eigen.unctions o. the
harmonic oscillator 6hich is our model .or the 3ond2stretching /i3ration o. a diatomic
molecule7 The most important di..erences 3et6een classical and 0uantum mechanics in
this pro3lem are descri3ed in the remainder o. Section #07,7
%.1'1% Q;antisation o" t$e energ0
An classical mechanics the energy o. the harmonic oscillator can ta4e any /alue, depending
upon the displacement .rom the e0uili3rium position 6hich initiates the motion7 An 0uan2
tum mechanics the energy le/els are 0uantised7 They are characterised 3y the 0uantum
,% An.rared Spectroscopy
2
2
2
num3er, v and gi/en 3y the e0uation1
E
v
= !v +
#
"h>
c
in energy units (#07,7*+
!v +
#
">,c in 6a/e num3ers (#07,7*a+
6here c is the /elocity o. light, v = 0 # 2 . . . 7 An '0uation (#07,7*a+, the su3script
c, ha/ing ser/ed its purpose in emphasising the .act that the 0uantum2mechanical
.re0uency is the same as the classical .re0uency, has 3een dropped to simpli.y the
notation7
There is a constant energy di..erence o. h> 3et6een ad@acent energy le/els7 As the
0uantum num3er v increases, the energy increases as a conse0uence o. the increased
amplitude and speed o. the motion, 6hile the .re0uency o. oscillation remains the same7
This point should 3e stressed7 The increase in energy o. a harmonic oscillator, in 3oth
the classical2 and the 0uantum2mechanical descriptions, arises as a result o. increased
potential energy at the etremes o. the motion, due to an increase in the amplitude o.
the /i3ration, accompanied 3y greater 4inetic energy, i7e7 atomic masses mo/ing .aster,
at the e0uili3rium geometry 6here all the energy is 4inetic energy7 There is no change o.
.re0uency7 These points are illustrated 0uantitati/ely in Bo #0727
%.1'1& :ero9point energ0
The .act that, although v can 3e Kero, the energy can ne/er 3e lo6er than
#
h> is a
remar4a3le departure .rom the classical situation 6here an energy o. Kero is possi3le7 This
0uantity o. energy, 6hich the 0uantum2mechanical oscillator cannot lose, is 4no6n as the
Bero+%oint energy7 At is responsi3le .or many o. the cases 6here the properties o. solids
di..er .rom those predicted 3y classical mechanics, especially at /ery lo6 temperatures7
;ote also that it is a necessary conse0uence o. the 9eisen3erg uncertainty principle
(Section ,7#0+7 A. the t6o masses .orming the oscillator 6ere stationary 6ith a separation
o. r
e
6e 6ould 4no6 the positions and the momenta (Kero+ o. each o. them simultaneously,
and that is not allo6ed7
%.1'1' Vi?rational eigen";n#tions
The Lnal important di..erence 3et6een the classical and the 0uantum2mechanical har2
monic oscillator concerns the eigen.unctions o. the latter (Digure #075+7 The pro3a3ility
o. Lnding the oscillator 6ith a particular distance, R, 3et6een the masses is a rather com2
plicated .unction (Bo #07,+7 This is compared 6ith the classical .unction .or v = #2
in
Digure #07?7 Whereas the ends o. the classical motion are precisely deLned, the 0uantum2
mechanical pro3a3ility .unction is not and allo6s the masses to go outside the rigid
3oundaries 6hich conLne the classical oscillator7 But the t6o pro3a3ility .unctions 3ecome
increasingly similar as energy increases Digures #075 and #07?7
%.1( R2TATI2N 26 A 3IAT2MIC M25ECU5E
An Section #07# 6e noted that linear molecules ha/e t6o degrees o. rotational .reedom
and non2linear molecules three7 At this point 6e must epand a little on these .acts
#
9
,5
Cl
2

#
2
&
2
m
e
c
h
a
n
i
c
a
l
C
l
a
s
s
i
c
a
l
'
n
e
r
g
y

X

#
0
2
0

(
J
+
'
n
e
r
g
y

#
0

,

(
c
m

#
+
:otation o. a <iatomic Colecule 2$5
,5 #-7?
,0 #57#
25 #27?
20 #07#
#5 -7?
#0 570
5 275
0 070
5 275
*0 20 0 20 *0
(R r
e
+ (pm+
6ig;re %.1) The eigen.unctions o. a harmonic oscillator .or v = 0 to *
,70
275
270
Classical
turning
point

#2
2
.or
#
9
,5
Cl
Classical
turning
point
#75
#70
075
070
#00 50 0 50 #00
(R r
e
+ (pm+
6ig;re %.1* A comparison o. the classical and 0uantum2mechanical 6a/e .unctions o. the har2
monic oscillator .or v = #2
since they ha/e important conse0uences .or A: spectroscopy7 An solution, and especially
in the gaseous phase, all molecules rotate a3out the three (t6o in the case o. linear
molecules+ mutually perpendicular aes through their centre o. mass7 The energy, E
Q
,
and angular momentum, A
Q
, associated 6ith these motions are 0uantised according to the
*0 An.rared Spectroscopy
e0uations (Bo #07#+1
E
Q
= h
2
Q !Q + #",%(
2
TR
2
= h
2
Q !Q + #",%(
2
: in energy units
(#07*7#+
hQ !Q + #",%(
2
c: /Q !Q + #" in 6a/e num3ers
(#07*7#a+
#
A
Q
= ZQ !Q + #"\
2
h,2(
(#07*72+
6here : is the moment of inertia, / the rotational constant and Q a 0uantum num3er that
can ta4e all positi/e integer /alues, including Kero7 And, since 6e are dealing here 6ith
angular momentum, each le/el has a degeneracy o. 2Q + #, the le/els 3eing characterised
3y the 0uantum num3er 5
Q
or simply 5 7 ;ote that since Q can e0ual Kero, the lo6est
energy state is also Kero, in contrast to the Kero2point energy o. the oscillator7 But the
uncertainty principle is not contra/ened 3ecause although the atoms are stationary they
could 3e any6here in their circular paths7 At is interesting to compare the energy2le/el
spacing .or the /i3rational ('0uation (#07,7*a++ and rotational ('0uation (#07*7#a++ le/els
o. a diatomic molecule7 'periment sho6s that .or
#
9I
,5
Cl, .or eample, the approi2
mately constant spacing o. the lo6er /i3rational le/els is 2$%$75 cm
#
7 The spacing
o. the rotational le/els increases as /Q !Q + #" 3ut / #0.? cm
#
so that the /i3ra2
tional spacing is some t6o orders o. magnitude greater than the rotational (Digure #07-+7
Thus the energy2le/el diagram consists o. a set o. 6idely and approimately e0ually
spaced /i3rational le/els, each o. 6hich is accompanied 3y a set o. much more closely,
3ut une0ually, spaced rotational le/els7 There.ore, i. the selection rules allo6 it, the A:
a3sorption 3and associated 6ith a change o. /i3rational 0uantum num3er 6ill ha/e, closely
8i3rational
energy (cm
#
+
:otational
energy (cm
#
+
-500
0
220
#,2
??
22
*500
0
220
#,2
??
22
#500
0
6ig;re %.1+ Lo6er /i3rational and rotational energy le/els o.
#
9I
,5
Cl
4
4
spaced on either side o. it, a Cne str1ct1re o. 3ands due to changes in rotational 0uan2
tum num3er7 This Lne structure may or may not 3e resol/ed7 ;ote that the energy2le/el
scale is purely schematic7 The energy o. a particular le/el is the sum o. the /i3rational
and rotational energies and only /ery high rotational le/els o. /i3rational le/el v =
n
o/erlap the stac4 o. rotational le/els 3ased on the net /i3rational le/el, v = n + #7
But
the o/erlap pro/ides an important path6ay .or the relaation o. molecules in ecited
/i3rational le/els7 ;ote also that the spacing o. the le/els is in/ersely proportional to the
molecular mass7
%.1(1% Eigen";n#tions o" t$e rigi/ rotator
When the atomic masses are epressed in terms o. the reduced mass, the 9amilto2
nian .or the rigid rotator is identical to the 4inetic energy operator o. the one2electron
atom (Bo #07#+7 The eigen.unctions are the spherical harmonics, R
lm
!# $", 6hich
are descri3ed in detail in Appendi 57 When descri3ing the angular momentum o. the rigid
rotator it is con/entional to replace l and m 3y Q and 5 (see Section *7%+7
%.1) SE5ECTI2N RU5ES 62R VI8RATI2NA5
AN3 R2TATI2NA5 TRANSITI2NS
We assume the idealised model o. a rigid rotator, 6here there is no increase in 3ond
length as the speed o. rotation increases and hence no interaction 3et6een rotation and
/i3ration7 An such a model the /i3rational and rotational motions are 0uite independent
and 6e can consider the /i3rational and rotational energy le/els and their 6a/e .unc2
tions separately7 This assumption, together 6ith the Born2"ppenheimer approimation
(Section ?7,+, ena3les us to 6rite the molecular 6a/e .unctions as products o. electronic,
/i3rational and rotational 6a/e .unctions1

total
= G
elec
G
/i3
G
rot
!#0.5.#"
and the selection rules .or the molecule as products o. the indi/idual electronic, /i3rational
and rotational selection rules7
According to Section %7-, 6e re0uire the time2independent interaction 3et6een the elec2
tric Leld o. the radiation, E, and the transition dipole moment 3et6een the initial and Lnal
rotation2/i3ration states o. the molecule7 We start 6ith the Lrst line o. '0uation (%7-7-+,
reproduced here as '0uation (#07572+ and use the Lrst line, rather than the second line,
o. that e0uation 3ecause 6e 6ish to introduce molecular rotation 6hich 6ill a..ect our
a3ility to ta4e the terms in "
0
and "

outside the integrations1
,;?
"
i.
= G
.
/i3
| "
0
!e
.
e
i
"| G
i
/i3
+ G
.
/i3
|

&
4
"

!e
.
e
"| G
i
/i3
(#07572+
4=#
At is use.ul to ma4e a num3er o. modiLcation to '0uation (#07572+7 The superscripts
. != Lnal" and i != initial" 6ill 3e replaced 3y the single (

+ and dou3le (

+ prime
mar4s respecti/elyP the notation normally used in this su3@ect and the appendage (e
.
e
i
+
6ill 3e dropped, since it is assumed throughout this chapter that 6e are dealing only
6ith the ground electronic state7 Also, since 6e are .ocussing attention on a diatomic
molecule,
there is only one normal co2ordinate, the 3ond stretching represented 3y r 7 With these
modiLcations '0uation (#07572+ 3ecomes1
" = G
/i3

G
rot
|"
0
|G
/i3

G
rot
+ G
/i3

G
rot
|r "

|G
/i3

G
rot

(#0757,+ We shall Lnd it important to identi.y the 0uantum num3ers associated 6ith
each o. the
/i3rational (v + and rotational (Q 5 + eigen.unctions, so 6e no6 6rite '0uation (#0757,+
in the .orm1
" = G
v
G
Q

5
|"
0
| G
v
G
Q

5
+ G
v
G
Q

5
|r "

| G
v
G
Q

5

(#0757*+ The dipole moment, "
0
, and its deri/ati/e 6ith respect to r , "

, are
constants 6ith
respect to r , since they are e/aluated at a Led /alue o. r , the e0uili3rium
internuclear
distance7 9o6e/er, they are /ectors in the r 2direction in space 6hich changes as the
molecule tum3les7 There.ore, they are .unctions o. the co2ordinates 6hich descri3e their
spatial orientation7 We adopt a polar co2ordinate system and call the internuclear direction
r and use # and $ to descri3e the orientation o. "
0
and "

, 6hich 6e shall 6rite as
.!# $" = sin # cos $, sin # sin $ and cos # .or the , y and K directions
respecti/ely
(Appendi -+7 The consideration o. molecular rotation also re0uires the co2ordinates, #
and $7 Thus, the /i3rational 6a/e .unctions, G
v
!r " and G
v
!r ", are .unctions o.
r 6hile the rotational .unctions, G
Q

5
!# $" and G
Q

5
!# $" depend only upon #
and $ (Bo #07#+7 We no6 ha/e1
" = G
v
!r "G
Q

5
!# $"|"
0
.!# $"| G
v
!r "G
Q

5
!# $"
+ G
v
!r "G
Q

5
!# $"|r "

.!# $"| G
v
!r "G
Q

5
!# $"
= G
v
!r "|G
v
!r " "
0
G
Q

5
!# $"|.!# $"| G
Q

5
!# $"
+ G
v
!r "|r | G
v
!r " "

G
Q

5
!# $"|.!# $"|G
Q

5
!# $"
(#07575+ 6here implies integration only o/er the co2ordinate(s+ speciLed in the 6a/e
.unctions7 We distinguish t6o cases7
Case /: G
v
!r " = G
v
!r "
This is the case o. a change o. rotational energy le/el 6ithout a change o. /i3rational
le/elP a pure rotational transition7 Since the /i3rational 6a/e .unctions are normalised
G
v
!r "|G
v
!r " = #7 But G
v
!r "|r |G
v
!r " = 0
]
so that only the Lrst term in
'0uation
(#07575+ can contri3ute to the transition dipole moment, pro/ided that neither "
0
nor
G
Q

5
!# $"|.!# $"|G
Q

5
!# $" are e0ual to Kero7 The Lrst condition re0uires that
the
molecule in its e0uili3rium nuclear conLguration has a permanent dipole moment so that
only heteronuclear diatomic molecules can sho6 a pure rotation spectrum7 The second
condition .or a pure rotation spectrum is that the third component o. the product, the
integration o/er # and $1
G
Q

5
!# $"|.!# $"|G
Q

5
!# $"
!#0.5.?"
does not e0ual Kero7 This 6ill pro/ide the rotational selection rule7 We Lrst note (Appen2
di 5+ that, apart .rom some multiplying constants, the three .unctions .(# $+ are three
spherical harmonics @ust li4e the three p2or3itals,
2p
,
2py
and
2pK
, 6hich may also 3e
]
r is an odd .unction (it changes sign on passing through r
e
+ 3ut the s0uare o. any 6a/e .unction must 3e e/en7 There.ore,
the integrand G
v
!r "|r |G
v
!r " is an odd .unction o. r and must 3e Kero7
6ritten in the .orms R
#+#
, R
##
and R
#0
7 The second .ormulation is the more con/enient
.or our present purposes and 6e use1
.
+
!# $" = sin # ep!+i$" .

!# $" = sin # ep!i$" and .

0
!# $"
= cos #
Since the rotational eigen.unctions are also spherical harmonics (Bo #07#+ the re0uired
integral turns out to 3e the integral o/er # and $ o. a product o. three spherical harmonics7
The integration o/er $ is simpleP 6e re0uire that 5

5

+ 5
.
= 0, 6here 5
.
is
the
5 2/alue o. the particular choice o. .(# $+, i7e7 +#, # or 0 .or .
+
, .

and .
0
respecti/ely7
When this condition is satisLed the integral o/er $ has a /alue o. 2( , other6ise it is Kero7
Since 5
.
= 0 or # this condition is usually 6ritten in the .orm1
5

5

5 = 0 # !#0.5.-"
An molecules 6ith no unpaired electrons the e..ects o. the selection rule on 5 are
only seen in the presence o. an electric Leld, 6hich partially li.ts the degeneracy o. the
5 le/elsP a phenomenon 4no6n as the Star4 e..ect (Johannes Star4 (#%-* I #$5-++7
The integration o/er # is more complicated, 3ut use o. t6o .ormulae gi/en in
Appendi 5 simpliLes the pro3lem7 The re0uired .ormulae are1
cos #
Q|5 |
!# " = A!Q 5 "
Q +#|5 |
!# " + B!Q 5 "
Q #|5 |
!# " (#0757%+
and
sin #
Q|5 |#
!# " = C!Q 5 "
Q +#|5 |
!# " <!Q 5 "
Q #|5 |
!# " (#0757$+
6here A!Q 5 ", /!Q 5 ", C!Q 5 " and E!Q 5 " are .unctions o. Q and 5 only7
When the operator .
0
!# $" is used 6e ha/e, .rom '0uation (#0757-+, the condition 5
= 0 and the matri element re0uires integration o/er t6o .unctions and cos # P
eplicitly1
Ant7 = 2(
Q

5
!# "| cos # |
Q

5
!# "
:eplacing cos # |
Q

5
!# " 6ith the right2hand side o. '0uation (#0757%+ gi/es1
Ant7 = 2( {A!Q 5 "
Q

5
!# "|
Q

+#5
!# " + B!Q 5 "
Q

5
!# "|
Q

#5

!# " }
There.ore, since the .unctions are orthogonal and normalised, the integral is Kero
unless Q

= Q

#7 When the operators .
+
!# $" or .

!# $" are used 6e ha/e the

con2 dition 5 = # and the matri element re0uires integration o/er t6o
.unctions and
sin # 7 Dor that integral 6e apply '0uation (#0757$+, 6hich con/eniently com3ines the sine
.unction and the change o. 5 /alue7 Again, the orthonormality o. the .unctions leads
to the selection rule1
Case 2: G
v
!r " = G
v

!r "
Q Q

Q

= # !#0.5.#0"
This is the case in 6hich there is a change o. /i3rational state 6hich may, or may not,
3e accompanied 3y a change o. rotational state7 Because o. the orthogonality o. the
/i3rational 6a/e .unctions, the Lrst term in '0uation (#07575+ is Kero and the transition
moment is gi/en 3y the second, 6hich implies that the transition moment 6ill 3e Kero
unless "

= 0, i7e7 the /i3ration must change the dipole moment o. the molecule7
The
Lrst term in the product is the integration o/er r 1
G
v
!r "|r |G
v
!r
"
6hich 6ill pro/ide the /i3rational selection rule7 =sing a result .rom Bo #07, to epress
rG
v
!r " in terms o. the .unctions G
v

#
!r " and G
v

+#
!r " 6e
o3tain1
G
v
!r "|r |G
v
!r " = ! G
v
!r "|G
v

+#
!r " + & G
v
!r "|G
v

#
!r "
(#0757##+
6here ! and & are constants7 Since the /i3rational eigen.unctions are orthogonal, the Lrst
integral on the right2hand side 6ill 3e Kero unless v

= v

+ #, and the second
integral 6ill 3e Kero unless v

= v

#, 6hich immediately gi/es us the selection
rule1
v = #
!#0.5.#2"
The integrals o/er # and $ are identical in 3oth terms o. '0uation (#07575+7 There.ore,
the rotational selection rules in the case o. /i3ration2rotation spectra are the same as they
are .or pure rotation spectraP in gas2phase spectra rotational transitions are .re0uently
seen as Lne structure surrounding a /i3rational a3sorption 3and7 Spectroscopists call
the transitions 6ith Q = #, 0 and +# the P 2, 32 and R+*ranches o. the
spectrum
respecti/ely7 With regard to the intensity o. rotational transitions 6e must also ta4e note
o. the degeneracy associated 6ith the angular momentum7 A rotational state characterised
3y the 0uantum num3er Q is !2Q + #"2.old degenerate (Chapter *+ so that the population
o. such a state, and hence the intensity o. transitions .or 6hich it is the initial state,
depends upon Q as 6ell as the BoltKmann .actor7
'0uations (#0757-+, (#0757#0+ and (#0757#2+ are the selection rules .or the rotational
and /i3rational spectra o. the idealised diatomic molecule7 At is 6orth reiterating that .or
an allo6ed rotational transition the molecule must ha/e a per&anent dipole moment,
6hereas .or an allo6ed /i3rational transition the /i3ration must 3e accompanied 3y a
change in dipole moment7
An conclusion, three remar4s should 3e made concerning the a3o/e selection rules and
the deri/ation o. them1
We ha/e de/eloped this 0uantum2mechanical analysis o. the /i3rational transition pro32
a3ility in the contet o. a diatomic molecule eecuting its 3ond2stretching /i3ration7
But the treatment is e0ually /alid .or any molecular /i3ration that is an eigen.unction
o. the /i3rational 9amiltonian operator, i7e7 a normal mode (see Section #07-7#+, and
.or 6hich "

is not Kero7 9o6e/er, it should 3e noted that real molecules are ne/er
harmonic oscillators (Sections #07? and #07%+ and there.ore they de/iate .rom that ideal
3eha/iour7#07%
Cany other su3tle aspects o. these selection rules emerge 6hen a group2theoretical
analysis is made7 Dor .urther details specialist tets, e7g7 9erK3erg
-
and 9ollas,
%
should
3e consulted7
Similarly, the selection rules .or the changes in /i3rational and rotational le/els that
accompany a change o. electronic state are an important and comple area o. spec2
troscopy .rom 6hich most o. our 4no6ledge o. the shapes o. molecules in their
electronically ecited states is deri/ed7 The 3oo4s 3y 9erK3erg
-
and 9ollas
%
gi/e
comprehensi/e treatments o. this su3@ect7
Dinally, 6e note that the selection rules .or the rotational transitions o. the rigid rota2
tor 6e ha/e .ound are those 6hich 6e should epect in /ie6 o. the esta3lished angular
momentum o. the electric dipole photon (see Section %7*75+ Since, .ollo6ing con/ention,
Q

characterises the upper state and Q

the lo6er, a transition 6ith Q = +#
corresponds to the addition to the rotator o. one unit o. angular momentum 6hile
Q = # cor2 responds to a loss o. angular momentum 3y the molecule7 The
selection rule on 5 ,
5 = #, reOects the t6o possi3le K2components o. the photonGs angular
momentum7
%.1)1% A semi9#lassi#al Aiew o" t$e sele#tion r;les
We ha/e t6o conditions to .ulLl i. there is to 3e a transition 3et6een t6o /i3rational
energy le/els as a result o. the a3sorption o. e2m radiation 3y a molecule1
The .re0uency o. the radiation, >, must 3e e0ual to the /i3rational .re0uency o. the
molecule, >7
The Bohr I 'instein condition must 3e satisLed, i7e7 the product o. h and > must
3e
e0ual to the energy gap 3et6een t6o /i3rational energy le/els7
These t6o re0uirements can 3e simultaneously satisLed7 A. a molecule in any /i3rational
state has a /i3rational .re0uency o. > then the gap, E, 3et6een t6o ad@acent energy
le/els, 0uantum num3ers v and v + #, is ('0uation (#07,7*++1
E = h>{!v + # +
#
" !v +
#
"} = h> !#0.5.#,"
2 2
Thus the t6o conditions are satisLed .or an a3sorption process in 6hich the 0uantum
num3er v is changed 3y +#, 6hich means that transitions 3et6een any t6o ad@acent
le/els o. the harmonic oscillator model o. a diatomic molecule can 3e stimulated 3y
e2m radiation o. .re0uency >P 3ut only, o. course, i. the oscillation o. the molecule pro2
duces an oscillating electric dipole7 A homonuclear diatomic molecule such as hydrogen
(9
2
+ or nitrogen (;
2
+ has no electric dipole moment and cannot there.ore interact 6ith
e2m radiation in the A: or micro6a/e regions as a conse0uence o. its /i3rational, or
rotational, motion7
A semi2classical interpretation o. the selection rules .or the rotational spectrum o. a
rotating dipole similar to that gi/en a3o/e .or the /i3rational spectrum o. the harmonic
oscillator is not possi3le7 This is 3ecause, in contrast to /i3rational .re0uency 6here 3oth
classical and 0uantum2mechanical deLnitions eist, there is no eact 0uantum2mechanical
deLnition o. rotational .re0uency7 There.ore, 6e do not epect to 3e a3le to epress the
true (0uantum2mechanical+ selection rule in classical terms7 There is a precise 0uantum2
mechanical description o. angular momentum, 3ut it does not imply the motion o. a
particle in a closed path and at a particular .re0uency a3out some central ais, as 6e can
see 6hen 6e thin4 o. the or3ital angular momentum o. a p electron or electron spin7
%.1)1& In"rare/ intensities
As in all 3ranches o. spectroscopy, the intensity o. a transition depends not only upon
the transition pro3a3ility 3ut also upon the population o. molecules in the initial, G

, and
Lnal, G

, states7 This can 3e readily determined .rom BoltKmannGs e0uation7 Dor
#
9
,5
Cl
at room temperature (,00 >+ .or eample, the v = 0 to v = # a3sorption 3and is
o3ser/ed
at 2%%57$ cm
#
, 6hich is e0ual to 5-,, #0
2,
J7 Thus, according to
BoltKmann1
;!v = #",;!v = 0" = ep!5-,, #0
2,
,,00 #.,%# #0
2,
" = 0.$-%5 #0
?
2
2U
,U
There.ore, in a sample o. one million molecules, there is only one molecule in the
v = # /i3rational state and $$$ $$$ in the v = 0 state7 This is a /ery .a/oura3le
situation .or a3sorption spectroscopy7 With such a large ecess o. molecules in the
lo6est state
pro3lems due to saturation do not occur in the in.rared1 contrast ;C: spectroscopy7
9o6e/er, .or /i3rations o. lo6 .re0uency and energy, there can 3e a signiLcant population
o. molecules in the v = # or v = 2 states and transitions .rom these states to
higher
/alues o. v are sometimes o3ser/edP especially 6ith samples at high temperatures7 Such
3ands are 4no6n as hot *ands7
%.1* REA5 3IAT2MIC M25ECU5ES
Though the model descri3ed in Sections #07, to #075 is a /ery use.ul starting point, a
momentGs reOection re/eals that there are important di..erences 3et6een the harmonic
oscillator and a real diatomic molecule7 We 4no6, .or eample, that i. 6e supply su.Lcient
energy to the molecule it 6ill /i3rate 6ith such a large amplitude that the atoms separate
at the etreme o. the /i3ration and the molecule decomposes7 Similarly, though it is
not 0uite so o3/ious, at /ery small 3ond lengths the potential energy o. the molecule
increases more rapidly than the para3olic cur/e indicates7 A rather general epression
.or the potential V !R" as a .unction o. the internuclear distance, R, can 3e o3tained 3y
epanding (R r
e
+ as a Taylor series a3out r
e
1
V !R" = V !r
e
" + !R r
e
"D V !r
e
",D R + !
#
"!R r
e
"
2
D
2
V !r
e
",D R
2
+ !
#
"!R r
e
"
,
D
,
V !r
e
",D R
,
+
(#07?7#+ A. 6e deCne the potential energy to 3e Kero at the e0uili3rium 3ond length,
the Lrst
term in the epansion is Kero7 The second term is Kero 3ecause there is no change o.
V !r
e
" 6ith R at r
e
(Digure #075+, so the Lrst non2Kero term is the 0uadratic term1
V !R" =
#
!R r
e
"
2
D
2
V !r
e
",D R
2
!#0.?.2"
.rom 6hich 6e see, 3y comparison 6ith '0uation (#07,7#+, that the .orce constant 4 =
D
2
V !r
e
",D R
2
and 6e 4no6 that this potential .unction gi/es rise to harmonic
oscillation7 Anclusion o. the higher terms pro/ides a representation o. the anharmonic
oscillator P this
is sometimes necessary to eplain more su3tle e..ects in /i3rational spectroscopy7 Some
eamples are discussed in Section #07%7
An practice, the V !R"1 R relationship proposed 3y Corse ('0uation (#07?7,+ and Digure
#07%+ is .re0uently used7 At pro/ides a simple 3ut 0uite accurate approimation to the
potential cur/e o. a real diatomic molecule .or small /alues o. r
e
R1
V !R" = E
e
Z# ep{a!r
e
R"}\
2
!#0.?.," E
e
is the energy di..erence 3et6een the dissociation energy and the lo6est
point o.
the V /ersus R cur/e (not the lo6est /i3rational le/el 6hich gi/es the eperimental
dissociation energy, E
0
+ and a is a constant7 At is possi3le, though di.Lcult, to sol/e the
SchroM dinger e0uation .or a Corse potential energy cur/e7 T6o aspects o. the solution
are o. particular interest in the present contet1
#7 The ne6 energy le/els are gi/en 3y the .ormula1
' = !v +
#
"h> !v +
#
"
2
x
e
h>
2 2
!olyatomic Colecules *-
W
a
/
e

n
u
m
3
e
r

(
#
0
?

m

#
+
5
!ara3ola (harmonic oscillator+
*
V = #2$$ #0
?
(#2-75 r+
2
,
<issociation
2
E
e
#
Corse cur/e
V = ,7-2 #0
?
n# epZ070#%- (#2-75 r+\T
2
0
#00 200 ,00 *00
Anternuclear distance (pm+
6ig;re %.1, The Corse cur/e .or a diatomic molecule
.rom 6hich it is clear that they are no6 no longer e0ually spaced7 x
e
is the anhar+
monicity constant P it is a measure o. the departure o. the real molecule .rom the ideal
harmonic oscillator7
27 The strict selection rule o. the harmonic oscillator no longer applies and transitions
ha/ing v = 2 , . . . are no6 possi3le, in addition to the original v = #7
Though the transitions 6ith v = # remain 3y .ar the strongest, transitions ha/ing
v = +2 are .re0uently seen in in.rared a3sorption spectra 6here they are 4no6n as
overtones7 Their .re0uencies are normally @ust less than t6ice the .re0uency o. the v =
+# transitions7 Transitions ha/ing v R 2 are much rarer and the intensity o. o/ertones
decreases rapidly 6ith increasing v 7 Dor eample, the Lrst o/ertone (v

= 0 v
=
2+ o. hydrogen chloride (9Cl+ has only #7? Y o. the intensity o. the .undamental (v
=
0 v

= #+7 Com*ination *ands, transitions in 6hich t6o .undamental /i3rations
are
simultaneously ecited, are also seen 6ith a much2reduced intensity7
%.1+ !25YAT2MIC M25ECU5ES
The num3er o. /i3rations, ,; I 5 or ,; I ?, increases rapidly 6ith the num3er o.
atoms (;+, in a molecule and the possi3ility o. o3ser/ing /i3rations o. di..erent types
arises7 An 6ater, .or eample, there are /i3rations associated 6ith the stretching o. the
t6o "I9
3onds and 6ith the changing o. the 9I"

I9 3ond angle7 An 3enKene there is a
/i3ration
in 6hich all si CIC 3onds gro6 longer or shorter simultaneously and the C
?
heagon is
said to eecute a *reathing /i3ration7 We need to consider the actual .orms o. the possi3le
/i3rations o. a polyatomic molecule in more detail7
%.1+1% Normal #o9or/inates< normal Ai?rations< Ai?rational
eigen";n#tions an/ eigenAal;es
An Section 572 6e noted that the epression o. SchroM dingerGs e0uation .or the
*% An.rared Spectroscopy
hydrogen atom in polar rather than Cartesian co2ordinates 6as a great aid to its
solution 3ecause
!olyatomic Colecules *$
the e0uation could then 3e separated into three e0uations, one in each o. the three co2
ordinates r, # and $7 The eigen.unctions are then .ound as products o. the solutions o.
the three separate e0uations, the radial .unction, :
nl
(r+ and the t6o angular .unctions,

lm
!# " and
m
!$"7 We adopt a similar approach to Lnd the solutions o. SchroM
dingerGs
e0uation .or the /i3rations o. a polyatomic molecule7
There is a set o. co2ordinates in 6hich the 6a/e e0uation is separa3le into ,; I
? (,; I 5+ separate eigen/alue I eigen.unction e0uations7 They are called the normal
co+ ordinates and are usually gi/en the sym3ol &
n
7 When the atoms mo/e along a
normal co2ordinate they are said to 3e eecuting a normal mode o. /i3ration and there
are no cross2terms in the 9amiltonian operator .or the potential or 4inetic energies
3et6een any t6o di..erent normal modes7 Since there are no cross2terms in the 9amiltonian
the normal modes do not interact 6ith each other, 6hich is 6hy the 6a/e e0uation can 3e
separated7 Cost importantly, the normal modes and their associated energies are the
eigen.unctions, G (&
n
+, and eigen/alues, E
n
, o. the 6a/e e0uation .or the /i3rational
pro3lem, @ust li4e those o. the harmonic oscillator 6hich 6e ha/e studied a3o/e1
9

n
G!3
n
" = E
n
G!3
n
"
!#0.-.#"
And, in @ust the same 6ay, 6e usually consider them to 3e harmonic, although 6e
4no6 that this is only an approimation7 'ach normal mode must 3elong to one o. the
symmetry species (irreduci3le representations+ o. the molecular point group
]
and they are
not too di.Lcult to en/isage7 A normal mode descri3es the mo/ement o. all the atoms
in the molecule, including the possi3ility that one or more atoms do not mo/e7 When
the atoms are /i3rating in a normal mode they all mo/e in phase, though not necessarily
6ith the same amplitudes, and pass through the e0uili3rium nuclear conLguration and
the turning points o. their motion simultaneously7 There.ore, although the motion may 3e
comple, it can 3e thought o. in terms o. a single displacement in 6hich all atoms are
simultaneously in/ol/ed and the 3asic theory o. the motion can 3e epressed in the same
.orm as that o. the simple 3ond stretching o. a diatomic molecule7 Thus, the eigen.unctions
G (&
n
+ ha/e eactly the same alge3raic .orm as those .or the diatomic molecule, 6hich
are descri3ed in Bo #07,, 6ith : replaced 3y &
n
7 And @ust as .or the hydrogen2atom
pro3lem, the solution .or the 6hole molecule is gi/en 3y the product o. the ,; I ? (,; I
5+ solutions1

total
= G!&
#
" G!&
2
"
G!&
,;?
"

G!&
n
" !#0.-.2"
n
9o6e/er, unli4e the hydrogen2atom case, each o. the ,; I ? (,; I 5+ separated
eigen2 /alue I eigen.unction e0uations is o. eactly the same .orm as '0uation (#07-7#+
and the total /i3rational energy o. the molecule is the sum o. the ,; I ? (,; I 5+ E
n
/alues, i7e7 the sum o. the energies o. the indi/idual modes, ta4ing account o. the
num3er o. 0uanta
(v
n
+ o. energy in that mode1
E
total
=

E
n
=
v
n
+
#

2
h>
n
!#0.-.,"
n n
]
Group theory has many important and /alua3le applications to A: spectroscopy and any tet on the theory o. molecular
/i3rations 6ill discuss these in detail7
%.1+1& Vi?rations o" real pol0atomi# mole#;les
An general, 6e do not o3ser/e the /i3rations o. indi/idual 3onds7 Thus, using 6ater as
our eample, 6e do not see a /i3ration 6hich corresponds to an oscillation in the length
o. one "I9 3ond7 The simple mathematical reason .or this is that such a /i3ration is
not a normal mode7 Durthermore, a change in the length o. one "I9 3ond a..ects the
other "I9 3ond 3ecause they share the oygen atom and also 3ecause any change o.
3ond length introduces some change in the electron distri3ution in a molecule7 The t6o
"I9 stretching /i3rations are there.ore co1%led and 6e do not o3ser/e their independent
.re0uencies in the in.rared spectrum o. 6ater7 When t6o systems, $
a
and $
3
say, 6hich
o3ey the la6s o. 0uantum mechanics are coupled then a miing ta4es place and t6o ne6
systems 6ith the 6a/e .unctions, G
+
and G

are .ormed, 6here1
G
+
= cos #.$
a
+ sin
#.$
3
G

= sin #.$
a
cos
#.$
3
We note that since cos
2
# + sin
2
# = #, the ne6 mied .unctions are al6ays
normalised (Section *75+7 The miing o. t6o /i3rations depends upon t6o .actors, the
magnitude o. the interaction causing the miing and the separation in energy (.re0uency+
3et6een the miing /i3rations7 The miing is at a maimum 6hen the t6o /i3rations to 3e
mied ha/e eactly the same energy, in 6hich case the t6o ne6 /i3rations contain
e0ual 0uantities o. the old com3ined in2phase and out2o.2phase7 The "I9 stretching
/i3rations o. 6ater are illustrated in Digure #07$, 6here the angle 3ending /i3ration has
3een included .or completeness7 The mo/ements o. the atoms are in/ersely proportional to
their masses and must 3e such as to 4eep the centre o. mass o. the molecule stationary7 The
o3ser/ed 6a/e num3ers o. the 3ands sho6 some important general characteristics7 The
symmetric stretch2
ing (,%,2 cm
#
+ is lo6er than the asymmetric (,$*2 cm
#
+ and the 3ending (?*% cm
#
+
is much lo6er than the t6o stretchings7 This reOects the di..erent .orce constants 6hich
are much larger .or 3ond stretching than .or angle 3ending (Ta3le #07#+7
What cannot 3e detected 6ithout more detailed analysis o. the data is the .act that
there is a miing o. the symmetric stretching and the 3ending /i3ration7 A change in
the "I9 3ond length changes the .orce constant .or the 9I"

I9 angle 3ending, and
/ice
/ersa7 There.ore, the t6o types o. /i3ration are coupled, 6hich is the same as saying
that the 3ond2stretching and angle23ending /i3rations are not themsel/es normal modes
3ecause they are lin4ed 3y energy terms in the 9amiltonian operator7 We can /ie6 this
as the process o. diagonalising a 2 2 matri (Appendi ,+, in 6hich the 3asis
states,
i7e7 the t6o modes, are com3ined in such a 6ay as to reduce the interaction to Kero and
symmetric stretching
n = ##*7$ #0
#0
s
#

,%,2 cm
#
asymmetric stretching
n = ##%72 #0
#0
s
#
,$*2 cm
#
a
n
g
l
e 3ending
n = #$7*# #0
#0
s
#
?*% cm
#
6ig;re %.1- The /i3rations o. the 6ater molecule
Colecule Bond
*
Angle
c
Colecule Bond
*
Angle
c
stretching 3ending stretching 3ending
9
2
" 9I" = -%0 9"9 = -0 9
2
S 9IS = *,0 9S9 = *5
;9
,
9I; = ?50 9;9 = 50 C9
*
CI9 = 5*0 9C9 =
*5
C"
2
C=" = #550 "C" = ?0 S"
2
S=" = $$5 "S" = %0
Ta?le %.1% The 3ond2stretching and angle23ending .orce constants
a
.or some small molecules
a
Cany more .orce constants are ta3ulated in sources such as '7B7 Wilson Jr, J7C7 <ecius and !7C7 Cross, 5olec+
1lar Vi*rations, CcGra629ill, ;e6 Ror4, #$55, and G7 9erK3erg, :nfrared and Raman S%ectra of Polyatomic
5olec1les, 8an ;ostrand, ;e6 Ror4, #$*57
*
The units o. the 3ond2stretching .orce constants are ;m
#
7
c
The units o. the angle23ending .orce constants are ;m7
The reason .or the di..erent units o. the t6o types o. .orce constant is the .ollo6ing7 The change o. a 3ond
length or 3ond angle are measured 3y )l and )# respecti/ely7 )# is measured in radians and there.ore has
no units7 The .orce constant relates the potential energy due to a change in 3ond length or 3ond angle to the
s0uare o. the change ('0uation (#0727*++, i7e7 8 =
#
4
l
!)l"
2
or
#
4
#
!)# "
2
, so that in order .or the dimensions
o.
2 2
the potential energy to 3e the same (mass length
2
time
2
+ in 3oth cases, the .orce constant .or angle 3ending
is usually multiplied 3y the lengths o. the t6o 3onds 6hich deLne the angle7
generate the t6o genuine normal /i3rational modes7 But there 6ill only 3e miing i.
the symmetry o. the t6o /i3rations is the same and 6e can see that this is the case in
this particular eample i. 6e /isualise the changing dipole moment associated 6ith each
/i3ration7 An a static 6ater molecule the dipole moment lies along a line in the plane
o. the molecule 3isecting the 9I"

I9 3ond angle7 When the molecule per.orms
either
symmetric stretching or angle23ending /i3ration the change in the dipole moment lies
along the same direction7 With the asymmetric stretching /i3ration, on the other hand, the
change in the dipole moment is directed at right2angles to the static dipole moment7 This
indicates that the asymmetric stretching /i3ration is o. a di..erent 4ind .rom the other
t6o /i3rationsP spectroscopists say it 3elongs to a di..erent symmetry s%ecies7 8i3rations
o. di..erent symmetry species cannot interact and mi, 3ut those o. the same species
can and usually do7 As 3e.ore, the degree o. their miing depends upon the interaction
3et6een them and the di..erence in their energies7 An the case o. the stretchingH3ending
/i3rations o. 6ater the miing is small, only # I 2 Y o. the one is .ound in the other7
But it is important to recognise that this phenomenon eists and that a 3and o3ser/ed in an
in.rared spectrum cannot al6ays 3e assigned to the stretching o. @ust one 3ond or a single
angle23ending /i3ration7
The .act that the direction o. the changing dipole moment o. the 6ater molecule is
di..erent .or di..erent /i3rations has important applications7 A molecule can only interact
6ith e2m radiation that is polarised in the same direction as a changing dipole moment in
the molecule7 There.ore, i. a molecule is irradiated 6ith plane polarised light it 6ill a3sor3
the light only i. it is orientated so as to .ulLl the a3o/e condition7 A. the structure o. a
solid sample (a crystal, .or eample+ is 4no6n then the orientation o. the sample necessary
.or a particular 3and to appear in the in.rared a3sorption spectrum can 3e used to assist
in the assignment o. the 3and7 Similarly, the metal2sur.ace selection rule (Section %7-7,+
depends .or its e.Lcacy upon the .act that an allo6ed A: transition can 3e related to the
direction o. a changing dipole moment 6ithin a molecule7
A typical spectrum o. a small molecule 6hich illustrates se/eral o. the most important
points a3out in.rared spectra is that o. 3romochloromethane (C9
2
BrCl+ (Digure #07#0+7
The assignment o. the 3ands is gi/en in Ta3le #0727 T6o car3on I halogen
stretching
2
9
,
5
# Br C Br
?
%
9
*
-
2
9
,
5
#
Br C Cl
?
9
*
-
%
,75 275 270 #75 #70 07% 07? 07*
Wa/e num3er (#0
,
cm
#
+
:eprinted 6ith permission o. Aldrich Chemical
Co7, Anc7
6ig;re %.1%. The in.rared a3sorption spectra o. di3romomethane and 3romochloromethane
Ta?le %.1& The assignment o. the in.rared spectra o. di3romomethane and 3ro2
mochloromethane (sho6n in Digure #07#0+
#7 C9
2
asymmetric stretch
C9
2
Br
2
f
,0?5
C9
2
BrCl
f
,0?0
27 C9
2
symmetric stretch ,00, 2$%?
,7 C9
2
scissors #,$0 #*0-
*7 C9
2
6agging ##$2 #22-
57 C9
2
t6isting #0$5 ##,0
?7 C9
2
roc4ing %#, %50
-7 CBr
2
asymmetric stretch ?,$ CICl stretch -,0
%7 CBr
2
symmetric stretch 5-% CIBr stretch ?05
$7 CBr
2
scissors #?$ CBrCl scissors 22$
f
Band positions in 6a/e num3ers (cm
#
+
/i3rations are /isi3le7 The t6o CI9 stretching /i3rations interact, as the "I9 stretches
in 6ater do, to .orm asymmetric and symmetric com3inations 6hich occur at ,0?0 and
2$%? cm
#
respecti/elyP the asymmetric stretch at the higher 6a/e num3er has the greater
intensity 3ecause it entails a greater change o. dipole moment than the symmetric stretch7
These are the highest 6a/e num3er 3ands in the spectrum7 The CICl stretch is .ound at
-,0 cm
#
and the CIBr e/en lo6er at ?05 cm
#
7 The decrease in 6a/e num3er in the
se0uence CI9 R CICl R CIBr reOects the .act that the .re0uency, and there.ore the 6a/e
num3er, is in/ersely proportional to the reduced mass o. the t6o atoms .orming the 3ond
('0uation (#07,7,++, though changes in the .orce constant also play a part7 The e..ect o. the
atomic mass can also 3e seen in the angle 3ending 6here the 9ICI9 scissoring /i3ration
is .ound at #*0- cm
#
6hile the ClICIBr scissoring is o.. the scale at 22$ cm
#
7 T6o
other signiLcant 3ands can 3e identiLed in this spectrum7 The intense C9
2
6agging at
#22- cm
#
and the less intense C9
2
roc4ing at %50 cm
#
7
The names o. these three types o. /i3ration arise in the .ollo6ing 6ay7 Amagine that
the plane containing the car3on, chlorine and 3romine atoms is at right2angles to the
plane containing the car3on and t6o hydrogen atoms7 A. the atoms in the ClICIBr plane
remain stationary then the /i3ration in 6hich the 9ICI9 3ond angle opens and closes
is the 9ICI9 scissoring7 A. the 9ICI9 plane mo/es to and .ro in such a 6ay that the
t6o hydrogens mo/e to6ards and then a6ay .rom a halogen atom, this is the 6agging
/i3ration7 A., on the other hand, the 9ICI9 plane mo/es .rom side2to2side at right2angles
to the ClICIBr plane, then this is the roc4ing /i3ration7
;ote that all ,; I ? = $ 3ands are allo6ed 3y the selection rules and all are seen
3ut
6ith /ery di..erent intensities, 6hich reOect the magnitude o. the change in dipole moment
associated 6ith the di..erent modes o. /i3ration7 The strong a3sorption o. the CICl (-+ and
CIBr (%+ stretching /i3rations is a conse0uence o. the large dipole moments o. these
3onds, 6hich there.ore undergo large changes during the /i3rational cycle7 But the change
is /ery small .or the C9
2
scissoring (,+ and t6isting (5+ /i3rations7 Andeed, unassigned
3ands stronger than the last t6o can 3e seen in the spectrum, one at approimately
#5?0 cm
#
, .or eample7 Such a 3and may 3e due to an impurity in the sample or to
an o/ertone or a com3ination 3and (Section #07?+7 The sum o. the 6a/e num3ers o. the
strong 3ands ? and - is #5%0 cm
#
, 6hich suggests that the #5?0 cm
#
3and may 3e due
to the com3ined ecitation o. these t6o /i3rations7 Compare the spectrum @ust descri3ed
6ith that o. di3romomethane and note the e..ect o. increasing the mass o. one halogen
atom on the .re0uencies7
%.1+1' C$ara#teristi# gro;p "re@;en#ies
An the last section the spectra o. C9
2
BrCl and C9
2
Br
2
6ere compared7 An Ta3le
#072 there is a close similarity in the 6a/e num3ers o. each o. the si /i3rations
attri3uted to the C9
2
group7 The .re0uencies o. /i3rations such as these, usually
in/ol/ing atoms on the periphery o. a molecule, do not change much 6hen the
remainder o. the molecule is changed and they there.ore constitute a /alua3le method in
molecular structure deter2 mination7 They are 4no6n as characteristic group .re0uencies
and lists o. them can 3e .ound in many 3oo4s de/oted to A: spectroscopy7
#$I##
An this
contet /i3rations in/ol/2
ing hydrogen, e7g7 the "I9 stretch in alcohols (,?00 cm
#
+, the ;I9 stretching o. the
;9
2
group (,*00 cm
#
+ are use.ul and easy to identi.y 3ecause, li4e the CI9 /i3ra2
tions, they lie near the upper etremity o. the spectrum7 Similarly, the 3ands o. CICl
(-25 cm
#
+, CIBr (?50 cm
#
+ and CIA (550 cm
#
+, 6hich are .ound near the
other
spectral etreme, pro/ide e/idence o. the presence o. halogen atoms7 A 3and that occurs
in the centre o. the spectral range (#-50 I #?00 cm
#
+ is the C=" stretch o.
aldehydes and 4etonesP it is particularly 6ell 4no6n7
%.1+1( 5arge mole#;les
'/erything that has 3een said a3o/e concerning the 6ater and 3romochloromethane
molecules is e0ually important in the in.rared spectra o. the larger molecules 6hich
are o. interest to chemists7 But as the num3er o. atoms in a molecule rises the spec2
trum 3ecomes increasingly di.Lcult to assign and interpret7 Coreo/er, 6hen many atoms
Anharmonicity 5,
are lin4ed together in a comple three2dimensional structure changes o. indi/idual 3ond
angles and 3ond lengths are not possi3le7 An 3enKene, .or eample, a single CICIC
3ond angle cannot change 6ithout some corresponding change in other CICIC angles
or CIC 3ond lengths7 Complicated /i3rations in/ol/ing many simultaneous changes o.
3ond angles and 3ond lengths are 4no6n as s;eletal /i3rations and, e/en 6hen their eact
nature is o3scure, they gi/e rise to a series o. in.rared a3sorption 3ands 6hich are highly
characteristic o. the molecule7 This Cnger%rint is /ery important in 0ualitati/e analysis
and structure determination7
%.1, ANHARM2NICITY
We ha/e .re0uently noted a3o/e that although the concept o. the harmonic oscillator is
a good model .or molecular /i3rations, all real molecules depart .rom this ideal and the
e..ects o. their anharmonicity must 3e ta4en into account 6hen 6e attempt to interpret
some o. the more su3tle, 3ut none the less important, e..ects seen in A: spectroscopy7 We
can distinguish t6o di..erent types o. anharmonicity7
Electrical anharmonicity has to do 6ith the pro3lem o. correctly representing the
molecule as an array o. electrical charges 6hich can interact 6ith e2m radiation7 An
'0uation (#07572+ the transition dipole moment is 6ritten in terms o. the dipole moment
plus its Lrst deri/ati/e 6ith respect to the normal co2ordinatesP in mathematical parlance,
the Taylor series epansion o. the dipole moment7 But these are simply the Lrst t6o terms
in the series and i. higher deri/ati/es 6ere included they 6ould allo6 transitions ha/ing
v R #7 Thus, the e..ect o. electrical anharmonicity is primarily to allo6 3ands to appear
6hich 6e 6ould not ha/e epected7
"echanical anharmonicity, .rom 6hich the ad@ecti/e mechanical is o.ten omitted,
descri3es the .act that the potential energy cur/e associated 6ith a molecular /i3ration
is not para3olic in the co2ordinate, i7e7 is not o. the .orm o. '0uation (#0727*+7 The
e..ects o. mechanical anharmonicity are seen in the /i3rational energy le/els and hence
3and .re0uencies7 Also, in some rather special cases 6here the anharmonicity results in
a miing o. /i3rational states, there can 3e 0uite dramatic e..ects upon 3and intensities7
Some classic eamples o. mechanical anharmonicity are eamined in the .ollo6ing t6o
sections7 Both in/ol/e car3on dioide7
%.1,1% 6ermi resonan#e
The assumption o. harmonic /i3rations pro/ides such a simpliLcation that it is in/aria3ly
the starting point .or the analysis o. A: spectra7 9o6e/er, the e..ects o. anharmonicity
can 3e large and 6e are sometimes .orced to recognise them7 The /i3rational spectrum o.
car3on dioide pro/ides a good eample7 =n.ortunately, this most .amous o. eamples
in/ol/es :aman spectroscopy,
#2
6hich is not discussed in this 3oo4, rather than A:7
9o6e/er, our primary o3@ecti/e is to illustrate ho6 anharmonicity can 3ring a3out the
miing o. /i3rational energy states and the .act that the e..ects o. this miing are seen
here in the :aman rather than A: spectrum is o. secondary importance7
The 3ands seen in the A: and :aman spectra o. car3on dioide (C"
2
+ under conditions
o. lo6 resolution are listed in Ta3le #07,7 Dor this linear molecule 6e epect to see
5* An.rared Spectroscopy
Ta?le %.1' The /i3rational spectrum o. car3on dioide under condi2
tions o. lo6 resolution
Code >(cm
#
+ <escription :HA: acti/e
>
#
#,*0 symmetric 3ond stretching :
>
2
??- angle 3ending A:
>
,
2,*$ asymmetric 3ond stretching A:
+
F
N
y+ +
o
+
6ig;re %.1%% The t6o components, >
2
and >
2y
, o. the dou3ly degenerate angle23ending /i3ration
o. car3on dioide
.our (, , 5+ .undamental /i3rations and 6e do 3ecause the angle 3ending is
dou3ly degenerate7 (The "=C=" angle can 3e de.ormed in either o. t6o planes at
right2angles to each other (Digure #07##+7+ 9o6e/er, 6hen the spectra are measured
under higher resolution the #,*0 cm
#
3and in the :aman spectrum is .ound to consist
o. t6o 3ands
o. approimately e0ual intensity centred at #2%5 and #,%% cm
#
7 This o3ser/ation appears
to 3e at odds 6ith theory7
The .ollo6ing is a simpliLed /ersion o. the eplanation suggested 3y 'nrico Dermi in
#$,#, since 6hen /ery many similar eamples ha/e 3een reported7 Although he 4ne6 >
2
and >
,
.rom in.rared spectroscopy, Dermi had no /alue .or >
#
so he determined the .orce
constant, 4, .or the C=" 3ond stretching .rom >
,
and using this and the atomic masses he
estimated that the symmetric stretch should lie some6here near #2,0 cm
#
P close to the
predicted Lrst o/ertone o. >
2
at approimately 2 >
2
= #,,* cm
#
7 Durthermore,
Dermi
4ne6 .rom the symmetry o. the o/ertone that it could interact 6ith >
#
7 The mechanism o.
the interaction is the anharmonicity, in particular cu3ic terms ('0uation (#07?7#++ 6hich
are neglected in the simple, harmonic oscillator theory7 The .ormulation o. the energy
matri (Appendi ,+ .or this interaction is slightly complicated 3y the .act that >
2
is a
dou3ly degenerate /i3ration and thus its Lrst o/ertone may correspond to three di..erent
ecitations7 Since >
,
had no part to play in the calculation, Dermi omitted it and 6rote
his 6a/e .unctions in the .orm (v
#
v
2
v
2y
+, 6here >
2
and >
2y
are the t6o
degenerate
components o. >
2
7 An this notation the singly ecited >
#
state is (#00+ and it may, in
principle, interact 6ith the three dou3ly ecited >
2
states (020+, (002+ and (0##+7 9o62
e/er, symmetry .or3ids an interaction 3et6een (#00+ and (0##+ and the energy matri
reduces to1
9

(#00+ (020+ (002+
(#00+ >
#
L L
(020+ L 2>
2
0
(002+ L 0 2>
2
(L is the interaction .or 6hich Dermi estimated a /alue o. *0 cm
#
7+
Anharmonicity 55
:ather than e/aluating the matri immediately, Dermi simpliLed it 3y com3ining the
t6o o/ertone .unctions into their sum and di..erence1

+
=

#
2
{!020" + !002"} and

=

#
2
{!020" !002"}
6hich reduces the matri to the .orm1
9

(#00+
+

(#00+ >
#

2L
0

+

2L 2>
2
0


0 0
2>
2
We re0uire the eigen/alues and eigen.unctions o. the 2 2 matri7 'ach 6ill 3e
a miture o. the :aman2allo6ed ecitation (#00+ and
+
gi/ing t6o ne6 ecited states
to 6hich :aman transitions are allo6ed 3y /irtue o. their component o. (#00+7 They
can easily 3e .ound using the method descri3ed in Appendi , i. the /alues o. L, >
#
and >
2
are 4no6n7 Since he had no relia3le /alue o. >
#
, Dermi simply noted that i. >
#
2>
2
6e epect the t6o ne6 /i3rational states to 3e separated 3y 2

2L = ##, cm
#
and
the corresponding spectral 3ands to 3e approimately e0ual in intensity7 These results
are 3oth in good agreement 6ith eperiment 6here the t6o :aman 3ands are almost
e0ual in intensity and the o3ser/ed > is #0, cm
#
7 An the light o. the /alue o. >
Dermi suggested that his estimate o. >
#
#2,0 cm
#
6as pro3a3ly a3out #00 cm
#
too lo67
An the last part o. his paper Dermi eplains the presence o. t6o .urther, /ery 6ea4
:aman 3ands in terms o. eactly the same type o. miing among groups o. three states1
(##0+, (0,0+ and (0#2+ in the case o. one 3and and (#0#+, (00,+ and (02#+ .or the other7
An each o. these states the molecule is already ecited 6ith at least one 0uantum o. >
2
and there are only - Y o. such molecules in the gas at room temperature, hence the /ery
lo6 intensity7
Dinally, 6e might note that, although a 0uantitati/e solution o. the car3on dioide
pro3lem re0uires a 0uantum2mechanical analysis, 6e can see in a simple classical /ie6
6hy there is an interaction 3et6een the /i3rations >
#
and >
2
and 6hy resonance is possi3le
6hen >
#
2>
2
7 As the molecule eecutes the angle23ending /i3ration, >
2
, the
oygen
atoms s6ing .rom one side o. the linear "=C=" conLguration to the other and 3ac4 again,
passing through the linear conLguration t6ice in each /i3rational cycle7 The centri.ugal
.orce arising .rom this motion o/er an arc o. a circle is at a maimum 6hen the molecule
is linear and acts in such a 6ay as to etend 3oth C=" 3onds simultaneously7 A. the
.re0uency o. this e..ect, 2>
2
, coincides 6ith that o. the symmetric 3ond stretching, >
#
, then 6e ha/e the ideal conditions .or resonance7
%.1,1& Vi?rational ang;lar moment;m an/ t$e Coriolis intera#tion
5? An.rared Spectroscopy
The mechanics o. 3odies undergoing simultaneous linear and rotational motion, 6as Lrst
in/estigated 3y Gaspard de Coriolis (#-$2 I #%*,+, a Drench physicist 6ho studied
the mo/ements o. air and 6ater on the sur.ace o. the earth7 The eponymous .orce 6hich
his 6or4 re/ealed is responsi3le, among other things, .or the 6hirling motions o.
tropical
2
2
2
m
" C "
"
" C "
(a+
(3+ (n
1
+
(c+ (n
,
+
6ig;re %.1%& Coriolis .orces on a single mass, (a+ the symmetric stretching /i3ration o. car3on
dioide (3+ and the asymmetric stretching /i3ration (c+
storms7 At also has some /ery interesting e..ects upon the spectra o. moleculesP 3ut Lrst
6e should clari.y its origin7
Consider an atom o. mass, m, 6hich is part o. a molecule rotating a3out an ais
through the centre " and perpendicular to the plane o. the paper (Digure #07#2(a++7 The
rotating molecule has angular momentum so that i. in the course o. a /i3ration the mass
mo/es to the right, increasing its distance .rom ", the speed o. mo/ement o. the mass
must 3e reduced to conser/e that momentum7 The slo6ing o. the mass 6ill appear to an
o3ser/er riding on the molecule, 6ho 6ill not 3e a6are o. the rotational motion as 6e
are una6are that the earth is rotating, as the response to a .orce in the direction indicated
3y the do6n6ards arro67 This is the Coriolis .orce and it has the potential to cause an
interaction 3et6een the /i3ration and rotation o. a molecule, as the .ollo6ing eamples
6ill sho67 Se/eral types o. Coriolis interaction can 3e distinguished7
-y%e I. Ta4ing car3on dioide as our eample 6ith K as the internuclear ais 6e
Lrst eamine the Coriolis .orces arising .rom the symmetric stretching /i3ration, >
#
,
(Digure #07#2(3++7 The hea/y, horiKontal arro6s represent the velocities o. the oygen
atomsP the car3on atom is stationary7 The molecule is rotating, end2o/er2end, and the
lighter, /ertical arro6s sho6 the resulting Coriolis .orces 6hich, in this case, produce
a coupling to the rotation rather than the /i3ration o. the molecule7 This has a /ery
small e..ect upon the rotational energy le/els 3ut is not normally considered to 3e a
Coriolis e..ect7
-y%e J. We continue 6ith our car3on dioide eample and eamine the e..ect o. Coriolis
.orces on the asymmetric stretching >
,
7 An this case (Digure #07#2(c++ the directions o.
the Coriolis .orces on each atom are such as to promote the 3ending /i3ration, >
2
, 3ut
6ith the .re0uency o. >
,
7 >
2
is a dou3ly degenerate mode and in order to appreciate .ully
the e..ect o. the Coriolis coupling it is necessary to eamine it in more detail7 We again
deLne the t6o components o. the /i3ration, >
2
and >
2y
, to occur in the K and yK planes
(Digure #07##+7 Anspection o. the Lgure sho6s that a rotation o. ( H2 a3out the K ais, in
either sense, con/erts one o. the angle23ending /i3rations into the other7 This suggests that
there is angular momentum a3out the K2ais associated 6ith the /i3ration and 6e can sho6
that this is indeed the case in the .ollo6ing manner7 We Lrst use Bo #07, to 6rite do6n
the harmonic oscillator eigen.unctions,
v
, .or the normal co2ordinate 0 6ith v = 0
21
#

0
= ZN ,( \
*
ep!
#
N
0
2
"
#

#
= ZN ,( \
*
!2N "0 ep!
#
N 0
2
"
#

2
= ZN ,( \
*
! 2N 0
2
#,
2" ep!
#
N 0
2
"
2
2
#
#
2
2
2
2
2
2
2
An accordance 6ith the concept o. the normal mode or normal co2ordinate (Section
#07-7#+, 6e can regard the /i3rational modes in the Lgure as displacements along a
single co2ordinate or y, 6ith the pro/iso that, to 4eep the centre o. gra/ity stationary, a
displacement o. the car3on atom o.
#2
C
#?
"
2
3y x is accompanied 3y displacement o. the
t6o oygen atoms 3y +
#
!#2,#?"x = +,xH%, and similarly .or y7 There are
simultaneous,
e0ual and opposite displacements o. the oygen atoms in the K direction7
We can no6 6rite do6n the appropriate .unctions to descri3e the three degenerate
/i3rationally2ecited states, , 6hich can 3e .ormed 3y adding t6o /i3rational 0uanta to
the >
2
/i3ration7 'ach is a product o. t6o harmonic oscillator eigen.unctions characterised
3y their 0uantum num3ers (v
2
v
2y
+ as su3scripts, the co2ordinates, 0, 3eing
replaced
3y or y, as re0uired1
#

##
= ZN ,( \
2
2N y ep!
#
N Z
2
+ y
2
\"

20
= ZN ,( \
2

02
= ZN ,( \
2

2N
2

#,

2N y
2

#,

ep!
#
N Z
2
+ y
2
\"
ep!
#
N Z
2
+ y
2
\"
We 4no6 .rom Chapters , and * that i. 6e are loo4ing .or angular momentum then
a polar co2ordinate system is more use.ul than a Cartesian and 6e use the plane2polar
system in 6hich1
r
2
=
2
+ y
2
= r cos $ and y = r sin $
Su3stituting r and $ .or and y 6e ha/e1
#

##
= ZN ,( \
2
2N r
2
sin 2$ ep!
#
N r
2
"
#

20
= ZN ,( \
2
2N r
2
cos
2
$
#,
2 ep!
#
N r
2
"
#

02
= ZN ,( \
2
2N r
2
sin
2
$
#,
2 ep!
#
N r
2
"
We shall loo4 .or .unctions 6hich are eigen.unctions o. the operator .or the K2component
o. angular momentum, l

K
= ih` D,D $ (see Chapters , and *+7 ;one o. the a3o/e
.unctions
can satis.y this re0uirement since they each gi/e a di..erent .unction 6hen di..erentiated
once 6ith respect to $7 But 6e can attempt to Lnd the .unctions 6e see4 3y ma4ing
com3inations7 !ro/ided that 6e ensure that they are normalised, any ne6 .unctions 6e
.orm 6ill remain
eigen.unctions o. the 9amiltonian operator, 9

, 3ecause all three .unctions,
##
,
20
and

02
, are degenerate7
20
and
02
are .unctions o. cos
2
$ and sin
2
$ respecti/ely and 6e
4no6 that cos
2
$ + sin
2
$ = #7 There.ore, the normalised sum1

#
#
2 # 2
0
=
2
{
20
+
02
} = ZN ,( \
2
!N
r
#" ep!
2
N r "
does not contain $ and is an angular momentum eigen.unction 6ith an eigen/alue o.
Kero, hence the su3script o. 0 0uali.ying the ne6 .unction7 This is the state 6hich 6e
called
+
in the pre/ious section7 9a/ing ta4en the sum o.
20
and
02
6e must also
ta4e their di..erence1

#
#
2 # 2

=
2
{
20

02
} = ZN ,( \
2
N r
cos 2$ ep!
2
N r "
+2
We note that
##
and

are .unctions o. sin 2$ and cos 2$ respecti/ely 6hich
is reminiscent o. Chapter , (Ta3le ,7#+, 6here 6e .ound that the .unctions (#H

( +
sin(n$+
and (#H

( +cos(n$+ 6ere not eigen.unctions o. the angular momentum operator (l

K
=
ih` D,D $+ 3ut that eigen.unctions such as1
# #

# #

2(

ep!

in$"
=

(
cos!n$" i
(
sin!n$"
could 3e .ormed .rom normalised com3inations o. them7 The ne6 .unctions remained
eigen.unctions o. the energy operator, 9

7 This suggests a similar approach here
]
so
6e .orm1

#
#
2 # 2
and1

+2
=
2
{

+ i
##
} = ZN ,2( \
2
N r
ep!
2
N r " ep!+2i$"

#
#
2 # 2
2
=
We no6 ha/e1
2
{

i
##
} = ZN ,2( \
2
N r
D
ep!
2
N r " ep!2i$"
and1
l

K

+2
= ih`
D$

+2
= +2h`
+2
D
l

K

0
= ih
`
D$

0
= 0
D
l

K

2
= ih
`
D$

2
= 2h
`

2
These are three eigen.unctions o. l

K
6ith eigen/alues, characterised 3y the
0uantum num3er, sym3ol l, o. +2, 0 and 2 respecti/ely7 All ecitations o. the
3ending /i3ra2 tion gi/e rise to angular momentum a3out the K ais so it is important
to include l in
the notation .or the /i3rational state o. the car3on dioide molecule gi/en in the .orm
(v
#
v
2
l
v
,
+7 The .unctions and
2
correspond to a slightly 3ent car3on dioide
molecule, 6hich is rotating around the K ais there3y gi/ing rise to a moment o. inertia
6here pre/iously there 6as none7 The state
0
has no angular momentum a3out K and
the di..ering interactions o. the three .unctions li.ts the triple degeneracy o. the (0, 2, 0+
state7 To a Lrst approimation (see 3elo6+ the sense o. rotation ma4es no di..erence to
the rotational energy le/els due to the end2o/er2end rotation o. the molecule, 3ut there
is a di..erence 3et6een l = 0 and l = 2 since the correction, E, to the total
energy, rotational plus /i3rational, is gi/en 3y1
E = !g
22
/"l
2
!#0.%.#"
The Lrst term in '0uation (#07%7#+ is the correction to the /i3rational energy in 6hich
g
22
is the anharmonicity constant (Section #07?+ .or the degenerate /i3ration >
2
7 The
second term is the correction to the rotational energy in 6hich / is the rotational constant
deLned 3y '0uation (#07*7#a+7 Since the /alues o. g
22
and / .or car3on dioide are
]
When .orming com3inations 3y adding and su3tracting .unctions, addition corresponds to the in2phase com3ination (phase
angle = 0+ 6hile su3traction corresponds to the out2o.2phase com3ination (phase angle = ( +7 When the com3ination
also in/ol/es i 6e are com3ining .unctions 6hich di..er in phase 3y +( H2 (+i+ or ( H2 (i+7 Compare the Argand
diagram in Appendi %7
07?2 and 07,$ cm
#
respecti/ely, the separation o. the l = 0 and l = 2 le/els 6ould
3e epected to 3e o. the order o. *70 cm
#
3ut this cannot 3e determined directly .rom
the spectrum 3ecause, as 6e ha/e seen a3o/e, the (02
0
0+ le/el is in Dermi resonance
6ith the (#0
0
0+, 6hich accounts .or the anomalously large o3ser/ed splitting o. 5#
cm
#
7 Durthermore, the resonance interaction causes the t6o states to mi in almost a # 1
# ratio (see 3elo6+ so that it is no longer correct to spea4 o. either o. them as 3eing
(02
0
0+ or (#0
0
0+7
-y%e X. An the last eample o. Coriolis coupling 6e eamined the angular momentum
associated 6ith the dou3ly ecited >
2
/i3ration7 An .act, e/ery o/ertone o. >
2
has angular
momentum and the t6o components o. the singly ecited >
2
state also undergo a Coriolis
interaction as a conse0uence o. their angular momentum a3out the K ais .or 6hich l =
#
(see pro3lem 5+7 As sho6n in Digure #07#,, the Coriolis .orces on the atoms con/ert one
component o. (0#
#
0+ into the other7 This is an eample 6here, e/en i. the energy o.
interaction (o..2diagonal matri element+ is small, the resulting splitting o. the energy
le/els can 3e large 3ecause, prior to the interaction, they 6ere degenerate7 At is .re0uently
called a Lrst order Coriolis pertur3ation and it remo/es the degeneracy o. the pairs o.
l
le/els7 This e..ect is 4no6n as l2type dou3ling7 Thus the t6o (0#
#
0+ energy le/els, 6hich
are degenerate in the a3sence o. /i3rational angular momentum, are split into t6o7 And
in the case o. the dou3ly ecited >
2
, the degeneracy o. (02
+2
0+ and (02
2
0+ is remo/ed
so that all three states ha/e di..erent energies7
To see in a simple 6ay ho6 this may come a3out, 6e note that since car3on dioide
is a linear molecule there is no moment o. inertia or angular momentum associated 6ith
rotation a3out the internuclear ais7 But the angle23ending /i3ration remo/es this linearity
and the molecule 3ecomes, momentarily, capa3le o. angular momentum 6ith respect to
rotation a3out that ais7 This pertur3s the energy le/els o. the molecule, especially, 3ut
not eclusi/ely, the rotational le/els7 =n.ortunately, there appear to 3e no eperimental
o3ser/ations o. l2type dou3ling in car3on dioide in the literature though there are .or
other molecules, e7g7 hydrogen cyanide (9C;+7 This may 6ell 3e 3ecause the splittings
are /ery small and normally measura3le only in micro6a/e spectroscopy 3ut the car3on
dioide molecule gi/es no micro6a/e spectrum since it has no permanent dipole moment7
The energy le/els associated 6ith some o. the interactions 6hich 6e ha/e discussed
a3o/e are represented in Digure #07#*7 The Lgure is illustrati/e rather than eact 3ecause
the energy le/els are determined 3y many su3tle e..ects o. anharmonicity 6hich ha/e
not 3een discussed a3o/e and these .actors result in a slightly larger /alue o. the Dermi2
resonance interaction (L in Section #07%7#+ than 6e Lnd in the .ollo6ing7 "n the sides o.
the diagram the estimated positions o. the le/els in the a3sence o. the Dermi resonance and
Coriolis coupling are sho6nP the three degenerate dou3le ecitations o. >
2
on the le.t at
"
C
"
6ig;re %.1%' Coriolis .orces on the nuclei o. a car3on dioide molecule rotating a3out the inter2
nuclear ais
#,%%72
'nergy
(cm
#
+
#,,$7#
(02
0
0+
(02
2
0+
#,,57#
(#0
0
0+
#,,*7?
#2%57*
6ig;re %.1%( The e..ect o. Dermi resonance and Coriolis coupling on some /i3rational energy
le/els o. car3on dioide (;ot to scale+
#,,$7# cm
#
and the singly ecited >
#
on the right at #,,*7? cm
#
7 The Dermi resonance
interaction o. (02
0
0+ and (#0
0
0+ mies these le/els and displaces them to #2%57* cm
#
and
#,%%72 cm
#
, 6here they are o3ser/ed eperimentally7 L = 5# cm
#
and the
/i3rational 6a/e .unctions a.ter the miing are .ound to 3e1
!#,%%.2" = 0.-2!02
0
0" + 0.?$!#0
0
0"
and
!#2%5.*" = 0.?$!02
0
0" 0.-2!#0
0
0"
The Coriolis interaction o. rotation and /i3ration lo6ers the t6o (02
2
0+ le/els a3out
* cm
#
to the eperimental /alue o. #,,57# cm
#
7 The loss o. the (02
+2
0+H(02
2
0+ degen2
eracy is not sho6n7
%.1- THE %B-7#787O CA5CU5ATI2N 26 IR S!ECTRA
An the second hal. o. the 20th century the 0uantity o. A:2spectral data increased rapidly and
the 0uantitati/e analysis o. that in.ormation, i7e7 the determination o. the .orce constant
.or each normal mode, gre6 in importance7 The determination o. .orce constants 6as
o. interest not only .or a complete assignment o. the spectrum 3ut also .or the light
6hich they could thro6 upon the strength o. chemical 3onds and on the .undamental
thermodynamic properties o. the molecules7 Cost calculations employed the DG2matri
method proposed 3y 'dgar Bright Wilson (#$0% I #$$2+ and 6hen, in the #$?0s,
they 6ere programmed .or computers many important ad/ances 6ere rapidly achie/ed7
Bands in the spectrum could then 3e 0uantitati/ely ascri3ed to mitures o. the
/i3rations o. chemically signiLcant groupings o. atoms in a molecule or to the 6hole
molecule in the case o. s4eletal /i3rations7 The .orce constants .ound could 3e related to
the strength o. 3onds, and the rigidity, i7e7 resistance to de.ormation, o. the molecule7
The mechanics
Bi3liography and Durther :eading ,#-
used in the calculations, 6hich 6ere 3ased upon an input o. atomic masses and trial
normal modes and .orce constants, 6as purely classical7 The trial .orce constants 6ere
empirical /alues deduced .rom those in the literature .or similar molecules and groupsP
they 6ere not calculated7
Core recently, as the po6er o. density2.unctional methods and a*+initio molecular
or3ital calculations has increased, molecular /i3rational energy le/els ha/e 3een deri/ed
using .orce constants calculated 0uantum mechanically .rom molecular 6a/e .unctions
and the use o. normal modes as a 3asis has 3een superseded 3y epressing the motions
o. the atoms in Cartesian co2ordinates7 8ery good theoretical A: spectra are no6 3eing
o3tained 3y this methodP su.Lciently good, in .act, to assign an a3solute conLguration to
each mem3er o. a pair o. optical isomers 3y comparison o. their theoretical and eper2
imental /i3rational circular dichroism (8C<+ spectra7
#2
(A 8C< A: spectrum is an A:
spectrum in 6hich the di..erential a3sorption o. le.t and right circularly polarised radia2
tion (Section %7272+, rather than the total a3sorption, is recorded against 6a/e num3er7+
9o6e/er, the assignment o. the spectral 3ands to particular 3ond2angle or 3ond2length
changes does not emerge as naturally as 6ith the earlier approach7
%.1%. THE S!ECIA5 CASE 26 NEAR IN6RARE3 S!ECTR2SC2!Y
%'
Ceasurements in the region o. the in.rared nearest to the /isi3le, i7e7 the 6a/elength
range % #0
-
to , #0
?
m @usti.y a 3rie. mention in this chapter .or t6o
reasons7 Drom the theoretical standpoint 6e should note that the a3sorption o. e2m
radiation in
this region is entirely due to the o/ertones and com3ination 3ands o. /i3rations in/ol/ing
hydrogen, rather than to .undamental /i3rations7 There are a /ery large num3er o. such
com3inations and o/ertones and though they are 6ea4 3ands they pro/ide strong spectra
6hen neat samples are measured in transmission or reOectance7 Generally, the spectral
3ands are 3road and lac4 the distincti/e .eatures o. mid in.rared spectra7 The second reason
concerns the applications o. ;A: spectroscopy 6hich are o. a /ery special nature7 When
analysed 3y means o. rather sophisticated statistical methods, ;A: spectra ha/e pro/ed
uni0uely /alua3le in 0uantitati/e analysis, especially the analysis o. .oods and agricultural
productsP e7g7 the amount o. 6ater and protein in grains, Oour, malt and 3eans7
%.1%% 8I85I2RA!HY AN3 6URTHER REA3IN
#7 ;7B7 Colthup, L797 <aley and S7'7 Wi3erley, :ntrod1ction to :nfrared and Raman S%ectrosco%y,
,rd edn, Academic !ress, Boston, #$$07
27 G7 9erK3erg, :nfrared and Raman S%ectra of Polyatomic 5olec1les, <7 8an ;ostrand Anc7,
!rinceton, #$*57
,7 !7:7 Gri.Lths and J7A7 de 9aseth, 9o1rier -ransform :nfrared S%ectrosco%y, Wiley, ;e6 Ror4,
#$%?7
*7 ;7 Sheppard, The 9istorical <e/elopment o. 'perimental Techni0ues in 8i3rational Spec2
troscopy, in 8and*oo; of Vi*rational S%ectrosco%y 8ol7 #, (eds J7C7 Chalmers and !7:7 Gri.2
Lths+, Wiley, Chichester, 20027
57 J7C7<7 Brand, Lines of Light, Gordon and Breach, =nited >ingdom, #$$57
?7 L7 !auling and '7B7 Wilson, :ntrod1ction to 31ant1m 5echanics, CcGra629ill Anc7, ;e6 Ror4,
#$,57
-7 G7 9erK3erg, S%ectra of Eiatomic 5olec1les, <7 8an ;ostrand Anc7, ;e6 Ror4, #$507
?2 An.rared Spectroscopy
2
%7 J7C7 9ollas, 8igh Resol1tion S%ectrosco%y, Butter6orths, London, #$%27
$7 L7J7 Bellamy, :nfrared S%ectra of Com%lex 5olec1les, ,rd edn, Chapman and 9all, London,
#$-57
#07 >7 ;a4amoto, :nfrared and Raman S%ectra of :norganic and Coordination Com%o1nds, *th edn,
Wiley, ;e6 Ror4, #$%?7
##7 G7 Socrates, :nfrared Charateristic .ro1% 9re71encies, 2nd edn, Wiley, Chichester, #$$*7
#27 A7 Aamouche, D7J7 <e/lin and !7J7 Stephens, Q. Amer. Chem. Soc., %&&, 2,*? (2000+7
#,7 B7G7 "s3orne, T7 Dearn and !797 9indle, Practical N:R S%ectrosco%y 0ith A%%lications in 9ood
and /everage Analysis, 2nd edn, Wiley, ;e6 Ror4, #$?,7
82D %.1% T$e re/;#e/ mass an/ t$e Hamiltonian operator "or t$e Ai?ration an/
rotation o" a /iatomi# mole#;le
Vi?ration
Consider Lrst the case o. the /i3rating dum323ell model o. a diatomic molecule
(Digure B#07#7#+7 The 4inetic energy, - , depends upon the masses o. the t6o nuclei
and the speed 6ith 6hich they are mo/ing, v
a#
and v
a2
7 The su3script QaG indicates that
the /elocity 6ith 6hich 6e are concerned is that directed along the internuclear ais1
- =
#
m
#
v
a#
2
+
#
m
2
v
a2
2
(B#07#7#+
2 2
The potential energy !V " depends upon the di..erence 3et6een the distance 3et2
6een the t6o nuclei !R" and the e0uili3rium distance !r
e
"7 Both atoms are su3@ect to
a restoring .orce e0ual to 4(R r
e
+, 6hich gi/es rise to a para3olic potential
energy
o. the .orm1
V =
#
4!R r
e
"
2
(B#07#72+ The occurrence o. t6o masses in the e0uation .or - presents
pro3lems and an
analysis o. the motion o. the molecule 6ould 3e easier i. the t6o masses could 3e
epressed as one 0uantity7 That o3@ecti/e can 3e realised in the .ollo6ing 6ay7
The masses m
#
and m
2
oscillate in phase on either side o. the centre o. mass in
such a 6ay that at all times1
m
#
r
#
= m
2
r
2
(B#07#7,+ The amplitude o. the motion o. the lighter mass is greater than that o.
the hea/ier
3y the ratio o. their masses7
R
r
#
r
2
m
#
m
2
centre o. mass
6ig;re 8%.1%1% The /i3rating dum323ell model
v
v
2 2
R
R
v
2
Boes .or Chapter #0 ?,
At any moment in time the 3ond length is R and1
R = r
#
+ r
2
(B#07#7*+ =sing the a3o/e e0uations 6e can epress r
#
and r
2
in terms o. R and m
#
and m
2
1 r
#
= m
2
R,!m
#
+ m
2
" and r
2
= m
#
R,!m
#
+ m
2
" (B#07#75+
Since the centre o. mass is stationary, the /elocity o. each mass is1
D r
#

m
2
DR

m
2
(B#07#7?+
and
v
a#
=
Dt
=
m
#
+ m
2

Dt

m
#
+ m
2
v
R
D r
2

m
#
DR

m
#
v
a2
=
Dt
=
m
#
+ m
2

Dt

m
#
+ m
2
v
R
6here v
:
is the rate o. change o. the 3ond length7 Anserting the a3o/e results into
'0uation (B#07#7#+ 6e ha/e1
m
#

m
2

2
m
2

m
#

2
- =
2

m
#
+ m
2
v
R
+
2

m
#
+ m
2
v
R
#

m
#
m
2

2
2
#

m
#
m
2

2
2
=
2 m
#
+ m
2

m
#
+
2
m
#
+ m
2

m
2
#

m
#
m
2

2

m
#
+ m
2

=
2 m
#
+ m
2
#
2

m
#
m
2

R
#
2
6here

2T

!Tv
R
"
or
2
Tv
R
(B#07#7-+
T = m
#
m
2
,!m
#
+ m
2
" (B#07#7%+
is the red1ced mass 6hich replaces m 6hile v
R
replaces v in the standard epression
.or the 4inetic energy o. a mo/ing mass7
Thus, the total /i3rational energy !E
/i3
" is gi/en 3y1
E
/i3
= V + - =
#
4!R r
e
"
2
+
#
!Tv
R
"
2
,T (B#07#7$+
2 2
so that, replacing Tv
R
3y !ih,2( "D,D R, the energy operator
9

is1
4
2
h
2
D
2
9

=
2
!R
r
e
"

%(
2
T

DR
2
(B#07#7#0+
Rotation
There are three properties o. interest 6hich are associated 6ith the end2o/er2end
?* An.rared Spectroscopy
rotation o. the dum323ell model (Digure B#07#72+7
The moment o. inertia (: +1
: = m
#
r
#
2
+ m
2
r
2
2
= TR
2
(B#07#7##+
R
r
#
r
2
V
t#
m
#
m
2
centre o. mass
6ig;re 8%.1%1& The rotating dum323ell model
V
t2
6here 6e ha/e used '0uation (B#07#75+, and the angular momentum, A, (see
Chapter *+1
A = m
#
r
#
v
t#
+ m
2
r
2
v
t2
(B#07#7#2+ The su3script QtG indicates that 6e are concerned 6ith the tangential
/elocity along
the circular path ta4en 3y each atom around the molecular centre o. mass7 The /elocity
is the length o. the path di/ided 3y the time ta4en to complete one re/olution 6hich
is the in/erse o. the .re0uency o. rotation, >
rot
, so that 6e ha/e1
v
t#
= 2( r
#
>
rot
and v
t2
= 2( r
2
>
rot
(B#07#7#,+ =sing this result 6e readily Lnd that1
A = 2( >
rot
!m
#
r
#
2
+ m
2
r
2
2
" = 2( >
rot
!:
#
+ :
2
" = 2( >
rot
:
(B#07#7#*+
and using '0uation (B#07#7##+1
A = 2( >
rot
TR
2
or A: (B#07#7#5+
6here A = 2( >
rot
is the angular /elocity in radians s
#
7
Dinally, a /ery similar de/elopment sho6s that the 4inetic energy (there is no
potential energy+ associated 6ith the rotational motion, E
rot
, is gi/en 3y1
E
rot
= 2(
2
>
2
TR
2
= 2(
2
>
2
: =
#
A
2
:
(B#07#7#?+
rot rot 2
'0uations (B#07#7##+, (B#07#7#5+ and (B#07#7#?+ sho6 the close and constant rela2
tionship 3et6een : A and E
rot
in classical mechanics7 We epect that relationship to
persist in 0uantum mechanics so that the 0uantisation o. the angular momentum and
energy 6ill go hand2in2hand, as they do .or the one2electron atom7 Andeed, 6e ha/e
here t6o particles rotating a3out their centre o. mass, eactly as in the one2electron
atom, apart .rom the .act that the distance 3et6een the t6o particles is constant and
their relati/e potential energy may 3e regarded as Kero in the rigid rotator approima2
tion7 (Actually, the 3ond 3ecomes longer as the .re0uency o. rotation increases, 3ut
6e shall not consider such reLnements to the theory here7+ There.ore, the 9amiltonian
operator is that .or a system 6ith 4inetic energy only and in Section ,7#,7* it 6as
sho6n that .or motion in the 2direction it is1
9

= !h
2
,%(
2
m"D
2
,D
2
Since 6e are dealing here 6ith three2dimensional motion,
9

3ecomes1
9

= !h
2
,%(
2
m"{D
2
,D
2
+ D
2
,D y
2
+ D
2
,D K
2
}
and the SchroM dinger e0uation
is1
!h
2
,%(
2
T"
2
= E (B#07#7#-+
in 6hich the three deri/ati/es o. the 6a/e .unction ha/e 3een 6ritten in the standard
a33re/iation as
2
and m has 3een replaced 3y the reduced mass, T7 The eigen/alues
o. this e0uation are deduced in many tets7 They are1
E
Q
=
h
2
Q !Q + #"
%(
2
TR
2
=
h
2
Q !Q + #"
%(
2
:

hQ !Q + #"
in 6a/e num3ers
%(
2
c:
(B#07#7#%+
6here Q is a 0uantum num3er 6hich can ta4e all positi/e integer /alues, includ2
ing Kero7
=sing '0uation (B#07#7#5+ 6e o3tain the e0uation .or the 0uantised /alues o. the
angular momentum as1
#
A
Q
= ZQ !Q + #"\
2
h,2( (B#07#7#$+
The eigen.unctions o. the energy or angular momentum operators are the same
and since this is a pro3lem 6ith spherical symmetry they are almost al6ays epressed
in polar coordinates (Appendi -+7 They are, in .act, the spherical harmonics 6hich
are descri3ed in detail in Appendi 57 There, l is used .or the 0uantum num3er
6hich 6e ha/e called Q here7 The 0uantum num3er m
l
6hich characterises the K2
component o. the angular momentum in spherical harmonic .unctions is called 5
Q
or simply 5 in rotational spectroscopy and 6e should note that e/ery le/el 6ith
total angular momentum characterised 3y Q is (2Q + #"2.old degenerate 6hich has
important implications .or the intensities o. the rotational Lne structure o. the A:
a3sorption 3ands7
82D %.1& Some n;meri#al /ata #on#erning t$e Ai?ration o" t$e
%
HI
')
Cl mole#;le
Fass;ming t$at it ?e$aAes as an $armoni# os#illatorG
The relati/e molecular masses are1
#
9 = #.00-%250 #.?-,5 #0
2-
4g
,5
Cl = ,*.$?%%5, 5%.0?- #0
2-
4g
6hich gi/e ('0uation (#07,75++ a reduced mass, T, o. #.?2?- #0
2-
4g7
2
The e0uili3rium internuclear distance, r
e
, is #2-75 pm and the v = 0 to v =
# transition is .ound at 2$% $-* m
#
6hich corresponds to a .re0uency, >, o. %.$?,0

#0
#,
9K7
'ntering these data in '0uation (#07,7,+ 6ith m replaced 3y T, 6e Lnd a .orce
constant, 4, o. 5#57$ ;m
#
7
The energy o. the lo6est /i3ration energy le/el o. the molecule, E
0
, is
#
h> =
2.$?$5 #0
20
J7
When the 9ICl 3ond is at its maimum (or minimum+ length all this energy
is potential energy so that at this point '0uation (#07,7#+ can 3e used to calculate
|R r
e| ma
, the maimum etension (compression+ o. the 3ond7 We Lnd1
|R r
e
|
ma
=

2E
0
##
4
= #.0-2$
#0

m !B#0.2.#"
This /alue o. |R r
e
|
ma
.or maimum etension (compression+ is :, the ampli2
tude o. the /i3ration, and the percentage change in 3ond length .or this /i3ration, the
Kero2point /i3ration, is :,r
e
= 0.0%* or %7* Y7
The rate o. change o. the internuclear distance, v
:
, is gi/en 3y '0uation (#0727-+
and its maimum /alue 6ill 3e that 6here the cosine .unction ta4es its maimum
/alue o. #707
This 6ill occur 6hen the 3ond length is at its e0uili3rium /alue !R = r
e
",
6hich is the instant at 6hich all the energy is 4inetic energy, the potential energy
3eing
Kero7 Thus1
v
:
!ma" = 2(>: = ?.0*2* #0
,
m s
#
!B#0.2.2"
The rate o. change o. the 3ond length is composed o. t6o terms, the /elocity o.
the hydrogen and chlorine atoms1
v
:
= v
9
+ v
Cl
!B#0.2.,"
Durthermore, in order that the centre o. mass does not mo/e, the motions o. the
t6o atoms must satis.y the e0uation1
v
9
,v
Cl
= m
Cl
,m
9
!B#0.2.*"
With the aid o. '0uation (B#0727,+ 6e can eliminate v
Cl
and o3tain, v
9
= 5.%-,#
#0
,
m s
#
7 The /alue o. v
Cl
is .ound to 3e #.?$2- #0
2
m s
#
7
These are the maimum /elocities achie/ed 3y the t6o atoms in the lo6est /i3ra2
tional state7 They correspond to the situation in 6hich all the /i3rational energy is
4inetic energy and the calculation can 3e chec4ed 3y e/aluating the e0uation1
E
0
=
#
!m
9
v
2
+ m
Cl
v
2
" !B#0.2.5"
2
9 Cl
The results o. the a3o/e calculations .or energy le/els 6ith 0uantum num3ers
v = 0 to 5 are gi/en in the ta3le 3elo67 To emphasise the .act that the 9ICl
molecule is not, in .act, an harmonic oscillator, the actual /alues o. the energy le/els
are gi/en
in the last column o. the ta3le7
2
v E
v
(ho+
(#0
20
J+
:
(#0
##
m+
:,r
e
Y
v
9
(ma+
f
(#0
*
m s
#
+
v
Cl
(ma+
(#0
2
m s
#
+
E
v
(o3s+
(#0
20
J+
0 27$?$ #70-2$ %7* 075%-, #7?$-2 27%??
# %7$0% #7%5%* #*7? #70#-, 27$,#% %7,$,
2 #*7%*- 27,$$2 #%7% #7,#,, ,7-%*$ #,7-#5
, 207-%? 27%,%- 227, #755,$ *7*-%* #%7,%2
* 2?7-25 ,72#%% 2572 #7-?#$ 570-%0 2,7-*5
5 ,27?** ,755%5 2-7$ #7$*-$ 57?#,$ 2%7*55
f
#0
*
m s
#
= 22 ,-*
mph7
;ote ho6 :, the amplitude o. the /i3ration, increases and recall that the .orces 6hich
oppose the compression o. the 3ond are not the same as those 6hich oppose its
etension7 This remo/es the eact proportionality 3et6een potential energy and 3ond
length causing the potential energy cur/e to de/iate .rom the ideal para3olic .orm
o. the harmonic oscillator7 This is mani.ested in the increasing di..erence 3et6een
E!o3s" and E(ho+7
82D %.1' Harmoni# os#illator eigen";n#tions an/ t$e Hermite pol0nomials
The solutions o. SchroM dingerGs e0uation .or the harmonic oscillator are o. the .orm1
G
v
!r " = ;
v
9
v
!

N r " ep!
#
N r
2
" (B#07,7#+
6here r = R r
e
, N = *(
2
T>
c
, h and ;
v
is a normalising constant gi/en 3y1
# #
;
v
= !N ,( "
*
!2
v
vU"

2
The .unctions 9
v
(

N r + are the 9ermite polynomials7 The Lrst .e6 mem3ers o.

the series ha/e the .ollo6ing .orms1
9
0
!

N r " = # 9
#
!

N r " = 2!

N r " 9
2
!

N r " = *!

N r "
2
2
9
,
!

N r " = %!

N r "
,
#2!

N r " 9
*
!

N r " = #?!

N r "
*
*%!

N r "
2
+ #2
9
5
!

N r " = ,2!

N r "
5
#?0!

N r "
,
+ #20!

N r "
2
and G
#2
(r +, 6hich is plotted in Digure #07?, contains 9
#2
!

N r " 6hich
is1 9
#2
!

N r " = *0$?!

N r "
#2
#,5#?%!

N r "
#0
+
#520?*0!

N r "
%
-0$?,20!

N r "
?
+ #,,05?00!

N r "
*
-$%,,?0!

N r "
2
+ ??52%0
There is a particularly use.ul recursion .ormula 6hich ena3les a mem3er o. the
series to 3e calculated .rom the t6o preceding mem3ers7 At is1
9
v +#
!

N r " = 2

N r 9
v
!

N r " 2v9
v#
!

N r "
(B#07,72+
2
=

A. 6e multiply throughout 3y ep!

#
N r
2
" and use '0uation (B#07,7#+ 6e can
Lnd a recursion .ormula .or the harmonic oscillator eigen.unctions1

G
v +#
!r " 2
;
v +#
N r G v!r
"
;
v
2v8
v #
!r "
;
v #
6hich can 3e rearranged to gi/e a result, 6hich 6e Lnd /ery use.ul in Section #0751
rG v!r " = {;
v
,2

!N "}{ZG
v +#
!r ",;
v +#
\ + Z2vG
v #
!r ",;
v #
\}
(B#07,7,+
!R285EMS 62R CHA!TER %.
#7 ConLrm '0uation (#0727,+ 3y di..erentiating '0uation (#07272+ 6ith respect to t and
su3stituting the result into '0uation (#0727#+7
27 =se '0uation (#0727%+ to complete the .ollo6ing ta3le1
Colecule FI9 stretch
a
(m
#
+
:educed mass
*
(atomic mass units+
Dorce constant
(;Hm
#
+
F9
n
"9
2
,?5 200
;9
,
,,, *00
C9
*
2$# *00
a
The 6a/e num3er gi/en is that o. the symmetric stretching, i7e7 the /i3ration in 6hich
all n FI9 3onds etend or contract simultaneously7
*
# a7m7u7 = #.??05 #0
2-
4g7
,7 By epanding the eponential (Bo ,7#+ o. the Corse .unction sho6 that the .orce
constant .or harmonic motion (4 in '0uation (#07,7#++ can 3e epressed as1
4 = 2E
e
a
2
*7 =nder conditions o. lo6 resolution the A: spectrum o. gaseous 9ICl at 25

C
sho6s a /ery strong, 3road a3sorption 3and centered at 2$$0 cm
#
7 =nder high
resolution the 3and can 3e resol/ed into a large num3er o. 3andsP those near the centre
o. the spectrum ha/e the .ollo6ing 6a/e num3ers (cm
#
+1
2$0?.% 2$2-.? 2$*%.* 2$?$.2 ,0#0.% ,0,#.? ,052.* and ,0-,.2.
<ra6 an energy2le/el diagram to interpret these data and calculate the 9ICl 3ond
length7 (Ans6er #2%7? pm+7
Note: -he ex%erimental data a*ove have *een slightly modiCed in order to remove
the small effects of com%licating %henomena 0hich have not *een descri*ed in this
cha%ter7
!ro3lems .or Chapter #0 ,25
57 Dollo6ing the method descri3ed in Section #07%72, 6rite do6n the .unctions
#0
and

0#
.or the /i3rational state o. car3on dioide, 6hich has one 0uantum o. energy
in the 3ending /i3ration >
2
7 By con/erting to plane2polar co2ordinates and .orming
normalised, comple com3inations o.
#0
and
0#
, sho6 that the /i3rational angular
momentum o. the state may 3e characterised 3y the 0uantum num3ers l = #7
?7 An Digure #07#0, the CICl (-+ and CIBr (%+ 3ands o. C9
2
BrCl are approimately e0ual
in intensity 3ut the t6o CIBr 3ands o. C9
2
Br
2
are /ery di..erent7 Suggest 6hy7
Chapter ##
Ele#troni# Spe#tros#op0
##70 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2-
##7# Atomic and molecular or3itals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2%
##72 The spectra o. co/alent molecules . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2$
##727# (

(

transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,2$
##7272 n

(

transitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,,0
##727, Transition2metal complees . . . . . . . . . . . . . . . . . . . . . . . . . . ,,0
##7, Charge trans.er (CT+ spectra . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,,0
##7* Cany2electron 6a/e .unctions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,,2
##75 The #s
#
2s
#
conLguration o. the helium atomP singlet and triplet states . . . . ,,,
##757# The energies o. the #s 2s ecited states o. the helium atom . . . ,,5
##7572 The one2electron energiesP operator
# 2 # 2

2

#

2

2

2,r
#

2,r
2
. . . . . . . . . . . . . . . . . . . . . . . . . ,,5
##757, The t6o2electron, i7e7 electron2repulsion, energyP operator #,r
#2
. . ,,?
##757* The total energies o. singlet and triplet state . . . . . . . . . . . . . . . ,,%
##7575 'lectron repulsion in the triplet and singlet states o. the ecited
helium atom1 a diagrammatic illustration . . . . . . . . . . . . . . . . . . ,,$
##757? Summary o. Section ##75 . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*#
##7? The ( 2electron spectrum o. 3enKene . . . . . . . . . . . . . . . . . . . . . . . . . . ,*#
##7- Selection rules . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,**
##7-7# 'lectron spin (multiplicity+ and transition pro3a3ility . . . . . . . . . ,**
##7-72 Spatial aspects o. transition pro3a3ility .or an allo6ed electronic
transition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*?
##7-7, The /i3rational .actor in the transition pro3a3ility . . . . . . . . . . . ,*-
##7% Slater determinants (Appendi ?+ . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*%
##7$ Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*%
!ro3lems .or Chapter ## . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,*%
%%1. INTR23UCTI2N
'lectronic spectroscopy is the oldest o. the spectroscopies and has played a central role
in the de/elopment o. our understanding o. the structure o. atoms and molecules7 The
6or4 o. Bunsen and >irchho.. in the #%?0s demonstrated that the a3sorption and emis2
sion o. light pro/ided a characteristic 3ar code .or each element 6hich could 3e used .or
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
-2 'lectronic Spectroscopy
0ualitati/e analysis7 Su3se0uent de/elopments ha/e made atomic spectroscopy one o. the
most important 0uantitati/e analytical methods a/aila3le to us7 At the turn o. the cen2
tury, ho6e/er, the sharp line spectra o. atoms 6ere o. central theoretical interest 3ecause
o. the challenge presented 3y their interpretation7 As 6e ha/e seen in Chapter 2, this
puKKle 6as Lnally sol/ed 3y 0uantum mechanics and since that time it has 3een clear
that no real understanding o. the electronic spectra o. atoms or molecules is possi3le
6ithout it7 An the Lrst hal. o. the 20th century technological ad/ances made the system2
atic study o. the electronic spectra o. molecules possi3le and the interpretation o. the
spectra 3ecame intimately lin4ed 6ith the 0uantum2mechanical theory o. the chemical
3ond7
The signiLcance o. electronic spectroscopy in modern science o.ten lies more in its
6ide range o. applications than in the .undamentals o. the su3@ect itsel.7 Thus, the
time scale o. electronic spectroscopy is /ery short (Section %7%+, so it Lnds applica2
tion in measuring the rates o. /ery .ast processes such as photosynthesis7 The transition
pro3a3ility o. electronic transitions can 3e /ery high (Section %7-+ and electronic spec2
troscopy is there.ore a /ery sensiti/e, 0uantitati/e tool in analytical chemistry, 3oth in
direct application and as a detection method in chromatography7 The discrimination and
precision o. electronic spectroscopy has pro/ided much o. our data on the composi2
tion o. etra2terrestrial 3odies and the /elocities at 6hich they are receding .rom us7
These are highly specialised su3@ects 6hich 6e can ta4e no .urther here7 The purpose
o. the remainder o. this chapter is to set out some o. the theoretical concepts 6hich
underlie our current understanding o. atomic and molecular electronic spectroscopy7
Since the 3asic .eatures o. the spectroscopy o. atoms and o. the transition metal ions
ha/e 3een descri3ed in Chapters 5 and - respecti/ely, in this chapter attention 6ill 3e
.ocused on the electronic spectra o. molecules, apart .rom the use o. the helium atom
to illustrate some important principles7 An Sections ##72 and ##7, 6e re/ie6 the ma@or
classes o. such spectra in a purely 0ualitati/e manner7 Dollo6ing that 6e outline the
0uantum2mechanical approach to the 0uantitati/e interpretation o. molecular electronic
spectra7
%%1% AT2MIC AN3 M25ECU5AR 2R8ITA5S
The atomic or3itals o. SchroM dingerGs hydrogen atom (Chapter 5+ and the molecular
or3itals de/eloped soon a.ter6ards 3y 9und and Culli4en (Chapter ?+ ha/e pro/ed to 3e
indis2 pensa3le starting points in the interpretation o. molecular electronic spectra7 The
simplest approach is to identi.y the energy o. an o3ser/ed a3sorption 3and 6ith the energy
di..er2 ence 3et6een the or3ital 6hich the electron initially occupied !$
i
" and the or3ital
6hich it Lnally occupies !$
.
"1
E!i

."
=
E
.

E
i
!##.#.#"
Although, as 6e shall see later, there are .undamental pro3lems 6ith this o/er2simpliLed
/ie6 o. electronic spectroscopy, it has ne/ertheless ser/ed as a use.ul concept on 6hich
to construct a 3road /ie6 o. the types o. electronic spectra 6hich 6e might epect atoms
and molecules to ha/e7 Durthermore, more sophisticated theories almost al6ays 3egin
.rom an or3ital /ie6 point and must return to or3itals 6hen an eplicit calculation o.
a 0uantity, e7g7 a transition pro3a3ility (Sections %7- and ##7-72+ is re0uired to interpret
a spectrum7
The Spectra o. Co/alent Colecules ,2$
%%1& THE S!ECTRA 26 C2VA5ENT M25ECU5ES
As 6e ha/e seen in Section ?7##, the molecular or3itals o. diatomic molecules may
3e descri3ed as ' and ( 3onding, '

and (

anti3onding and non3onding, n, depend2
ing upon the type and phase o. their atomic or3ital o/erlap7 The same essential .ea2
tures may 3e recognised in larger molecules and a generalised energy2le/el diagram
3ased on them can 3e dra6n (Digure ##7#+7 "n the 3asis o. this diagram, in a simple
or3ital /ie6 6e epect that electronic transitions 6ill increase in energy in the order
n

(

(

(

(

'


'

(

'

'

7 This corresponds 6ell 6ith the eperi2

mental o3ser/ations, though transitions in/ol/ing ' and '

or3itals are rarely seen since
they lie in the .ar ultra/iolet, 6ell outside the range o. con/entional la3oratory spec2
trometers 6hich are normally limited to 6a/elengths greater than 200 nm, i7e7 energies
less than

?00 4 J mol

#
or

?7, e87 The /ast ma@ority o. spectra o3ser/ed and used in

chemical applications 6here transition metal ions are not in/ol/ed are there.ore either n

(

, (

(

or charge2trans.er transitions (see Section ##7,+7
%%1&1% ( (

transitions
As .ar as spectroscopy is concerned, the archetypal ( 2electron systems are the linear con2
@ugated polyenes and the aromatic hydrocar3ons7 The 9uM c4el theory (Section #27#+ is
the simplest 6ay o. o3taining the relati/e energies o. the ( 2electron molecular or3itals o.
such molecules7 At is also the starting point .or methods 6hich introduce electron repulsion
into the scheme7 As one 6ould epect .rom the 3eha/iour o. an electron on a ring or in a
3o (Sections ,7, and ,7?+, the spacing o. the energy le/els diminishes as the length o. the
elec2 tronGs path, linear or circular, increases7 An particular, the gap 3et6een the highest
occupied C" (9"C"+ and the lo6est unoccupied C" (L=C"+ decreases, 6hich is
reOected in the electronic spectrum 3y a shi.t o. the lo6est energy a3sorption 3and to
longer 6a/elengths, i7e7 lo6er energiesP
#2
a discussion o. the spectra o. linear con@ugated
molecules appears in Bo ,7?7
The di..erence 3et6een the energies o. the L=C" and the 9"C", as calculated 3y
the 9uM c4el theory, correlates 6ell 6ith the o3ser/ed Lrst a3sorption 3and in the case
o. linear con@ugated systems and 0uite 6ell .or the aromatic hydrocar3ons (Section #27#75,
Digure #27*+7 9o6e/er, the apparent success o. these correlations o6es much to the sim2
ilarity o. the series o. molecules comparedP attempts to impro/e the correlation or etend
the spectral interpretation to other 3ands or other molecules 6as not success.ul7 At 6as
s
p
'nergy
n
p
s
Anti3onding
;on3onding
Bonding
6ig;re %%1% The order o. energy le/els in small co/alent molecules
-* 'lectronic Spectroscopy
soon realised that the pro3lem lay in the lac4 o. eplicit consideration o. electron repulsion
and, 6ith the ad/ent o. computers, a systematic analysis o. the spectra o. the aromatic
hydrocar3ons pro/ided a satis.ying interpretation o. their spectraP this is descri3ed in
detail in Section ##7?7
%%1&1& n (

transitions
By deLnition, n or lone2pair electrons play little or no role in chemical 3onding and
there.ore their energies remain approimately constant .rom molecule to molecule7 They
are close to those in the isolated atom and lie in the energetic centre o. the energy le/el
diagram (Digure ##7#+7 Thus, in a simple or3ital energy /ie6 an n2or3ital constitutes a
9"C" o.
constant energy and the /ariation in the position o. an n

(

transition is a .unction o.
the changing energy o. the (

L=C", 6hich decreases as the length o. the con@ugated
chain increases7 This concept has pro/ided a clear interpretation o. the n (

transitions
o3ser/ed in the spectra o. con@ugated car3onyl compounds7
#2
Core sophisticated analysis
o. such spectra 6as hampered 3y the .act that the n2or3itals could not 3e readily
incorporated into a ( 2electron theory that included electron repulsion7 9o6e/er, later
methods, 3ased upon the same principles 3ut including the ' as 6ell as the ( electrons,
pro/ided a more /ersatile and comprehensi/e interpretation o. the spectra o. organic
molecules7
%%1&1' Transition9metal #omplexes
The interpretation o. the spectra o. the transition metal complees is /ery specialised and
di..ers signiLcantly .rom that o. co/alent molecules in se/eral important respects7 Durther2
more, the theoretical analysis o. the spectra is intimately lin4ed 6ith the eplanation o.
other properties o. these compounds, nota3ly their magnetism7 There.ore, the spectra o.
transition metal complees are discussed in Chapter -, 6hich is de/oted to all aspects o.
the electronic structure o. these compounds7
%%1' CHARE TRANS6ER FCTG S!ECTRA
Cany, though not all, electronic transitions in/ol/e a redistri3ution o. charge7 (But note
that a redistri3ution o. charge is not essential .or a transition dipole moment, Appendi
$7+ ;ormally, electrons mo/e .rom one part o. a molecule to another and the process
is descri3ed as intramolec1lar charge trans.er7 An eample o. this is the comple ion
ZDe
AA
(2,2

23ipyridene+
,
\
2
+
6hich a3sor3s strongly at 522 nm7 (?
=
%-00 l mol

#
cm

#
+7 An
the transition responsi3le .or the a3sorption the electron is trans.erred .rom the .errous iron
atom to the 3ipyridene ligands, lea/ing the iron in the .erric state7 This is a metal2to2ligand
charge trans.er (CLCT+ and such transitions Lnd important applications in analytical chem2
istry on account o. their speciLcity and sensiti/ity7 LCCT transitions are also important,
e7g7 the intense purple o. the ZCn"
*
\

ion7
An etreme cases the charge is essentially trans.erred .rom one molecule to anotherP
intermolec1lar charge trans.er7 A /ery dramatic eample o. this is the 3lood2red solution
produced 6hen a colourless solution o. heamethyl 3enKene is added to a .aintly yello6
solu2 tion o. chloranil7 The electron is trans.erred .rom the chloranil to the heamethyl
3enKene7
Charge Trans.er (CT+ Spectra ,,#
"utside the range o. the human eye are the charge trans.er to sol/ent (CTTS+ transitions o.
some inorganic ions, especially the halide ions7 An these transitions an electron is trans.erred
.rom the halide ion to the 6ater molecules in its immediate /icinity7 This much is agreed,
3ut there remains some uncertainty concerning the eact nature o. the or3ital in 6hich the
electron ends its @ourney7
A. the intensity o. the charge2trans.er 3and o. a solution o. t6o su3stances, an electron
donor < and an electron acceptor A, is studied as a .unction o. the concentrations o. A
and <, it can 3e readily esta3lished that there is an e0uili3rium 3et6een separate A and
< and a 6ea4 comple o. the t6o, A


<
+
, in 6hich there is an apprecia3le trans.er o.
charge .rom < to A1
A
+
<

A


<
+
!##.,.#"
The comple A

<
+
is usually /ery 6ea4ly 3onded and can only 3e isolated in ecep2
tional circumstances7 At is the charge trans.er process itsel. 6hich is responsi3le .or the
sta3ility o. the comple as :7S7 Culli4en pointed out in #$527 A. 6e descri3e the states
on either side o. the a3o/e e0uili3rium 6ith 6a/e .unctions $!A + <" and $!A

<
+
",
then Culli4en proposed that the ground state o. the comple (
g
+ 6ould 3e a state 6hich
6as largely $!A + <" 6ith a small admiture o. $!A

<
+
", 6hile .or the ecited
state !
e
" the re/erse 6ould 3e the case7 9e 6rote the ground and ecited state 6a/e
.unctions as1
and

g
=
cos #

$!A
+
<"
+
sin #

$!A


<
+
" !##.,.2a"

e
= sin # $!A + <" cos # $!A

<
+
" !##.,.23"
=se o. the sine and cosine .unctions as multiplying coe.Lcients ensures that the t6o
6a/e .unctions are orthogonal and normalised, pro/ided that it is assumed that the t6o
3asis .unctions, $!A
+
<" and $!A


<
+
", are also orthonormalP e/en though this is not
usually the case7 Culli4enGs 6a/e .unctions sho6 ho6 the ground state o. the comple
is sta3ilised 3y an admiture o. the charge trans.er state in a 6ay 6hich is essentially
0uantum mechanical7
Culli4en also estimated the energy o. the charge trans.er a3sorption 3and ! E" as the
ionisation energy o. the donor !:
<
" minus the electron a.Lnity o. the acceptor !E
A
" and
other contri3uting terms ! " 6ith an e0uation o. the .orm1
E = :
<
E
A
!##.,.,"
The e0uation predicts that a graph o. E against :
<
.or a series o. donors and a single
acceptor, or the corresponding plot .or a series o. acceptors and a single donor 6ill 3e
a straight line and this is .ound to 3e approimately true in practice7 There are ho6e/er,
considera3le de/iations .rom the epected linearity and slope 6hich are the result o. the
.act that the last term, , also /aries 6ith A and <7 This suggests that 6e eamine it in
a little more detail7
The contri3utions made 3y the ionisation energy and the electron a.Lnity (recall that it
is the uncon/entional 6ay in 6hich electron a.Lnity is deLned 6hich results in it appearing
in this e0uation 6ith the negati/e sign+ are clear7 There are t6o ma@or contri3utions to
7 The Lrst is the Coulom3ic attraction !E
C
" 3et6een the negati/e charge created on the
acceptor and the positi/e charge on the donor7 The second part is the 0uantum mechanical
or resonance sta3ilisation !E
:
", 6hich results .rom the miing o. the t6o 3asis .unctions,
$!A
+
<" and $!A


<
+
" and ma4es
g
lo6er in energy than $!A
+
<" and
e
higher
-? 'lectronic Spectroscopy
E
A
E
C
:
<
8
'
n
e
r
g
y
?
5

e
A

+ <
+
A + e + <
+
*
E
:
,
. (A

<
+
+
2 E
#

g
E
:
0
. (A + <+ A + <
0 2 * ?
A < distance
6ig;re %%1& 'nergy cur/es .or a charge2trans.er comple
than $!A

<
+
"7 9o6 the interaction o. the 3asis states $!A + <" and $!A

<
+
" splits
their energy cur/es apart 6hen the composite states ('0uations (##7,72a+ and (##7,723++ are
.ormed is illustrated in Digure ##727 An its essence this is @ust the same as the sta3ilisation
6hich results 6hen t6o hydrogen atoms com3ine their #s 6a/e .unctions to .orm 3onding,
'
#s
, and anti3onding, '

#s
, molecular
or3itals7
%%1( MANY9E5ECTR2N 4AVE 6UNCTI2NS
The electrons themsel/es ha/e played a rather insigniLcant role in the 3rie. sur/ey o.
electronic spectroscopy a3o/e7 But, 6ith the nota3le eception o. the hydrogen atom
and some ions o. the early mem3ers o. the periodic ta3le, atoms and molecules contain
many electrons each o. 6hich .eels the repulsion o. all the other electrons in the system
(Section 57-+7 These electron2repulsion energies are large and re0uire eplicit considera2
tion7 A. the t6o electrons o. the helium atom are placed opposite each other in the Lrst
Bohr or3it o. the atom, the energy o. the repulsion 3et6een them is *.,5 #0

#%
J or
2.?2

#0
,
4J mol

#
P the energy o. the attraction o. each to the dou3ly charged nucleus
is, o. course, .our times as large7 Although this is a /ery artiLcial model, the energies
determined are o. the same order o. magnitude as those o3tained 3y more sophisticated
calculations (Ta3le ##72+ and, clearly, the repulsion energy cannot 3e ignored7
Since the energy due to interelectronic repulsion is so large, the description o. any one
electron depends upon the positions o. all the others and the 6a/e .unction descri3ing
the electronic state o. an atom or molecule must there.ore 3e a 6a/e .unction 6hich
includes all the electrons7 Thus, the 6a/e .unction o. the helium atom in its ground state,
conLguration #s
2
, must 3e something o. the .orm !9e g7s7"
=
$
#s
L!#"

$
#s
K!2"7 We ta4e
the product, and not the sum, o. the t6o atomic 6a/e .unctions 3ecause 6a/e .unctions
represent pro3a3ilities7 But, as it stands, this is not su.Lcient7 An Section 27% 6e sa6 that
6e cannot ascri3e a tra@ectory or path to an electron and one conse0uence o. this is that
6e cannot Q4eep trac4G o. an electron7 Since 6e cannot .ollo6 an electron along a path
2
6e cannot e/er 3e sure 6hich o. many electrons 6e are o3ser/ingP 6e cannot distinguish
them 6ith a la3el as 6e can identical classical o3@ects7 At is important to understand that
this is a .undamental pro3lem, not a practical one, and our helium atom 6a/e .unction
must there.ore contain the second possi3le 6ay o. assigning electrons # and 2 to or3itals
$
#s
L and $
#s
K , i7e7 $
#s
K!#"

$
#s
L!2"7
We no6 ha/e t6o 6ays o. com3ining these t6o parts o. the 6a/e .unction1

#
or1

+
!9e g7s7"
=

!9e g7s7" =
2
{
$
#s
L!#"

$
#s
K!2"
+
$
#s
K!#"

$
#s
L!2"
}
!##.*.#a"

#
2
{$
#s
L!#" $
#s
K!2" $
#s
K!#" $
#s
L!2"} !##.*.#3"
The t6o results are /ery di..erent7 (The .actor

#
ensures that the 6a/e .unction
remains normalised7+ A. 6e ta4e the positi/e sign the echange o. electrons does not
change the sign o. (9e g7s7+, 3ut i. 6e ta4e the negati/e sign the sign changes1

#
3ut1
!

#2

+
!9e g7s7"
=

#
2
{
$
#s
L!2"

$
#s
K!#"
+
$
#s
K!2"

$
#s
L!#"
} =

+
!9e g7s7"
!

#2

!9e g7s7"
=
2
{
$
#s
L!2"

$
#s
K!#"

$
#s
K!2"

$
#s
L!#"
} =

!9e g7s7"
6here !

#2
is the operator .or the echange o. electrons # and 27 The 6a/e
.unction

+
(9e g7s7+ does not change sign and is said to 3e symmetric 6ith respect to electron
echange 6hile the 6a/e .unction

(9e g7s7+ changes sign and is antisymmetric 6ith
respect to that operation7 &uantum mechanics tells us that 3oth possi3ilities cannot co2
eist in nature, 3ut does not say 6hich one is, in .act, .ound7 9o6e/er, eperiment sho6s
that it is the .unction 6hich is antisymmetric 6ith respect to electron echange,

(9e
g7s7+, 6hich is .ound in our uni/erse and this gi/es rise to a la6 6hich may 3e stated1
Cany2electron 6a/e .unctions are antisymmetric 6ith respect to electron echange7
This is, in .act, @ust another 6ay o. stating the !auli principle 3ecause i. t6o electrons
could occupy the same atomic or3ital 6ith the same spin then1

#

!9e g7s7"
=
2
{
$
#s
L!2"

$
#s
L!#"

$
#s
L!2"

$
#s
L!#"
} =
0
and the 6a/e .unction /anishes7
The .act that atomic and molecular or3itals can 3e occupied 3y not more than t6o
electrons 6ith their spins paired has a pro.ound inOuence upon the structure o. atoms
and molecules and thus upon the 6hole o. chemistry7 At also plays an important role in
electronic spectroscopy and it is this aspect o. the !auli principle 6hich 6e must eamine
in this chapter7 We again use the eample o. the helium atom7
%%1) THE %s
%
&s
%
C2N6IURATI2N 26 THE HE5IUM AT2MK
SIN5ET AN3 TRI!5ET STATES
Though it is not al6ays possi3le, 6e Lnd it /ery con/enient here to separate the electronic
6a/e .unctions o. the #s
#
2s
#
conLguration o. the helium atom into spin and space parts7
Dor the space part, there are t6o 6ays o. descri3ing the assignment o. the t6o electrons,
# and 2, to the t6o atomic or3itals ($
#s
and $
2s
+1
$
#s
!#" $
2s
!2" and $
2s
!#" $
#s
!2"
2
2
Dour com3inations o. the spin .unctions o. the t6o electrons are possi3le1
L!#" L!2" K !#" K!2" L!#" K!2" and K!#" L!2"
As 6e ha/e seen a3o/e, 0uantum mechanics is 0uite adamant a3out the e..ect upon
a 6a/e .unction o. the echange o. identical particles7 A 6a/e .unction must 3e clearly
symmetric or antisymmetric 6ith respect to such an operation7 The t6o space 6a/e
.unctions a3o/e change one into the other and hence ha/e no identiLa3le symmetry in this
respect7 They also imply that 6e can assign a 4no6n electron to a particular or3ital7 Both
these .acts are 0uite unaccepta3le and must 3e remo/ed 3y ta4ing the t6o com3inations1

#
and

+
=


=
2
{
$
#s
!#"

$
2s
!2"
+
$
2s
!#"

$
#s
!2"
}
!##.5.#a"

#
2
{
$
#s
!#"

$
2s
!2"

$
2s
!#"

$
#s
!2"
}
!##.5.#3"

+
is clearly symmetric 6ith respect to electron echange 6hile

is antisymmetric
and these .unctions are potentially accepta3le pro/ided that, 6hen they are com3ined 6ith
accepta3le spin .unctions, the total 6a/e .unction is antisymmetric7 When 6e chec4 the
spin .unctions .or symmetry 6ith respect to electron echange 6e see that the Lrst t6o are
symmetric 6hile the last t6o change one into the other7 We resol/e the pro3lem, as 3e.ore,
3y ta4ing normalised com3inations o. the pro3lem .unctions and o3tain a symmetric (
+
+
and an antisymmetric (

+ spin .unction1

#
+
=


=
2
{
L!#"

K!2"
+
K!#"

L!2"
}
(##7572a+

#
2
{
L!#"

K!2"

K!#"

L!2"
}
(##75723+
We should also note that
+
and

are eigen.unctions o. S

, the operator .or the

total spin angular momentum (Chapter *+, 6hereas L!#" K!2" and K!#" L!2" are
not7
A complete 6a/e .unction .or the #s
#
2s
#
conLguration o. the helium atom must 3e a
product o. a spin .unction and a space .unction, so 6e ha/e eight possi3le .unctions and
the re0uirement .or antisymmetry applies to the total 0ave f1nction, space spin, not to
the indi/idual space or spin parts (i. they can 3e separated as they are in this eample+7 At
is easy to chec4 .or antisymmetry 3ecause the product o. t6o symmetric or t6o antisym2
metric .unctions gi/es a symmetric .unction, 6hereas an antisymmetric .unction results
.rom com3ining a symmetric 6ith an antisymmetric .unction7 The possi3ilities are set
out in Ta3le ##7#7 We Lnd that there is one accepta3le 6a/e .unction (
#
+ .ormed .rom
the symmetric space and the antisymmetric spin part and three accepta3le .unctions (
,
+
.ormed .rom the antisymmetric space and the symmetric spin parts7 The three .unctions
are said to .orm the three components o. a tri%let 6hilst the other .unction is a singlet1
#
=
#
{$
#s
!#" $
2s
!2" + $
2s
!#" $
#s
!2"} {L!#" K!2" K!#" L!2"} (##757,a+
L!#" L!2"
,
=
#
{$
#s
!#" $
2s
!2" $
2s
!#" $
#s
!2"}{L!#" K!2" + K!#" L!2"} (##757,3+
K!#" K!2"
#
2
2 2
Ta?le %%1% The possi3le com3inations o. space and spin .unctions .or the #s
#
2s
#
conLguration o.
the helium atom
Spin 6a/e .unctions Space 6a/e .unctions
Symmetric
+
Antisymmetric

Symmetric
L!#" L!2" , unaccepta3le , accepta3le
# symmetric antisymmetric

=

2
{
L!#"

K!2"
+
K!#"

L!2"
}
K!#" K!2"
Antisymmetric
.unctions .unctions
# accepta3le # unaccepta3le


=

2
{L!#" K!2" K!#" L!2"} antisymmetric symmetric
.unction .unction
Durthermore, recalling our discussion o. angular momentum in Chapter *, it is clear
that the spin .unctions L!#" L!2",

#
{L!#" K!2" + K!#" L!2"} and K!#" K!2" ha/e
K2
components o. spin angular momentum o. +#, 0 and # respecti/ely7 The three symmetric
spin .unctions are there.ore the three components o. a spin system ha/ing a total spin
0uantum num3er, S, e0ual to #7 The singlet is a spin state 6ith S = 07 These t6o states are
the lo6est t6o ecited states o. the helium atom and .rom the point o. /ie6 o. electronic
spectroscopy 6e need to 4no6 their energies7
%%1)1% T$e energies o" t$e %s &s ex#ite/ states o" t$e $eli;m atom
9a/ing deduced the 6a/e .unctions 6hich descri3e t6o o. the ecited states o. the helium
atom 6e should no6 3e a3le to calculate the energies o. the states7 The most signiLcant
contri3utions to the energies are the 4inetic energy, the attraction 3et6een the nucleus
and the electrons and the interelectronic repulsion7 An atomic units (Appendi #+ the
9amiltonian operator is1

2
2 2 #
9

=
2

2

r
#

r
2
+
r
#2
!##.5.*"
An this 9amiltonian the Lrst t6o terms are the operators .or the 4inetic energies o.
electrons one and t6o respecti/ely7 The third and .ourth terms represent the attraction o.
each electron .or the nucleus 6hich has a charge o. +27 The Lrst .our terms each in/ol/e
only one electron and are there.ore o.ten 4no6n as the one+electron terms or operators7
Since r
#2
is the distance 3et6een the electrons, the last term is the interelectronic repulsionP
it is clearly a t0o+electron term7
%%1)1& T$e one9ele#tron energiesK operator

%

%
&

%

&
&

&,r
%

&,r
&
& &
A. electron repulsion is neglected, the electronic energy is that o. t6o electrons occupying
the #s and 2s atomic or3itals o. a hydrogen2li4e atom 6hich has a nuclear charge o.
N = +27 This energy, potential plus 4inetic, is gi/en 3y the .ormula 3elo6, in 6hich N
is the nuclear charge and n the principal 0uantum num3er (Section 575+1
E!N n"
=
2

!N,n"
=
2
{
!*,#"
+
!*,*"
} =
2.5'
9
!9artrees"
# 2 #
n=#2
;ote that the energy is negati/e7 The system is more sta3le than the isolated particles
at rest 6ould 3e7
%%1)1' T$e two9ele#tron< i1e1 ele#tron9rep;lsion< energ0K operator %,r
%&
The triplet 6a/e .unction 6here the t6o electrons ha/e L spin components is1

#
LL
=
2
{
$
#s
!#"

$
2s
!2"

$
2s
!#"

$
#s
!2"
}
L!#"L!2"
!##.5.5"
and the electron repulsion energy integral to 3e e/aluated (':
trip
+ is1
':
trip
=
#
#s 2s
2s #s #2 #s 2s 2s #s
2

$ !#"
$
!2" $ !#"
$
!2"|#,r
|$ !#" $
!2" $ !#"
$
!2"
L!#"L!2"|L!#"L!2"
;ote that the integration implied 3y must 3e carried out .or 3oth electrons and o/er
3oth their space and their spin .unctions7 These t6o types o. integration can 3e separated
3ecause #,r
#2
only operates on the spatial part o. the 6a/e .unction7 We consider the
integration term23y2term7 Ta4ing the Lrst term on the le.t o. the operator 6ith the Lrst on
the right in the a3o/e integral 6e ha/e1
$
#s
!#" $
2s
!2"|#,r
#2
|$
#s
!#" $
2s
!2" L!#"L!2"|L!#"L!2"
= $
#s
!#" $
2s
!2"|#,r
#2
|$
#s
!#" $
2s
!2" L!#"L!#" L!2"L!2"
= $
#s
!#" $
2s
!2"|#,r
#2
|$
#s
!#" $
2s
!2" Q
#s2s
6here the third line .ollo6s .rom the second 3ecause the spin .unctions are ortho2normal
and Q
#s2s
is simply a sym3ol .or the electron repulsion integral 6hich precedes it7 Later,
6e shall gi/e it a numerical /alue7 A. 6e e/aluate the integral .ormed .rom the second
term on the le.t and the second on the right 6e get an etremely similar result, 6ith
electron # no6 in the 2s or3ital and electron 2 in the #s7 Since all electrons are identical,
this term must ha/e eactly the same /alue as the one to 6hich 6e ha/e assigned the
sym3ol Q
#s2s
7 We shall return to gi/e a physical meaning to the integral 6hen 6e ha/e
e/aluated another o. a di..erent .orm7 The Lrst term on the le.t and the second on the
right gi/e the .ollo6ing contri3ution to the integral1
$
#s
!#" $
2s
!2"|#,r
#2
|$
2s
!#" $
#s
!2" L!#"L!2"|L!#"L!2"
= $
#s
!#" $
2s
!2"|#,r
#2
|$
2s
!#" $
#s
!2" L!#"L!#" L!2"L!2"
= $
#s
!#" $
2s
!2"|#,r
#2
|$
2s
!#" $
#s
!2" @
#s2s
The second term on the le.t and the Lrst on the right gi/e a similar result so that 6e
Lnally o3tain1
':
trip
=
#
#s2s #s2s #s2s #s2s #s2s #s2s
2
{
Q
+ Q @ @ } = Q @
!##.5.?"
'actly the same result is o3tained .or the other t6o triplet 6a/e .unctions7 At is
appropriate at this point to attempt to o3tain a physical picture o. the meaning o. these
t6o2electron repulsion integrals7 Q
#s2s
is 0uite straight.or6ard 3ut it may 3e help.ul i. 6e
epress the integral to 3e e/aluated in a more .amiliar .orm1
Q
#s2s
= {$

#s
!#" $
#s
!#"|#,r
#2
|$

2s
!2" $
2s
!2"} dv
#
dv
2
2 #
;ote that the integration has to 3e carried out o/er all three spatial co2ordinates o.
3oth electrons, i7e7 si integrations in total, and the t6o 6a/e .unctions ($
#s
and $
2s
+ and
the distance 3et6een the electrons (r
#2
+ must all 3e epressed in the same co2ordinate
system7 Since the pro3a3ility o. Lnding electron # at a particular point in space is gi/en
3y $
#s

!#"$
#s
!#", 6e ha/e in the epression .or Q
#s2s
the pro3a3ility distri3utions
.or
electrons # and 2, the .ormer in $
#s
and the latter in $
2s
7 The operator is the in/erse
distance 3et6een the t6o electrons7 Thus, the physical interpretation o. the integral is that
6e ta4e the product o. an element o. the distri3ution o. electron # and an element o. the
distri3ution o. electron 2, di/ide 3y the distance 3et6een them and sum up (integrate+
all such terms7 This is eactly the procedure 6e 6ould adopt i. 6e 6ished to calculate
the repulsion o. t6o charge distri3utions in classical electrostatics (Digure ##7,+7 Thus
Q
#s2s
represents a classical Coulom3ic repulsion energy and is there.ore 4no6n as a
Co1lom* integral7
But 6hat o. @
#s2s
J An this integral the distri3utions o. the t6o electrons are not
gi/en 3y the product o. an atomic or3ital .unction and its comple con@ugate 3ut 3y the
product o. one atomic or3ital .unction and the comple con@ugate o. anotherU "nce 6e
ha/e accepted, as 6e must do, that $

#s
(#+$
2s
(#+ also descri3es the spatial distri3ution
o. electron # and $

2s
(2+$
#s
(2+ that o. electron 2, then 6e can /ie6 the integration to
o3tain the contri3ution to the electron repulsion in @ust the same manner as 6e /ie6ed
the calculation o. Q
#s2s
7 The .undamental di..erence lies in the .act that the description
o. an electron distri3ution as a product o. t6o di..erent .unctions is an entirely 0uantum2
mechanical conceptP it has no classical counterpart7 The eistence o. integrals such as
@
#s2s
is one o. the most important reasons .or the di..erence 3et6een the results o.
classical and 0uantum mechanical calculations7 Because it arises as a result o. the .act
that, in 0uantum mechanics, 6e ha/e to allo6 .or the echange o. electrons 3et6een
or3itals, @
#s2s
is usually called an exchange integral7
We can no6 calculate the contri3ution o. electron repulsion to the energy o. the singlet
state7 We ha/e to e/aluate1
':
sing
=
#
#s 2s
2s #s #s 2s 2s #s
*

$ L!#"
$
K!2" $ K!#"
$
L!2" $ K!#"
$
L!2" + $ L!#"
$
K!2"
|#,r
#2
|$
#s
L!#" $
2s
K!2" $
2s
K!#" $
#s
L!2" $
#s
K!#" $
2s
L!2" + $
2s
L!#" $
#s
K!2"
An this integration terms o. eactly the same .orm as the Q
#s2s
and @
#s2s
.ound a3o/e
arise7 But among the #? terms there are others o. a type 6e ha/e not yet encountered7
element o.
density o.
electron 2
r
#2
nucleus
6ig;re %%1' The Coulom3 integral J
#s2s
element o.
density o.
electron #
Dor eample, the Lrst term on the le.t o.
|
#,r
#2
|
and the second on the right gi/e1
$
#s
L!#" $
2s
K!2"|#,r
#2
|$
2s
K!#" $
#s
L!2"
= $
#s
!#"$
2s
!2"|#,r
#2
|$
2s
!#"$
#s
!2" L!#"K !2"|K!#"L!2"
= $
#s
!#"$
2s
!2"|#,r
#2
|$
2s
!#"$
#s
!2" L!#"|K!#" K!2"L!2" = 0
6here the integral /anishes 3ecause the spin .unctions are orthogonal7
The Lnal result .or the electron repulsion energy o. the singlet state is1
':
sing
=
#
#s2s #s2s #s2s #s2s
*
{
*Q
+ *@ } = Q + @
!##.5.-"
%%1)1( T$e total energies o" singlet an/ triplet state
Dortunately, the integrals Q
#s2s
and @
#s2s
are not particularly di.Lcult to e/aluate7 They
depend upon the nuclear charge (N+, 6hich determines the etension in space o. the t6o
spherical atomic or3itals, and are .ound to 3e1
Q
#s2s
= N!#-,%#" = 0.*20 '
9
and @
#s2s
= N!#?,-2$" = 0.0** '
9
Armed 6ith these Lgures 6e can complete the Lrst three ro6s o. Ta3le ##727 At is
immediately clear that, 3ecause @
#s2s
enters the singlet energy epression 6ith a positi/e
sign and the triplet energy epression 6ith a negati/e sign, the calculated energies o. the
t6o states should di..er 3y 2@
#s2s
! E
=
0.0%% '
9
=
0.,%*

#0

#%
J"P the triplet 3eing
the lo6er7 &ualitati/ely, this .act is completely su3stantiated 3y eperiment, though 6e
shall see 3elo6 that a 0uantitati/e comparison eposes a 6ea4ness in our theory7 The
di..erence in energy o. the singlet and triplet states arising .rom the same electronic con2
Lguration is 0uite general and has /ery 6idespread implications7 Since the /ast ma@ority
o. co/alent molecules ha/e all their electrons paired in their ground state they ha/e singlet
ground states7 9o6e/er, the ecitation o. any one o. those electrons can gi/e rise to either
a singlet (spins still paired+ or a triplet (spins parallel+ state, 6ith the triplet state al6ays
2@ lo6er in energy than the singlet7 Since the selection rule strongly .or3ids transitions
3et6een the singlet ground state and a triplet ecited state (Section ##7-+, transitions to
triplet states are much less .re0uent than those to singlet states7 But i. a molecule does
enter a triplet ecited state then its transition to the ground state is .or3idden and it may
remain in the ecited state .or a time that can 3e as long as seconds7 The singlet ecited
state, on the other hand, returns to the ground state in a time o. the order o. #0

$
s7 The
eceptional li.e o. the ecited triplet state o..ers the energy2rich molecule a long time in
6hich to react and much photochemistry proceeds .rom this .act7
Ta?le %%1& The energies o. the #s
#
2s
#
states o. the helium atom
Triplet Singlet
"ne2electron energy
('
9
+
27500
#0
#%
(J+
#07%$$
('
9
+
27500
#0
#%
(J+
#07%$$
Coulom3 energy, Q
#s2s
+07*20 +#7%,# +07*20 +#7%,#
'change energy, @
#s2s
070** 07#$2 +070** +07#$2
Total (sum Lrst three ro6s+ 27#2* $72?0 270,? %7%-?
'perimental energy 27#-5 $7*%- 27#*? $7,?0
Charge correlation
0705# 0722- 07##0 07*%*
A /ery important .act must 3e stressed7 The di..ering energies o. the t6o states 6ith
di..erent electron pairings, singlet (spins antiparallel+ and triplet (spins parallel+ is only
an indirect result o. the di..erent spin pairings7 Because o. the !auli principle the spatial
distri3utions o. the electrons in the t6o states di..erP 3ecause o. that their electron repulsion
energies di..er and hence their total energies di..er7 The singletHtriplet energy di..erence
is not a conse0uence o. a magnetic interaction 3et6een the t6o electrons7 These thoughts
lead us on to consider the last t6o ro6s o. Ta3le ##727
The true energies o. the helium singlet and triplet states can 3e o3tained .rom the
electronic spectrum o. the atom7 The last ro6 o. the ta3le gi/es the di..erence 3et6een
theory and eperiment, 6hich arises as .ollo6s7 Since the electrons are charged they mo/e
such that they 4eep out o. each otherGs 6ay, i7e7 their motions are correlated7 'pressed
in another 6ay, the #s and 2s or3itals o. a t6o2electron atom di..er .rom those o. a one2
electron atom 3ecause the motion o. one electron is modiLed 3y the repulsion o. the other7
We do not .ully allo6 .or this .act 6hen 6e calculate @
#s2s
and Q
#s2s
using $
#s
and $
2s
since these are one2electron or3itals 6ith a Cxed, spherical distri3ution7 A comparison o.
the singlet2triplet energy di..erence (
=
0.02$ '
9
+ and 2 @
#s2s
!
=
0.0%% '
9
" already re/eals
that there is a pro3lem7 This modiLcation o. the electronic motion gi/es rise to the charge
correlation energy, 6hich is the ma@or reason .or the discrepancy 3et6een theory and
eperiment7 ;ote that the correlation energy o. the singlet is approimately t6ice that o.
the triplet7 This is due to the .act that in the triplet state the electrons are already 4ept
more apart than in the singlet, so the e..ect o. correlation is smaller7
%%1)1) Ele#tron rep;lsion in t$e triplet an/ singlet states o" t$e ex#ite/
$eli;m atom
'
: a /iagrammati# ill;stration
The di..ering electron distri3utions 6hich result in the di..ering energies o. the singlet and
triplet ecited states o. helium are illustrated in Digures ##7*(a+ and ##7*(3+7 The .ollo6ing
normalised, singlet and triplet radial .unctions .orm the 3asis o. our plot1

sing
= %{ep!2r
#
" Z# r
2
\ ep!r
2
" + ep!2r
2
" Z# r
#
\ ep!r
#
"} (##757%+

trip
= %{ep!2r
#
" Z# r
2
\ ep!r
2
" ep!2r
2
" Z# r
#
\ ep!r
#
"} (##757$+
Since the atomic or3itals in/ol/ed are spherically symmetrical, the radial co2ordinates
o. the t6o electrons (r
#
and r
2
+ gi/e all the in.ormation 6e re0uire7 To represent the
pro3a3ility o. Lnding an electron at a particular radius (r +, i7e7 in the shell 3et6een r
and r + )r 6hich increases as r
2
, 6e multiply each o. the a3o/e .unctions 3y r
#
and r
2
and s0uare the result7 Thus, the .unctions plotted are {r
#
r
2

sing
}
2
and {r
#
r
2

trip
}
2
7 r
#
is plotted on the /ertical and r
2
on the horiKontal aisP 3oth in atomic units7
Any point on either diagram there.ore represents the momentary situation in 6hich the
distance o. each electron .rom the nucleus is gi/en 3y the pro@ection o. the point upon
the rele/ant aisP the pro3a3ility that such a situation 6ill pertain can 3e determined .rom
'0uations (##757%+ or (##757$+ and ascri3ed to each point7 A. su.Lcient point pro3a3ilities
are calculated .or any particular atomic state a set o. contours may 3e dra6n, as sho6n
in the Lgures7 The most nota3le di..erence 3et6een the t6o Lgures is the Kero pro3a3ility
along the r
#
= r
2
line in the triplet in contrast to the mar4ed pea4 at r
#
= r
2
0.5 a
o
in
the singlet7 Clearly, the pro3a3ility that r
#
= r
2
is much higher in the case o. the singlet,
6hich accounts .or the higher electron repulsion in that state7 ". course, t6o electrons
Singlet
070*
070%
07#2
07#?
07#2
070%
07#?
070*
Triplet
070*
070%
07#2
07#?
0720
070%
07#?
0720 07#2
070*
r
#
(
a
o
+
r
#
(
a
o
+
?
5
*
,
2
#
0
0 # 2 , * 5 ?
r
2
(a
o
+
(a+
?
5
*
,
2
#
0
0 # 2 , * 5 ?
r
2
(a
o
+
(3+
6ig;re %%1( 'lectron distri3ution in the #s
#
2s
#
singlet and triplet states o. helium
The ( 2electron Spectrum o. BenKene %5
ha/ing the same /alue o. their radial co2ordinate can reduce their mutual repulsion 3y
mo/ing in such a 6ay that they are positioned on opposite sides o. the nucleus7 And in the
real atom that is 6hat they do7 But this ang1lar correlation cannot ta4e place in our simple
mathematical model 3ecause our or3itals are deLned to 3e spherically symmetrical and
do not permit a non2spherical electron distri3ution7 To introduce an element o. angular
correlation 6e 6ould ha/e to use p2or3itals in our 6a/e .unctions7 Calculations using
p2or3itals do indeed result in a reduction in energy7
At is also possi3le to include the correlation energy in a more eplicit manner, @ust as
James and Coolidge did .or the hydrogen molecule (Section ?7%+7
%%1)1* S;mmar0 o" Se#tion %%1)
The reader may .eel that the arcane pro3lem o. the ecited states o. the helium atom has
recei/ed .ar too much attention in the preceding paragraphs7 At is true that the pro3lem
is not one 6ith 6hich many chemists are concerned, 3ut it does raise a num3er o. /ery
important points 6hich may 3e summarised as .ollo6s1
#7 An 0uantitati/e 6or4 it is not su.Lcient to consider that the energy o. an ecited state
is gi/en simply 3y the di..erence in energy 3et6een t6o or3itals, molecular or atomic7
'lectron repulsion terms are /ery large and must 3e ta4en into account7
27 Because o. the inOuence o. electron spin on electron spatial .unctions, i7e7 the !auli
principle, electron repulsion in a triplet state is al6ays some6hat less than in the
corresponding singlet state7 There.ore, the energy o. the triplet state is al6ays lo6er,
as 9und Lrst noted7
,7 The energy di..erence 3et6een singlet and triplet is due to electron repulsion7 At is
there.ore /ery much larger than any energy 6hich might arise 3ecause o. a direct
interaction o. the electron spins through their magnetic properties7
*7 The .act that singlet2triplet transitions are strictly .or3idden (in molecules 6here spin2
or3it coupling is small+ means that, once created, triplet states can ha/e a /ery long
li.etime 6hich is important in photochemistry7
%%1* THE ( 9E5ECTR2N S!ECTRUM 26 8EN:ENE
The ( (

electronic spectrum o. 3enKene pro/ides a good illustration o. the 6ay in
6hich interelectronic repulsion a..ects the spectra o. systems o. more general chemi2
cal interest7 The 9uM c4el molecular or3ital theory o. the ( 2electron structure o.
3enKene (Section #27#+ gi/es an energy2le/el scheme .or the molecule in 6hich 3oth the
highest occupied C"s and the lo6est unoccupied C"s are a degenerate pair (Digure
##75+7 Core
sophisticated theories gi/e the same result since the ( 2electron energy le/el pattern is
determined 3y symmetry7 The .orms o. the si molecular or3itals, in order o. increasing
energy (K is a negati/e 0uantityU+, are1

G
#
= {
#,
#
?
}{
$
#
+
$
2
+
$
,
+
$
*
+
$
5
+
$
?
}
E
=
L
+
2K
G
2
= {
2
}{
$
2
+
$
,

$
5

$
?
}
E
=
L
+
K 9"C"

+#H?
#H?
#H?
6
+2H#2
+#H?
+#H?
#H?
0
#H#2
#H#2
4
+2H#2
#H#2
#H#2
+#H2
#H2
#H2
5
+#H2
0
+#H#2
+2H#2
3
+#H#2

0
#H2
2
+#H2
#H#2 #H#2
2H#2

)#H?
#H2
+#H2
0
)#H?
)#H?
1
)#H?
)#H?
)#H?
6ig;re %%1) ( 2electron energy le/els and molecular or3itals .or 3enKene

G
,
= {
#,

G
*
= {
#,
#
#2}{2$
#
+ $
2
$
,
2$
*
$
5
+ $
?
} E = L + K 9"C"
#2}{2$
#
$
2
$
,
+ 2$
*
$
5
$
?
} E = L K L=C"
G
5
= {
2
}{
$
2
+
$
,

$
5
+
$
?
}
E
=
L

K L=C"

G
?
= {
#, ?
}{
$
#

$
2
+
$
,

$
*
+
$
5

$
?
}
E
=
L

2K
An a simplistic /ie6 there.ore, the spectrum o. 3enKene at lo6er energies 6ould con2
sist o. .our transitions .rom the t6o 9"C"s to the t6o L=C"s, all ha/ing the same
energy7 The eperimental Lnding (Digure ##7?+, ho6e/er, 3ears no relation to this predic2
tion7 Three singlet 3ands are seen 6ith maima at approimately 25? nm (,% 000 cm

#
+,
200 nm (*% 000 cm

#
+ and #%0 nm (5* 500 cm

#
+P the last is dou3ly degenerate7
9o6
does this ariseJ The discrepancy is directly attri3uta3le to the e..ect o. electron repulsion
on the energy le/els o. the molecule, 6hich is 3est considered in t6o stages7 Dirst, as 6e
ha/e seen a3o/e (Section ##75+, the energy o. an ecited electronic state depends not only
upon the energies o. the or3ital the electron lea/es and that 6hich it enters 3ut also on
the Coulom3 and echange integrals 3et6een those or3itals7 An a general .ormulation
2
6e
6rite the energy di..erence 3et6een an ecited singlet state (
#

i 4
+, in 6hich an electron

nm m
#
S,, S*
S2
S#
T#
#%0 h575 #0
?
200 h*7% #0
?
25? h,7% #0
?
,*5 h27$ #0
?
S0
The dashed and solid /ertical lines indicate
.or3idden and allo6ed transitions respecti/ely7
6ig;re %%1* The ( 2electron spectrum o. 3enKene
has 3een promoted .rom molecular or3ital
i
to
4
, and the ground state (
#

0
+ as1
# # # #
E!
#

i 4
"
=

|
9

|



|
9

|

=
E
E
Q
+ 2@
!##.?.#"
i4
i4 0 0 4 i i4 i4
6here E
i
and E
4
are the molecular or3ital energies, 6hich also contain electron2repulsion
terms, and Q
i4
and @
i4
are the corresponding Coulom3 and echange integrals7 The
e/aluation o. the energy di..erence ('0uation (##7?7#++ is di.Lcult, 3ut 3y ma4ing a series
o. @ustiLa3le approimations in the calculation o. all the electron2repulsion terms the
.ollo6ing energies may 3e determined1
and
E!
#

2
E!
#

2
*
" = E!
#

, 5
5
" = E!
#

, *
" = 5.$2, e8
" = ?.#2- e8
These results sho6 immediately that the .our transitions do not all ha/e the same
energy7 And there is a second e..ect o. electron repulsion 6hich 6e must ta4e into
account7 The states |
#

i 4
are not eigen.unctions o. the 9amiltonian operator (9

+,
6hich includes electron2repulsion terms, and this causes a miing o. the states through
o..2diagonal matri elements (Appendi ,+, 6hich may 3e calculated using the .ormula
2
1
# #


i4
|
9

|

@l

= 2
@
!#"
4
!2"|#,r
#2
|
l
!#"
i
!2"
@
!#"
4
!2"|#,r
#2
|
i
!#"
l
!2" (##7?72+
=sing the same approimate electron2repulsion terms as 3e.ore 6e calculate that1
# # # #


2*
|
9

|

,5
=
#.02, e8 and


,*
|
9

|

25
=
0.%#% e8
All other o..2diagonal terms are .ound to 3e Kero7 We can no6 set up an energy matri
(Appendi ,+ .or the interaction o. the .our lo6est ( 2electron ecited states o. 3enKene7
#
57$2, #702, 070 070
#
#702, 57$2, 070 070
#
070 070 ?7#2-
07%#%
# # #

#

#

#

#
#
At is1
9

He8 |
#

2

2*
|


,5
|


,*
|
#
*
|

,5
|
,

*
|
2

5


25
|
070 070

07%#% ?7#2-
We can diagonalise the t6o 2 2 su32matrices separately to o3tain the .ollo6ing .our
energies7 Since the interactions occur only 3et6een states 6ith e0ual on2diagonal matri
elements 6e readily Lnd1

#
B
2u
!L
#
L
3
"P
# #
2
{
2 *


,5
}
E
=
5.$2,

#.02,
=
*.$0 e8

,$ 500 cm

#
#
B
#u
!p
#
L
a
"P

# #
2
{
, *
+

25 } E = ?.#2- 0.%#% = 5.,# e8 *, 000 cm

#
#
'
#u
!K
#
B"P
# #
2
{
2

*
+

,5
}
E
=
5.$2,
+
#.02,
=
?.$5 e8

5? 000 cm

#
#
'
#u
!K

#
B"P
# #
2
{
, *


25
}
E
=
?.#2-
+
0.%#%
=
?.$5 e8

5? 000 cm

#
The sym3ols
#
B
2u
etc7 are the symmetry la3els o. the statesP L, p, K and K

are la3els
.or the 3ands proposed 3y '7 ClarP and
#
L
a
,
#
L
3
and
#
B are those proposed 3y
J7:7 !latt7 All are 6idely used 3y practical spectroscopists7 These results are in
reasona3le, 0uantitati/e agreement 6ith eperiment7 They illustrate the magnitude o.
the electron repulsion energy and 3ear 6itness to the .act that no satis.actory interpretation
o. electronic spectra is possi3le 6ithout ta4ing it eplicitly into account7 Currell
2
has gi/en
a detailed description o. the methods outlined a3o/e .or the interpretation o. the spectra
o. 3enKene, the aromatic hydrocar3ons and other ( 2electron systems7
%%1+ SE5ECTI2N RU5ES
=nder conditions o. high resolution, a3sorption o. light, 6hich results in a change o.
electronic state accompanied 3y a Lne structure due to changes in /i3rational and rotational
0uantum num3er, may 3e o3ser/ed in gas2phase molecules7 The detailed analysis o. this
structure has pro/ided much /alua3le in.ormation a3out the geometry o. small molecules
in their ecited electronic states7 9o6e/er, in general chemical spectroscopy, 6hich is
usually per.ormed on samples in solution, only /i3rational Lne structure is resol/edP and
that only in a small percentage o. samples7 There.ore, 6e shall conLne our attention here
to the selection rules .or electronic transitions and the associated /i3rational Lne structure7
Consider Lrst the e..ect o. electron spin on transition pro3a3ility, using the helium atom
as an eample7
%%1+1% Ele#tron spin Fm;ltipli#it0G an/ transition pro?a?ilit0
An Section ##7* ('0uation (##7*7#3++ 6e .ound that the correct 6a/e .unction .or the
helium atom in its ground electronic state, 6hich is a singlet state, is1

#

i
=
2
{
$
#s
L!#"

$
#s
K!2"

$
#s
K!#"

$
#s
L!2"
}
!##.-.#"
= {$
#s
!#"$
#s
!2"}

#
2
{
L!#"K !2"

K!#"L!2"
}
Selection :ules %$
#
#
# #
#
The superscript Q#G has 3een introduced to indicate the singlet state and the su3script
QiG 3ecause it .orms the initial state in a spectroscopic transition7 The corresponding 6a/e
.unctions .or ecited states in 6hich an electron has 3een promoted .rom a # s to a 2p
or3ital (compare '0uations (##757,++ are1
#

.
=
2
{
$
#s
!#"

$
2p
!2"
+
$
2p
!#"

$
#s
!2"
}
2
{
L!#"

K!2"

K!#"

L!2"
}
(##7-72a+
,

.
=
2
{$
#s
!#" $
2p
!2" $
2p
!#" $
#s
!2"}
L!#" L!2"
2
{L!#" K!2" + K!#" L!2"} (##7-723+
K!#" K!2"
6here '0uation (##7-72a+ is the singlet and '0uation (##7-723+ the triplet7
# # ,
As an eample 6e shall e/aluate the transition moments
.
|"

|
i
and
.
|"

|
#

i
6here
"

= e!r
#
+ r
2
" (Appendi $+ paying particular attention to the inOuence
o. the electron spins7 Dor the singlet ecited state1
# #
"
S
=
e


.
|
r
#
+
r
2
|

i


#
=
e
2

$
#s
!#"

$
2p
!2"
+
$
2p
!#"

$
#s
!2"
|
r
#
+
r
2
|
$
#s
!#"$
#s
!2"

#

2

L!#"K !2"

K!#"L!2"
|
L!#"K !2"

K!#"L!2"

We can e/aluate the space and spin parts o. " separately and .or the space part 6e Lnd1
= $
#s
!#"|r
#
|$
#s
!#" $
2p
!2"|$
#s
!2" + $
2p
!#"|r
#
|$
#s
!#" $
#s
!2"|$
#s
!2"
+ $
2p
!2"|r
2
|$
#s
!2" $
#s
!#"|$
#s
!#" + $
#s
!2"|r
2
|$
#s
!2" $
2p
!#"|$
#s
!#"
= 0 + $
2p
!#"|r
#
|$
#s
!#" + $
2p
!2"|r
2
|$
#s
!2" + 0 3ecause $
m
!#"|$
n
!#" = )
mn
= 2 $
2p
!#"|r
#
|$
#s
!#" 3ecause all electrons are identical7
The integration o/er spin gi/es1
L!#"|L!#" K!2"|K!2" L!#"|K!#" K!2"|L!2"
K!#"|L!#" L!2"|K!2" + K!#"|K!#" L!2"|L!2"
= # 0 0 + # = 2
We Lnally ha/e1

# #

"
S
=
e
2

2

$
2p
!#"
|
r
#
|
$
#s
!#"

2

2
=
e 2

$
2p
!#"
|
r
#
|
$
#s
!#"

Dor the triplet Lnal state1
, #
"
T
=
e


.
|
r
#
+
r
2
|

i


=
e
2

$
#s
!#"

$
2p
!2"

$
2p
!#"

$
#s
!2"
|
r
#
+
r
2
|
$
#s
!#"$
#s
!2"

#

2

L!#"K !2"
+
K!#"L!2"
|
L!#"K !2"

K!#"L!2"

*
The space part o. the integral gi/es1
= $
#s
!#"|r
#
|$
#s
!#" $
2p
!2"|$
#s
!2" $
2p
!#"|r
#
|$
#s
!#" $
#s
!2"|$
#s
!2"
+ $
2p
!2"|r
2
|$
#s
!2" $
#s
!#"|$
#s
!#" $
#s
!2"|r
2
|$
#s
!2" $
2p
!#"|$
#s
!#"
= 0 $
2p
!#"|r
#
|$
#s
!#" + $
2p
!2"|r
2
|$
#s
!2" 0 = 0
Durthermore, the spin part o. the integral also gi/es Kero since1
L!#"|L!#" K!2"|K!2" L!#"|K!#" K!2"|L!2"
+ K!#"|L!#" L!2"|K!2" K!#"|K!#" L!2"|L!2"
= # 0 + 0 # = 0
There.ore, on 3oth counts 6e Lnd that the singlet triplet transition is .or3idden
and 6e can say that, pro/ided that spin2or3it coupling can 3e neglected, any transition in
6hich there is a change o. multiplicity is .or3idden7 At is not al6ays possi3le to separate
the space and spin .unctions as 6e ha/e done here, 3ut the result is 0uite general and can
3e demonstrated using appropriate Slater determinants (Section ##7% and Appendi ?+ as
6a/e .unctions7
%%1+1& Spatial aspe#ts o" transition pro?a?ilit0 "or an allowe/
ele#troni# transition
To proceed .urther 6ith the spatial aspects o. molecular transition moments 6e 3uild upon
the discussion o. transition pro3a3ility in Appendi $ and Sections %7? and %7-7 The case
o. an allo6ed electronic transition, 6hich may or may not 3e accompanied 3y changes
in /i3rational le/els, is Case 2 o. the discussion in Section %7-7# 6here 6e ha/e deduced
that the transition dipole moment ("
i.
+ is gi/en 3y '0uation %7-7#0 6hich 6e repeat here
.or con/enience1
"
i.
=
G
.
/i3
|
G
i
/i3

"
0
!e
.
e
i
"
!##.-.,"
"
0
(e
.
e
i
+ is the /alue o. the integral G
.
elec
|"

|G
i
elec
e/aluated at the
e0uili3rium
nuclear conLguration7
"

is the dipole moment operator and it is important to note that

the integral etends o/er the electronic co2ordinates only7 The integral

G
.
/i3
|
G
i
/i3

is the
o/erlap o. the /i3rational 6a/e .unctions o. the initial and Lnal states, 6hich is important
in the analysis o. the /i3rational structure o. small molecules 3ut rarely in the spectra o.
large molecules7
To illustrate the calculation o. the electronic matri element 6e ta4e the case o. the
transition .rom a highest occupied (9"C"+ to a lo6est unoccupied (L=C"+ ( 2electron
molecular or3ital o. 3enKene7
The ( 2electron coe.Lcients o. the C"s G
2
and G
5
are sho6n in Digure ##7-7 The
y2component o. the transition moment integral, -
y
, 3et6een these t6o or3itals is1

G
2
|

0
4
y
4 |
G
5
=
e

#
!$
2
+
$
,

$
5

$
?
"
|
y
2
+
y
, +
y
5 +
y
? |
#
!

$
2
+
$
,

$
5
+
$
?
"
2 2
4
6here e is the electronic charge7 Since the atomic or3itals ($
i
+ are normalised, i. 6e
neglect o/erlap, i7e7 assume that $
i
|$
@
= )
i@
, 6e can separate the integral into .our parts
and 6rite1
-
y
=
#
e{ $
2
|y
2
| $
2
+ $
,
|y
,
|$
,
+ $
5
|y
5
| $
5
+ $
?
|y
?
|$
?
}
2
2

occupied C"
unoccupied C"
0
0
R
#
c
? 2
+c
+c c
2 5
5
,
c
*
0
+c
c
+c
F
0
electron transition density
0
m
m
25
+m
+m
0
6ig;re %%1+ The electron transition density .or a ( (

transition in 3enKene
A. the co2ordinate origin is the centre o. the ring then y
2
= y
?
= y
,
= y
5
and i. 6e
set y =
#
:
y
, 6here : is the CIC 3ond length and the su3script indicates that the moment
lies in the y2direction, then1
-
y
=
#
e
{
$
2
|
#
:
y
|
$
2
+
$
,
|
#
:
y
|
$
,
+
$
5
|
#
:
y
|
$
5
+
$
?
|
#
:
y
|
$
?
} * 2 2 2 2
# # #
=
*
e
{
*

2
:
y
} =
2
e:
y
An de/eloping the a3o/e epression .or -
y
6e ha/e assumed that the ( 2electron tran2
sition density in the region o. each car3on atom 4, $
4
|$
4
, is located at the position
o. the atomic nucleus7 A similar e/aluation o. -

.or the 2 5 transition results in a
transition moment o. Kero in that direction7 Dor the , * transition 6e Lnd -
y
= +
#
e:
y
and -

= 07 An the pre/ious section 6e .ound that t6o o. the Lnal 3enKene ecited states
(
#
B
#u
and
#
'
#u
+ 6ere .ormed .rom the sum and di..erence o. the states
#

,
*
and
#

2 5
respecti/ely, so that .or the transition to
#
B
#u
the transition moment is proportional to
# # #
+
2
e:
y

2
e:
y
= 0, i7e7 the transition is .or3idden7 But .or the transition to '
#u
the tran2
sition moment is proportional to
+
#
e:
y
!

#
e:
y
"
=
e:
y
, i7e7 the transition is allo6ed7
2 2
To o3tain an a3solute /alue .or the transition moment in the y2direction 6e 6ould need
to e/aluate e:
y
at the e0uili3rium nuclear conLguration and the /i3rational o/erlap inte2
gral, 6hich is discussed in the .ollo6ing Section7 9o6e/er, such calculations are rarely
per.ormed 3ecause the 0uality o. the electronic 6a/e .unctions seldom @ustiLes more
than a semi20uantitati/e estimate o. the transition moment, the most /alua3le in.ormation
3eing the direction o. the moment, 6hich is usually /ery easy to Lnd and in the case o.
symmetrical molecules is possi3le using group theory alone7
%%1+1' T$e Ai?rational "a#tor in t$e transition pro?a?ilit0
The /i3rational .actor ( G
.
/i3
|G
i
/i3
+ in "
i.
has 3een discussed in Section %7- and Bo
%72 and 6ill not 3e ta4en .urther here7 We simply note that the Dranc4 I Condon
principle applies to the /i3rational structure o. polyatomic molecules, @ust as it does to
diatomics, though the analysis is naturally more complicated7 The calculation o.
/i3rational o/erlap
integrals presents .ormida3le pro3lems, not the least o. 6hich is the necessity o. 4no6ing
the ground and ecited state potential sur.aces7 Such calculations ha/e rarely 3een carried
out and then only on molecules much smaller than 3enKene7 An the particular case o. 3en2
Kene, the y2polarised transition .or 6hich a non2Kero transition moment 6as .ound a3o/e
is one o. the pair 6hich ta4e the molecule to the
#
'
#u
state7 The other mem3er o. the pair is
2polarised7 The high symmetry o. the molecule is responsi3le .or the .act that the transi2
tions to the t6o states o. lo6est energy (
#
B
#u
and
#
B
2u
+ are .or3idden7 9o6e/er,
/i3rations 6hich remo/e this symmetry 3y distorting the ring can ma4e the transitions
allo6ed as descri3ed under Case , o. Section %7-7#7 Both o. these .or3idden 3ands sho6
/i3rational Lne structure 6hich has 3een studied in detail7 Currell gi/es an account o.
this 6or47
2
%%1, S5ATER 3ETERMINANTS FA!!EN3ID *G
At is clear that there are nU (.actorial n+ 6ays o. placing n electrons in n or3itals so that
the proper description o. a many2electron atom or molecule leads to a /ery complicated
6a/e .unction7 Slater sho6ed that a many2electron 6a/e .unction 6ith all the re0uired
antisymmetry could 3e 6ritten most concisely in the .orm o. a determinant7 We shall not
6or4 6ith SlaterGs methods hereP Appendi ? contains a 3rie. introduction7 The principal
reason .or mentioning Slater determinants here is to emphasise that only a many2electron
6a/e .unction, 6hich may 3e 6ritten as a single Slater determinant or as a sum o. such
determinants, is an ade0uate description o. an atom or molecule as .ar as its electronic
spectrum is concerned7
%%1- 8I85I2RA!HY AN3 6URTHER REA3IN
The material in Section ##75 o6es a great deal to J7W7 Linnett7 Dor an ecellent discussion
and illustration o. electron repulsion and correlation in the helium atom see his 3oo47
,
At is un.ortunate that there appear to 3e /ery .e6, i. any, modern treatments o. the theory
o. the electronic spectra o. molecules7 The sources # I 2 and * I ?, ho6e/er, present
/ery thorough discussions o. the topic and contain all the essential details7
#7 S7D7 Cason, 31arterly Revie0s of the Chemical Society, %), 2%- (#$?#+7
27 J7;7 Currell, -he -heory of the Electronic S%ectra of 4rganic 5olec1les, Cethuen, London,
#$?,7
,7 J7W7 Linnett, Wave 5echanics and Valency, Cethuen, London, #$?07
*7 9797 Ja..eb and C7 "rchin, -heory and A%%lications of Ultraviolet S%ectrosco%y, Wiley,
;e6
Ror4, #$?27
57 C7 Sandor.y, Electronic S%ectra and 31ant1m Chemistry, !rentice 9all, 'ngle6ood Cli..s, #$?*7
?7 G7 9erK3erg, Electronic S%ectra of Polyatomic 5olec1les, 8an ;ostrand, ;e6 Ror4, #$??7
<etails concerning the e/aluation o. one2 and t6o2electron matri elements 3et6een 6a/e .unctions
epressed as Slater determinants are gi/en 3y
-7 :7 <audel, :7 Le.e3/re and C7 Coser, 31ant1m Chemistry, Anterscience, ;e6 Ror4, #$5$7
!R285EMS 62R CHA!TER %%
#7 ConLrm '0uation (##757-+ .or the electron2repulsion energy o. the singlet state o. the
ecited helium atom7
2
!ro3lems .or Chapter ## ,*$
27 An Section ##7-7# the transition pro3a3ility .or the transition .rom
#

i
to
,

.
in the
helium atom is calculated using the .unction

#
{L!#"K !2" + K!#"L!2"} as the spin
.unction .or the ecited state7 :epeat the calculation using the spin .unction L!#"L!2"7
,7 Dollo6ing the calculation o. transition moments .or 3enKene in Section ##7-72, calcu2
late the transition dipole moments .or the , 5 and 2 * transitions7
*7 ConLrm, .ollo6ing the calculation in Section ##7-72, that the inclusion o. o/erlap
terms in the calculation o. the transition dipole moment o. 3enKene results in a small
contri3ution to -
y
6hich opposes that due to the other terms7
57 The electronic spectrum o. the 3romide ion in acetonitrile sho6s t6o a3sorption 3ands
at energies corresponding to *5 $00 cm

#
and *$ ,00 cm

#
7 The iodide ion gi/es 3ands
at *0 %00 cm

#
and *% 500 cm

#
7 These 3ands ha/e 3een assigned to charge trans.er
.rom the halide ion to the sol/ent7 'plain 6hy t6o CT 3ands are seen and sho6
that this assignment is in agreement 6ith the .act that the 3ands o. lo6est energy
in the atomic spectra o. 3romine and iodine are .ound at ,?%5 cm

#
and -?0, cm

#
respecti/ely7
Z9int1 What is the lo6est energy state (i7e7 ground electronic state+ o. a halogen
atom and 6hat separates it .rom the state net highest in energyJ A. necessary, see
Section 57$ .or .urther in.ormation7\
?7 The ( (

a3sorption 3and o. ethene (9
2
C
=
C9
2
+ is .ound at < = #?2 nm 3ut it
mo/es a .e6 nanometres to longer 6a/elengths 6hen the planarity o. the molecule is
remo/ed 3y t6isting a3out the dou3le 3ond, usually 3y steric e..ects7 At is di.Lcult to
separate the e..ect o. the t6isting .rom that o. the su3stituent groups causing it, 3ut
6e can estimate the .ormer in the .ollo6ing 6ay7
Gi/en that the ( 2electron molecular or3itals o. ethene as calculated 3y the 9uM c4el
method (Section #27#+ are (
=

#
{
$
#
+
$
2
}
and (

=

#
{
$
#

$
2
}
, determine their
2 2
energies 3y calculating

(
|
9

|
(

and

(

|
9

|
(

using the 9uM c4el approimationsP

$
#
|
9

|
$
#
=
$
2
|
9

|
$
2
=
L and

$
#
|
9

|
$
2
=
$
2
|
9

|
$
#
=
K 7 ZE!( "
=
L
+
K and
E!(

"
=
L

K \7 Con/ert the /alue o. < to energy and .rom that Lgure determine
K 7 (We sho6 in Section #27# that this primiti/e approach to the calculation o. a3sorp2
tion energies, neglecting electron repulsion, can 3e 0uite success.ul e7g7 Digure #27*+7
There is a 6ell2esta3lished relationship .rom 6hich the /alue o. K at a particular angle
(K
#
+ can 3e calculated .rom its /alue at #
=
07 At is1
K
#
= K
o
cos!# "
;o6, assuming that nothing apart .rom K changes, calculate the shi.t in the a3sorp2
tion maimum 6hich results .rom a t6ist o. #0

7 Rou should Lnd a /alue o. approi2

mately 2 nm7
Chapter #2
Some Spe#ial Topi#s
#270 Antroduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,52
#27# The 9uM c4el molecular or3ital (9C"+ theory . . . . . . . . . . . . . . . . . . . .
.
,52
#27#7# The 3asis o. 9uM c4elGs approach . . . . . . . . . . . . . . . . . . . . . .
.
,52
#27#72 The method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,5,
#27#7, 9uM c4elGs assumptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
.
,5*
#27#7* <etermination o. 9C" energies and A" coe.Lcients . . . . . . . . . ,5*
#27#75 Applications o. 9C" energies . . . . . . . . . . . . . . . . . . . . . . . . ,5-
#27#7? Applications o. 9C" coe.Lcients . . . . . . . . . . . . . . . . . . . . . . ,?#
#27#7- Some Lnal comments on the 9uM c4el theory . . . . . . . . . . . . . . .
.
,?2
#272 Cagnetism in chemistry . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,?,
#2727# Cagnetic suscepti3ility1 diamagnetism and paramagnetism . . . . . . ,?*
#27272 Cagnetic suscepti3ility1 .erromagnetism and anti.erromagnetism . . ,?5
#2727, Cagnetic Lelds and dipoles1 some deLnitions . . . . . . . . . . . . . . ,?5
#2727* The magnetic e..ect o. electronic or3ital motion . . . . . . . . . . . . . ,??
#27275 The conse0uences o. chemical 3onding . . . . . . . . . . . . . . . . . . ,?%
#2727? The magnetic e..ect o. electron spin . . . . . . . . . . . . . . . . . . . . ,?$
#2727- Cagnetism in practice . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,-0
#2727% Systems o. interacting molecular magnets . . . . . . . . . . . . . . . . . ,-*
#2727$ A note o. 6arning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,-?
#2727#0 An application . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,--
#27, The 3and theory o. solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,-%
#27,7# The tight 3inding approimation . . . . . . . . . . . . . . . . . . . . . . . ,-%
#27,72 The electron I gas (.ree2electron+ approimation . . . . . . . . . . . . . ,%#
#27,7, Colecular and ionic solids . . . . . . . . . . . . . . . . . . . . . . . . . . . ,%?
#27,7* Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,%-
#27,75 Cetals, insulators and semiconductors . . . . . . . . . . . . . . . . . . . ,%-
#27,7? "ptical properties o. solids . . . . . . . . . . . . . . . . . . . . . . . . . . ,$0
#27,7- Cechanical properties o. solids . . . . . . . . . . . . . . . . . . . . . . . . ,$0
#27* Bi3liography and .urther reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,$0
!ro3lems .or Chapter #2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ,$-
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
$? Some Special Topics
%&1. INTR23UCTI2N
This chapter is concerned 6ith three important topics 6hich, although they might ha/e
3een accommodated in other chapters, are pro3a3ly 3est discussed separately7 'ach o.
them has had a /ery signiLcant impact upon our understanding o. chemical structure and
the concepts upon 6hich they are 3ased are no6 so deeply im3edded in our descriptions
o. molecular and material properties that they .orm a part o. the e/eryday language o.
chemistry7 They also pro/ide some o. the 3est eamples o. the 6ay in 6hich 0uite simple
0uantum mechanical concepts can enhance our understanding o. the properties o. large
molecules, materials and metals that are o. paramount interest to 3iologists, materials
scientists and engineers in the 6ider 6orld o. applied science and technology7
%&1% THE HU
C
C=E5 M25ECU5AR 2R8ITA5 FHM2G
THE2RY
The 9uM c4el theory Lnds a place here .or se/eral reasons, 6hich are 6orth noting at
the outset7 Ats place 6ould 3e @ustiLed 3ecause it 6as the Lrst molecular or3ital theory
that could 3e applied to large molecules7 At is a theory that can 3e implemented 6ithout
the aid o. a computer and is there.ore an ideal test 3ed on 6hich to study some o. the 3asic
principles and procedures o. the C" theory7 An addition, some ,0 years a.ter its 3irth it
.ormed the starting point .or a /ery success.ul theoretical interpretation o. the electronic
spectra o. the aromatic hydrocar3ons, 6hich included electron repulsion terms, and .or
the etended 9uM c4el theory, 6hich has 3een 6idely used 3y organo2metallic chemists
as an aid to the interpretation o. the chemical reactions and structures o. their
compounds7
%&1%1% T$e ?asis o" H;C #>els approa#$
We sa6 in Section ?7#572 ho6 the .ormation o. sp
2
hy3rids 3et6een the 2s and 2p A"s
o. a car3on atom gi/es rise to three hy3ridised or3itals lying in a plane and ideally suited
to .orming , ' 3onds to neigh3ouring atoms 6ith 3ond angles in the plane o. approi2
mately #20

7 The remaining, unhy3ridised 2p A" is a/aila3le .or .orming a ( 2electron

structure7 The geometries and special properties o. the aromatic hydrocar3ons and con@u2
gated polyenes may 3e interpreted in terms o. this type o. hy3ridisation o. their car3on
atoms7 An #$,# 'rich 9uM c4el (#%$? I #$%0+ proposed that the energies and 6a/e
.unctions o. the ( 2electron system could 3e calculated using an approach in 6hich the
' 2electron system 6as disregarded, apart .rom the role 6hich it plays in esta3lishing the
molecular geometry7 Though o3/iously not a complete theory, 9uM c4elGs approach
has 3een /ery success.ul 3ecause so many o. the distinguishing chemical and physical
properties o. the con@ugated hydrocar3ons are ( 2electron properties7 9uM c4elGs
@ustiLcation o. this approach 6as 3ased on the .ollo6ing reasoning1
The ' 3onds 3et6een sp
2
2hy3idised car3on atoms and their neigh3ours all lie in the
molecular plane .ormed 3y the car3on atoms and they are symmetrical 6ith respect to
reOection in that planeP i7e7 the phase o. the 6a/e .unction 6hich descri3es a particular '
3ond is the same a3o/e the plane as 3elo6 it7 An contrast, the phase o. the unhy3ridised
2p A" 6hich lies at $0

to the plane changes sign upon reOection in the plane so that
any molecular or3itals .ormed 6ith such 2p A"s 6ill 3e antisymmetric7 There.ore,
there can 3e no 3onding 3et6een ' and ( or3itals in planar con@ugated molecules7


C $ 9 $



The 9uM c4el Colecular "r3ital (9C"+ Theory $-
The ' electrons occupy the space in the plane o. the molecule 6hilst the ( electrons are
concentrated a3o/e and 3elo6 that plane7 The t6o types o. electrons mo/e in di..erent
regions o. space7
The energies o. the ' electrons in/ol/ed in strong ' 3onds are, on the 6hole, lo6er
than those o. the ( electrons 6hich are in/ol/ed in the 6ea4er ( 3onds7
The Lrst o. the a3o/e reasons, that in/ol/ing symmetry, is the most po6er.ul argument
.or treating the ' and ( electrons separately7
%&1%1& T$e met$o/
Thus, the pro3lem 6hich 6e ha/e is to Lnd the set o. ( 2electron C"s (
a
+ .ormed as
linear com3inations o. car3on 2p
K
A"s, one .rom each car3on atomP i7e7 6hat are the
/alues o. the coe.Lcients, C
ai
, in the epression1

a
= C
a#
$
#
+ C
a2
$
2
+ C
a,
$
,
+ + C
an
$
n


C
ai
$
i
i
An order to Lnd the 3est /alues o. these coe.Lcients 6e use the criterion, pro/ided 3y
the /ariation theorem (Appendi 2+, that the 3est 6a/e .unction 6e can o3tain is the one
6hich gi/es the lo6est energy7 There.ore, 6e Lrst 6rite do6n the epectation /alue o.
the energy (E
a
+ calculated 6ith the 6a/e .unction (
a
+ as1
E
a
=
a
|9

|
a
,
a
|
a
=
C
ai
$
i

9 C
a@
$
@
C
ai
$
i

C
a@
$
@
i @ i @
=

C
ai
i

a@

i
|

|
@

@ i
C
ai

C
a@
$
i
|$
@

@


C
ai
i

C
a@
9
i@
@ i
C
ai

C
a@
S
i@
@
;ote that there are n
2
terms in the numerator and the denominator o. the a3o/e epres2
sion .or E
a
7 The epressions 9
i@
and S
i@
are simply sym3ols .or the integrals $
i
|9

|$
@
and $
i
|
$
@

respecti/ely and at some stage in the calculation they ha/e to 3e e/aluated7 9o62
e/er, 3e.ore 6e do that 6e apply the criterion that the coe.Lcients 6e re0uire are those
6hich gi/e the lo6est /alue o. E
a
7 We do this 3y di..erentiating the a3o/e epression
.or E
a
and setting the result to Kero7 This procedure is descri3ed in detail in Appendi 27
9ere 6e need only note that the process leads to a set o. n simultaneous linear e0uations
all e0ual to Kero1
C
a#
!9
##
E
a
S
##
" + C
a2
!9
#2
E
a
S
#2
" + C
a,
!9
#,
E
a
S
#,
" + + C
an
!9
#n
E
a
S
#n
" =
0
C
a#
!9
2#
E
a
S
2#
" + C
a2
!9
22
E
a
S
22
" + C
a,
!9
2,
E
a
S
2,
" + + C
an
!9
2n
E
a
S
2n
" =
0
1 1 1 1
1 1 1 1
C
a#
!9
n#
E
a
S
n#
" + C
a2
!9
n2
E
a
S
n2
" + C
a,
!9
n,
E
a
S
n,
" + + C
an
!9
nn
E
a
S
nn
" =
0
An order to sol/e these e0uations 9uM c4el made some drastic assumptions7
#
When
6e apply the theory 6e shall see ho6 .ar these 6ere @ustiLed in terms o. the insight
6hich the 9uM c4el theory gi/es us7 Dirst, 6e descri3e each one in turn7
%&1%1' H;C #>els ass;mptions
S
i@
= $
i
|$
@
is an o/erlap integral, it is a measure o. the etent to 6hich the 2p
K
A"s
on car3on atoms i and @ occupy the same region o. space and is there.ore closely related
to the ( 2electron 3onding 3et6een atoms i and @7 When i = @ 6e ha/e the o/erlap o. an
A" 6ith itsel. 6hich is unity .or a normalised 6a/e .unction7 There.ore, S
ii
= #.07 The
o/erlap integrals 6here i = @ are not di.Lcult to calculate and it is .ound that .or ad@acent
car3on atoms S
i@
0.257 Dor car3on atoms separated 3y t6o 3onds the /alue o. S
i@
is
much smaller and it drops o.. rapidly 6ith distance7 9uM c4el set all o/erlap, e/en
that
3et6een neigh3ouring car3on atoms, to Kero7 This is 0uite a drastic assumption7
The integrals 9
i@
= $
i
|9

|$
@
are /ery comple since the 9amiltonian operator consists
o. many terms representing the energy o. a single ( 2electron mo/ing in the a/eraged Leld
o. all the ' 2electrons and all the other ( 2electrons7 But its essential physical content is the
energy o. interaction 3et6een the t6o A"s, $
i
and $
@
6hich, 6here $
i
is ad@acent to $
@
,
represents the ( 2electron 3onding energy 3et6een the t6o car3on atoms7 The integral is
o.ten called the resonance integral and 3ecause it represents the 3onding energy 3et6een
t6o car3on atoms it is a negati/e 0uantity7 When i = @ the integral represents the energy
o. an electron in a car3on 2p
K
A", 3ut in the molecule rather than in a .ree car3on
atom7 9uM c4el assumed that the /alue o. 9
i@
.or car3on atoms separated 3y t6o or
more 3onds 6as su.Lciently small to 3e neglected7 9e did not attempt to calculate 9
ii
and
9
i@
(i
ad@acent to @+ 3ut epressed them in parametric .orm as indicated in Ta3le #27#7 With these
assumptions the secular e0uations 3ecome much simpler 3ut, since the simpliLcations
depend upon the particular geometry o. the molecule (6hich atoms are ad@acent to 6hich
other atoms+, the simpliLcation is not readily appreciated 6hen it is epressed in a general
.orm7 There.ore, let us assume that 6e are dealing 6ith the special case o. the 3utadiene
molecule Digure #27#7
%&1%1( 3etermination o" HM2 energies an/ A2 #oe"B#ients
Dor 3utadiene 9uM c4elGs approimations lead to the .ollo6ing secular e0uations7 ;ote
that, in 9uM c4el theory, no allo6ance is made .or the .act that the t6o end 3onds o. the
molecule
Ta?le %&1% 9uM c4elGs approimations
i = @ i ad@acent to @ i not ad@acent to @
S
i@
(o/erlap integral+ #70 070 070
9
i@
(interaction integral+ L K 070
9 9
6ig;re %&1% trans Butadiene
9
#
C
C
2
9
,
C
C
*
9
9
C
a#
K
+
C
a2
!L

E
a
"
+
C
a,
K
C
a2
K
+
C
a,
!L

E
a
"
are not the same as the central 3ond7 ;ote also, that the e0uations .or the cis isomer are
exactly the same as those .or the trans7
C
a#
!L E
a
" + C
a2
K = 0
= 0
+
C
a*
K
=
0
C
a,
K
+
C
a*
!L

E
a
"
=
0
To proceed .urther it is use.ul to di/ide all .our e0uations 3y K 7 Since K is an
energy this step is tantamount to adopting K as our energy unit and epressing all other
energies
in terms o. it7 Setting !L

E
a
",K
=
6e then ha/e1
C
a#
+ C
a2
= 0
C
a#
+
C
a2

+
C
a,
=
0
C
a2
+
C
a,

+
C
a*
=
0
C
a,
+
C
a*

=
0
These are .our simultaneous e0uations .rom 6hich 6e hope to determine the /alues o.
the coe.Lcients C
a#
, C
a2
, C
a,
and C
a*
7 We should also note that, since 6e do not 4no6 E
a
,
is also un4no6n7 There is a trivial solution to our pro3lem, C
a#
=
C
a2
=
C
a,
=
C
a*
=
0.0P
3ut this is clearly not 6hat 6e re0uire7 Drom the theory o. simultaneous e0uations 6e
4no6 that in order .or there to 3e a non+trivial solution the determinant .ormed 3y the
.actors 6hich multiply the coe.Lcients C
ai
in the a3o/e e0uations must 3e e0ual to Kero1

# 0 0


# 0


# # 0


# # 0


0 # #

=

# #

#

0 #


0 #


0 #


0 0 #



#

# #

#

0 #

=








#



#

#


+
#

#



#


0

#

0

=
2
!
2
#"
2
#!
2
#" =
*
,
2
+ # = 0.0
At this stage in a 9C" calculation 6e are al6ays con.ronted 6ith the pro3lem o.
Lnding the roots o. a polynomial, the order o. 6hich is the num3er o. car3on atoms7 An
the present case, the easiest 6ay to a solution is to Lrst set y =
2
and sol/e .or y, 6hich
gi/es y = 0.,%#$- and 27?#%0,7 The positi/e and negati/e s0uare roots o. these /alues
o. y gi/e the roots = !L E
a
",K = 0.?#%0, and #7?#%0,7 "r in terms o. L and K P
E
a
= L 0.?#%0,K and L #.?#%0,K 7 ;ote that although 6e 3egan 3y loo4ing .or the
lo6est /alue o. E
a
6e ha/e .ound not one 3ut .our /alues .or that 0uantity7 ;aturally,
6e could simply ta4e the lo6est one, 3ut it is interesting to consider the signiLcance o.
the others7 We shall return to that su3@ect later7 "ur immediate tas4 is to determine the
coe.Lcients 6hich go 6ith each o. the energy /alues7 To do this 6e return to the secular
e0uations epressed in terms o. and su3stitute one o. the /alues o. 6hich 6e ha/e
.ound into all fo1r e0uations7 Let us choose = 0.?#%0, gi/ing '0uation (#27#7#+1
0.?#%0,C
a#
+ C
a2
= 0
C
a#

0.?#%0,C
a2
+
C
a,
=
0
C
a2

0.?#%0,C
a,
+
C
a*
=
0
C
a,

0.?#%0,C
a*
=
0
!#2.#.#"


The Lrst e0uation pro/ides a simple relationship 3et6een C
a#
and C
a2
and the last does
the same .or C
a,
and C
a*
7 By su3stituting these results into e0uations 2 and , any three
coe.Lcients can 3e epressed in terms o. the other one7 Dor eample, C
a2
= 0.?#%0,C
a#
P
C
a,
= 0.?#%0,C
a#
P C
a*
= C
a#
7 But note that the a3solute /alues o. the C
ai
are not
.ound, only their relati/e /alues7 This is 3ecause the e0uations are all e0ual to Kero, i7e7
they are homogeneo1s7 Dortunately, 6e ha/e one .urther criterion 6hich must 3e satisLed
and 3y means o. 6hich 6e can L the a3solute /alues o. the coe.Lcients7 The C"
a
must 3e normalised i. it to 3e satis.actory .rom the physical /ie6point1

a
|
a
=
i
C
ai

C
a@
$
i
|$
@

@ i
C
ai

C
a@
)
i@
=
@

!C
ai
"
2
i
6here 6e ha/e used the .act that, in 9uM c4el theory, the o/erlap integrals are e0ual
to unity 6hen i = @ and Kero other6ise7 =sing the normalisation condition and the
relati/e
/alues o. the coe.Lcients gi/en a3o/e their a3solute /alues can 3e determined7 When this
procedure is repeated .or each o. the /alues o. the results gi/en in Ta3le #272 are .ound7
As a chec4 o. the calculation o. the C" coe.Lcients, the energy o. the corresponding
or3ital can 3e calculated1

2
|9

|
2
= 0.?0#5$
#
+ 0.,-#%$
2
0.,-#%$
,
0.?0#5$
*
|9

|0.?0#5$
#
+ 0.,-#%$
2
0.,-#%$
,
0.?0#5$
*

= L{2.0 !0.?0#5 0.?0#5 + 0.,-#% 0.,-#%"}
+ K {2.0 !0.?0#5 0.,-#% 0.,-#% 0.,-#% + 0.,-#% 0.?0#5"}
= L + 0.?#%0K
Although 6e set out to determine one energy /alue, the lo6est, 6e regard the .our
energies a3o/e and the associated C"s (6a/e .unctions+ as .our possi3le ( 2electron
energy le/els .or 3utadiene7
The a3o/e e0uations .or the C"s and the energy2le/el diagram (Digure #272+ illustrate
a num3er o. important points1
Since K is a negati/e 0uantity, 3ecause it represents the ( 2electron 3onding energy
3et6een t6o ad@acent car3on atoms,
#
is the C" o. lo6est energy and
*
the highest7
The order o. the energy le/els .ollo6s the num3er o. nodes, i7e7 changes in sign 3et6een
one coe.Lcient and the net7 Thus
#
has no nodes 3ut
*
has three7
The term L is common to all the energies 6hich split out .rom that /alue in a symmet2
rical pattern as illustrated in Digure #2727 L is the energy o. a non23onded 2p
K
electron
o. car3on and C"s o. energy greater than L are ( 2anti3onding 6hile those 3elo6 L
are ( 23onding7
Ta?le %&1& The 9uM c4el or3itals and energies .or 3utadiene

*
= 0.,-#%$
#
0.?0#5$
2
+0.?0#5$
,
0.,-#%$
*
L #.?#%0K

,
=
0.?0#5$
#

0.,-#%$
2

0.,-#%$
,
+
0.?0#5$
*
L

0.?#%0K

2
=
0.?0#5$
#
+
0.,-#%$
2

0.,-#%$
,

0.?0#5$
*
L
+
0.?#%0K

#
=
0.,-#%$
#
+
0.?0#5$
2
+
0.?0#5$
,
+
0.,-#%$
*
L
+
#.?#%0K
'nergy
a #7?#%0,3
a 07?#%0,3
a
a + 07?#%0,3
a + #7?#%0,3
6ig;re %&1& ( 2'lectron energy le/els .or 3utadiene
'ach car3on atom contri3utes one ( electron and 3e.ore 3onding each has an energy
o. L7 All .our o. them can enter 3onding or3itals and sta3ilise the molecule7 The
sta3ilisation due to the ( 2electrons ( E
(
+ is1
E
(
= *L 2 !L + #.?#%0,K" 2 !L + 0.?#%0,K" = *.*-2#2K
The energies and coe.Lcients, illustrated a3o/e .or the case o. 3utadiene, are the primary
results o. a 9uM c4el theory calculation7 An the net section 6e eamine some o. the
6ays in 6hich these data can 3e used to interpret eperimental results7
%&1%1) Appli#ations o" HM2 energies
8he energies of indi9idual "Os
As a general rule, ( 23onding is 6ea4er than ' 23onding and ( 2anti3onding less anti3ond2
ing than ' 7 There.ore the ( 2electron energy le/els o. a molecule lie near the energetic
centre o. gra/ity and, in particular, the highest occupied C" (9"C"+ is usually a ( 2
electron or3ital7 The ma@or eception to this is the presence o. non23onding C"s in
car3onyl compounds and heterocycles7 Similarly, the lo6est unoccupied C" (L=C"+ is
almost in/aria3ly a ( or3ital and the energies o. these frontier or*itals may 3e epected
to correlate 6ith the eperimental ionisation energy and electron a.Lnity o. the molecule7
A. these properties cannot 3e measured directly, the reduction and oidation energies o.
the molecule can sometimes 3e measured 3y electrochemical techni0uesP in the case o.
the aromatic hydrocar3ons this has 3een done /ery success.ully7 All that need 3e said here
a3out these methods is that the molecule (C+ is dissol/ed in an electrically conducting
solution (e7g7 acetonitrile containing tetraethylammonium perchlorate+ 6hich is placed in
an electrochemical cell 6here the negati/e potential re0uired to .orm C

, or the positi/e
potential re0uired to .orm C
+
, is measured7 The potentials so measured correlate 6ell
6ith the 9uM c4el 9"C" and L=C" energies as Digure #27, sho6s7
2
The slopes o. the
t6o correlations also ena3le us to determine /alues o. K o. 2%- 4J mol

#
and #$- 4J
mol

#
.or the reduction and oidation potentials respecti/ely7 We shall return to comment upon
the di..ering /alues o. K gi/en 3y the /arious correlations 6ith eperimental data in
Section #27#7-7
red #
o #
"

i
d
a
t
i
o
n

o
r

r
e
d
u
c
t
i
o
n

(

+

e
n
e
r
g
y

(
4
J

m
o
l

#
+
,00
250
200
e
#H2
3 = 2%- 4J mol
#50
#00
50
e
#H2
3 = #$- 4J mol
0
072 07, 07* 075 07? 07- 07% 07$ #70 #7#
Colecular or3ital (9"C" or L=C"+ energy (3+
G7J7 9oi@tin4, Rec. -rav. Chim7, ++, 555 (#$5%+7
:eproduced 3y permission o. Wiley28C97
6ig;re %&1' Correlation o. 9uM c4el 9"C" and L=C" energies 6ith polarographic oidation
and reduction potentials
2
"O energy differences
At is tempting to thin4 that the energy di..erence 3et6een the 9"C" and L=C" 6ill
3e a measure o. the energy o. the lo6est energy 3and in the electronic spectrum o.
the molecule7 9o6e/er, as 6e ha/e seen in Chapter ##, this is an o/ersimpliLed /ie6
since it does not allo6 .or the /ery signiLcant energies 6hich arise .rom interelectronic
repulsion7 ;e/ertheless, the L=C" I 9"C" energy di..erence ( E+ does ma4e a /ery
signiLcant contri3ution to the corresponding electronic spectral 3and and 6e do Lnd a
good correlation 3et6een calculated and o3ser/ed E in many cases7 The eample o.
the %ara23and (
#
L
a
+ o. the aromatic hydrocar3ons is sho6n in Digure #27*7
,
A /alue o.
K
=
25- 4J mol

#
can 3e deduced .rom the slope o. the graph7
8otal ( -electron energy
The hydrocar3ons 6here electron delocalisation is possi3le are distinguished .rom their
3rethren that do not ha/e delocalised ( 2electron systems 3y the important property o.
additi/ity o. 3ond energies7 This can 3e seen 6hen 6e compare heats o. com3ustion7
Where there is no delocalisation, each 3ond type, CI9, CIC, C
=
C etc7, can 3e assigned
a heat o. com3ustion and the total heat o. com3ustion o. the molecule can 3e 6ritten
as a sum o. the indi/idual contri3utions .rom each 3ond7 Dor a molecule 6ith electron
delocalisation, such as 3enKene, this is not possi3le, the molecule 3eing .ound to 3e more
sta3le, i7e7 to ha/e a smaller heat o. com3ustion, than the sum o. the indi/idual 3ond
contri3utions, ,E!CIC" + ,E!C
=
C" + ?E!CI9"1
]
Ta3le #27, lists some typical data
illustrating this discrepancy7
*
]
The thermochemical argument is eplained in more detail in Bo #27#7
The 9uM c4el Colecular "r3ital (9C"+ Theory #0,
3 = 25- 4J mol
#
BenKene
Calculated
, *5#
"3ser/ed
, ,02
(4J mol

#
+
#*$
(K +
2700
;aphthalene 5 *%* 5 22$ 255 ,7?%
<iphenyl ? ?,# ? ,,, 2$% *7,%
Anthracene - 5#, - #5* ,5$ 57,2
!henanthrene - 5#? - #0# *#5 57*5
!yrene % *0# - $*? *55 ?75#
Chrysene $ 55* $ 0*% 50? -7#$
!erylene #0 *,0 $ $02 52% %725
"
3
s
7

#
L
a

(
p
+

3
a
n
d

e
n
e
r
g
y

(
4
J

m
o
l

#
+
*50
*00
,50
,00
250
200
07* 07? 07% #70 #72 #7*
'nergy di..erence (L=C" 9"C"+ (3+
'7 9eil3ronner and J7;7 Currell, Q. Chem. Soc7, 2?## (#$?2+7
:eproduced 3y permission o. The :oyal Society o. Chemistry7
6ig;re %&1( Correlation o. the L=C" I 9"C" energy di..erence 6ith the energy o. the %ara
3and o. some aromatic hydrocar3ons
,
Ta?le %&1' <elocalisation energies (<L'+ o. some aromatic hydrocar3ons
Compound 9eat o. Com3ustion (4J mol

#
+ <i..erence 9uM c4el
<L'
;aturally, the discrepancy has 3een associated 6ith the .act that 6e do not 3elie/e
there are three dou3le and three single car3on2car3on 3onds in 3enKene7 :ather, 6e 4no6
.rom eperiment that all the car3on2car3on 3onds are the same and that the molecular
structure should 3e represented 3y something intermediate 3et6een, or some com3ination
o., the t6o >e4uleb structures 6hich 6e can dra67 This is the cause o. the
additional sta3ility o. the molecule o/er and a3o/e that o. one o. the >e4uleb structures7
This etra sta3ility, the di..erence 3et6een the eperimental com3ustion energy and
the sum o. 3ond contri3utions, is called the resonance or delocalisation energy7 Some
comparisons o. theory and eperiment are listed in Ta3le #27,7
The heat o. com3ustion .or a particular >e4uleb structure o. localised single and dou3le
3onds 6as calculated 3y >lages .rom the .ollo6ing /alues .or indi/idual 3onds, 6hich
he deduced .rom eperimental calorimetric data1 E!CI9"
=
22? 4J mol

#
, E!CIC"
=
'

p
e
r
i
m
e
n
t
a
l

d
e
l
o
c
a
l
i
s
a
t
i
o
n

e
n
e
r
g
y

(
4
J

m
o
l

#
+
#0* Some Special Topics
20? 4J mol

#
and E!C
=
C" = *$# 4J mol

#
6ith some additional corrections .or spe2
cial structural .eatures, e7g7 * 4J mol

#
.or a 3enKene ring7
]
Thus the calculated heat o.
com3ustion .or 3enKene is1
?E!CI9" + ,E!C
=
C" + ,E!CIC" + * !.or ring"
? 22? + , *$# + , 20? + * = ,*5# 4J mol

#
But eperimental heat o. com3ustion = ,,02 4J mol

#
There.ore delocalisation energy = #*$ 4J mol

#
The energies o. the three 9C" le/els occupied 3y the si ( electrons o. 3enKene are
L + 2K , L + K and L + K and the occupied ( or3ital o. ethene has an energy o. L + K 7
There.ore, the theoretical /alue 6ith 6hich this eperimental delocalisation energy is
to 3e compared, the 9uM c4el ( 2electron energy o. 3enKene minus that o. three
ethene molecules, is1
?.0L + %.0K ,!2.0L 2.0K" = 2.0K
A graph o. calculated /ersus eperimental delocalisation energies .rom 6hich a /alue
o. K = ?* 4J mol

#
can 3e deri/ed is sho6n in Digure #2757
?00
500
3 = ?* 4J mol
#
*00
,00
200
#00
2 , * 5 ? - % $
Calculated delocalisation energy (3+
D7 >lages, Chem7 /er7, ,&, ,5% (#$*$+7 :eproduced 3y permission o. Wiley28C97
6ig;re %&1) Correlation o. calculated and eperimental delocalisation energies .or some aromatic
hydrocar3ons
*
]
There are many su3tle corrections o. this .orm to allo6 .or special aspects o. the structures7 There.ore, the data in Ta3le #27,
cannot 3e reproduced using only the three 3ond energies gi/en7 Dor more in.ormation see D7 >lages, Chem. /er., :2, ,5%
(#$*$+7
%&1%1* Appli#ations o" HM2 #oe"B#ients
Charge densities and bond orders
The s0uare o. the A" coe.Lcient C
ai
measures the participation o. the particular car3on
2p
K
A", $
i
on car3on atom i, in the C"
a
and, in particular, the proportion o. the
electron delocalised in
a
6hich may 3e said to 3e present in $
i
7 Since each C" normally
accommodates t6o electrons, the charge density in $
i
(0
ii
+, 6hich is due to the occupation
o.
a
, is 2C
ai
2
7 Dor the total charge density on car3on atom i (&
ii
+ this must 3e
summed o/er all occupied or3itals1
&
ii
= 2

!C
ai
"
2
a occ.
The 3ond order, !
i@
, is o3tained in an analogous manner1
!
i@
=
2

C
ai
C
a@
a occ.
The meaning o. the 3ond order may 3e appreciated 3y noting, Lrstly, that .or a sig2
niLcant /alue o. !
i@
3oth C
ai
and C
a@
must also ha/e signiLcant /alues7 Secondly, i. the
t6o A" coe.Lcients ha/e the same sign they ma4e a positi/e contri3ution to the 3ond
order 6hereas i. they are o. opposite signs the contri3ution is negati/e7 Since a change o.
sign on going .rom atom i to atom @ implies a node 3et6een the t6o atoms .or that C",
negati/e contri3utions to !
i@
are anti3onding contri3utions 6hile positi/e contri3utions are
3onding7 There.ore, a large positi/e 3ond order indicates a strong ( 23ond 3et6een the t6o
atoms concerned 6hile a negati/e /alue indicates an anti3ond7 The charge densities and
3ond orders .or 3utadiene calculated .rom the C"s in Ta3le #272 are gi/en in Ta3le #27*7
T6o points a3out Ta3le #27* are 6orthy o. comment1
The charge density in the ground state is #70 on each car3on atom7 This is 0uite
generally true .or a large class o. compounds, 6hich are 4no6n as alternant7 All the
aromatic hydrocar3ons that contain no L/e2 or se/en2mem3ered rings and all the linear
polyenes are alternant hydrocar3ons7
The 3ond order o. the terminal 3onds is t6ice that o. the central 3ond, in star4 contradic2
tion to the 9uM c4el approimation o. the same resonance integral (K + .or all CIC
3onds7
As .ar as applications are concerned, it seems natural to assume that positi/ely charged
reactants (electrophiles+ 6ill pre.erentially attac4 those atoms o. a molecule 6here the
Ta?le %&1( ( 2electron charge densities and 3ond orders .or 3utadiene
C" 0
##
p
#2
0
22
p
2,
2 electrons in
*
+0.2-?* 0.**-2 +0.-2,? 0.-2,?
2 electrons in
,
+
0.-2,?

0.**-2
+
0.2-?*
+
0.2-?*
2 electrons in
2
+
0.-2,?
+
0.**-2
+
0.2-?*

0.2-?*
2 electrons in
#
+
0.2-?*
+
0.**-2
+
0.-2,?
+
0.-2,?
&
##
!
#2
&
22
!
2,
Ground state
a
+
#.0000
+
0.%$**
+
#.0000
+
0.**-2
a
C"s
#
and
2
only are occupied in the ground electronic state7
electron density (&+ is high 6hile negati/ely charged reactants (nucleophiles+ 6ill see4
out atoms 6here & is lo67 This assumption is 3ased upon the simple concept that the
Coulom3ic energy o. the t6o reacting molecules 6ill 3e lo6ered 3y the approach o.
oppositely charged atoms and raised 3y the con/erse7 This simple analysis contains much
more than a grain o. truth, 3ut the progress o. a chemical reaction .rom reactants to
products is a /ery complicated process in 6hich the ma@or role is played 3y the energy
di..erences 3et6een the reactants, the transition state(s+ and the products7 Dor molecules
to 6hich the 9uM c4el theory is applica3le, and .or many others, >lopman
5
has sho6n
that the interaction o. atom r o. a nucleophile (:+ 6ith atom s o. an electrophile (S+ may 3e
epressed in the .orm1
E
=
&
r
&
s
,?<
+
2!C
9"C"
C
L=C"
K"
2
,!E
9"C"

E
L=C"
"
r s r s
E is the energy change due to the interaction o. r and s7 The Lrst term on the right
is the Coulom3ic term representing the interaction 3et6een the total charges (assumed to
3e opposite+ on the atoms r and s 6hich are separated 3y a distance <7 ? is the dielectric
constant o. the sol/ent7 The second term contains the product o. the coe.Lcient o. the
9"C" o. the nucleophile at the interacting atom (r+ and the coe.Lcient o. the L=C"
o. the electrophile at atom s multiplied 3y K 7 The denominator is the energy di..erence
3et6een the 9"C" and L=C"7 The many and /aried applications o. this e0uation, and
others li4e, it are largely responsi3le .or the eplosi/e gro6th in our understanding o.
organic chemical reactions 6hich too4 place in the second hal. o. the 20th century7 The
results lea/e no room .or dou3t as to the /alue o. the 9uM c4el C" coe.Lcients in
the interpretation o. organic chemical reactions7 This is .ar too etensi/e a su3@ect .or
us to enter into here 3ut, .ortunately, Dleming
?
has pro/ided us 6ith a splendid and
reada3le account to 6hich interested readers should turn .or .urther in.ormation and
conLrmation o. the 3ald statement in the last sentence7
"ur last eample o. a correlation o. 9uM c4el theory 6ith eperiment 6ill also
ser/e to illustrate the 6ay in 6hich the theory can 3e etended to ta4e account o. (
2electron systems in/ol/ing atoms other than car3on, such as nitrogen and oygen7 A. 6e
call the hetero2atom F, then 6e ha/e to ascri3e to it appropriate /alues o. L
F
and K
F
7
Since K
C
is our unit o. energy, 6e deLne these t6o 0uantities in terms o. K
C
and t6o ne6
parameters, h
F
and 4
F
, as .ollo6sP allo6ing only .or CIF 3onds1
L
F
= L
C
+ h
F
K
C
K
F
= 4
F
K
C
A good discussion o. h
F
and 4
F
and a ta3le o. /alues may 3e .ound in Streit6ieser7
-
The correlation in 0uestion is that o. ( 2electron 3ond order 6ith the car3onyl stretching
.re0uency in aldehydes, 4etones and 0uinones7 Since the mass o. the atoms and the ' 2
3onding are a constant .eature, 6e epect the .re0uency o. the C
=
" stretching /i3ration
to increase linearly 6ith the 3ond order7 Digure #27?,
%
in 6hich the 3ond orders 6ere
calculated 6ith h
"
= #.2 and 4
"
= 2.0, conLrms this epectation7
%&1%1+ Some Bnal #omments on t$e H;C #>el t$eor0
The simplicity o. the 9uM c4el theory and the 6ide range o. important chemical
compounds to 6hich it is rele/ant ensured its etensi/e application .rom the outset7 Dor
such a simple theory its success has 3een remar4a3le7 9o6e/er, it is only .air to say
that the success
Cagnetism in Chemistry #0-
Aldehydes
>etones
&uinones
C
=
"

6
a
/
e

n
u
m
3
e
r

(
c
m

#
+
#%00
#-50
#-00
#?50
#?00
07-5 07%0 07%5 07$0 07$5 #700
C=" p2electron 3ond order
G7 Berthier, B7 !ullman and J7 !ontis, J7 Chim7 Phys7, (-, ,?- (#$52+7 :eproduced 3y permission
o. Wiley28C97
6ig;re %&1* Correlation o. C=" ( 3ond order 6ith car3onyl stretching .re0uencies
5
is in an important sense a result o. the parameterisation o. the theory and o. the .act that
our epectations o. the results are not o/erly high7 This is illustrated most clearly in the
di..erent /alues o. K 6hich result .rom the applications descri3ed a3o/e7 We do not Lnd,
and .or such a simple theory 6e should not epect to Lnd, the same /alue o. K .rom each
application7 This is 3ecause K is a composite parameter representing the electron2nucleus
attraction, the interelectronic repulsion and the 4inetic energy7 These three .orms o. energy
ma4e di..erent contri3utions to the eperimental energies 6ith 6hich the results o. the
9uM c4el calculations are compared7 This su3@ect has 3een discussed in detail 3y
Currell, >ettle and Tedder
$
6ho, ta4ing the su3@ect .urther, sho6 ho6 the inclusion o. the
all2 important electron repulsion terms ma4es the theory .ar more 0uantitati/eP 3ut also
.ar more compleU
%&1& MANETISM IN CHEMISTRY
The .act that many atomic nuclei possess magnetic properties made possi3le the chemi2
cal applications o. nuclear magnetic resonance spectroscopy (Chapter $+, 6hich has had
such a pro.ound e..ect upon the determination o. molecular structure7 But the magnetic
moments o. nuclei are /ery small and the ma@or, macroscopic magnetic phenomena, some
o. 6hich ha/e 3een 4no6n since anti0uity, are due to the spin and or3ital motion o. elec2
trons7 An this section 6e shall 3e concerned only 6ith QelectronicG magnetism7 "ur tas4
is to study the 6ay in 6hich the magnetic properties o. atoms mani.est themsel/es in
molecules and etended solids, and ho6 the magnetic 3eha/iour o. such materials can 3e
used to etract in.ormation a3out their electronic structures7 The study o. magnetism dates
#0% Some Special Topics
3ac4 to the #$th century 6hen the classical phenomena o. %aramagnetism diamagnetism
and ferromagnetism 6ere identiLed and deLned7 Core recently, especially in the second
hal. the 20th century, the study o. the magnetic properties o. chemical compounds has
3een stimulated 3y t6o .actors7 The gro6ing understanding o. the connection 3et6een
magnetism and chemical structure has sho6n that magnetism can 3e a /alua3le tool in the
elucidation o. the Lner details o. molecular electronic structure, and the use o. magnetic
materials in many technological de/ices has pro/ided a strong applied2science stimulus
to research into chemical magnetism7
%&1&1% Magneti# s;s#epti?ilit0: /iamagnetism an/ paramagnetism
%.
A. a su3stance is placed in a magnetic Celd o. strength 8 (units A m

#
+ then a magnetic
moment o. magnitude 5 (A m

#
+ 6ill 3e induced in that su3stance7 The relationship
3et6een 8 and 5 , 6hich is 4no6n as the magnetisation, is1
5 = H8 !#2.2.#"
6here H (chi+ is the vol1me magnetic s1sce%ti*ility, 6hich is dimensionless7
The magnetic ]1x density 6ithin the su3stance, / (Tesla

T
=
J C

#
s m

2
+, is related
to the strength o. the applied Leld and the magnetisation 3y1
/ = T
o
!8 + 5" = T
o
!# + H "8 !#2.2.2"
6here T
o
is the vac11m %ermea*ility 6hich is deCned to ha/e the /alue *( #0

-
J C

2
m

#
s
2
7 A. H R 0 8 and 5 add to increase / 6ithin the magnetised su3stance 6hich is
then said to 3e %aramagnetic7 A. H P 0 the su3stance is said to 3e diamagnetic7
<iamagnetism is .ound in all materials7 The electrons are al6ays in motion and their
motion constitutes an electric current7 When the material is su3@ected to a magnetic Leld,
the motion o. the electrons is pertur3ed and, according to LenKGs la6, in such a 6ay that
the /ery small magnetic Leld 6hich results .rom this pertur3ation o. the electric current
opposes the Leld 6hich caused it7 Thus, the induced magnetisation opposes and there.ore
reduces the magnetic Leld 6ithin the material 6hich is the characteristic 3eha/iour o. a
diamagnetic su3stance7 The e..ect is largely independent o. temperature7
Though e/er2present, the diamagnetism can 3e o/er6helmed 3y the magnetic e..ects o.
unpaired electrons, i. there are any, gi/ing rise to paramagnetism7 The magnetic properties
o. a purely diamagnetic su3stance are ind1ced 3y an applied magnetic Leld, 3ut in the case
o. a paramagnetic su3stance each molecule or atom already has a %ermanent magnetic
moment and the o3ser/ed 3ul4 magnetic moment arises .rom the partial alignment o. these
molecular (atomic+ moments 3y the applied Leld7 T6o characteristics o. paramagnetic
materials stand out7 Dirstly, the induced moment (5 + adds to the magnetic Leld (8 + and,
secondly, paramagnetism, in contrast to diamagnetism, is /ery temperature2dependent7
The reason .or the mar4ed temperature dependence is not .ar to see47 The indi/idual
atomicHmolecular magnets o. 6hich the material is composed tend to align themsel/es
6ith the applied Leld, there3y increasing / (Bo #272+7 But this alignment is opposed 3y
the thermal motion o. the atomsHmolecules 6hich increases 6ith increasing temperature7
Thus, paramagnetism decreases as temperature increases according to a la6 disco/ered
3y !ierre Curie (#%5$ I #$0?+1
H = C, - !#2.2.,"
Cagnetism in Chemistry #0$
C is the Curie constant o. the material and - is the a3solute temperature7 Though
many paramagnetic su3stances .ollo6 the Curie la6 many others .ollo6 the Curie2Weiss
(!ierre Weiss, #%?5 I #$*0+ la61
H = C,!- #" !#2.2.*"
6here # is the Weiss constant7 The suscepti3ility o. paramagnets sho6s little or no depen2
dence upon the applied Leld7
-em%erat1re+inde%endent %aramagnetism (t7i7p7+ is a .orm o. paramagnetism 6hich, as
its name implies, does not depend on temperature7 =nli4e normal paramagnetism, this
.orm o. paramagnetism is not the result o. the alignment o. magnetic moments already
present in the su3stance7 Li4e diamagnetism, it is the result o. or3ital electronic motion
ind1ced 3y the applied Leld7 T7i7p7 di..ers .rom diamagnetism in that 6hile the latter
in/ol/es the use o. ground2state or3itals only, the .ormer re0uires the use o. ecited2state
or3itals and is there.ore o. signiLcance only in those molecules or atoms 6here there are
ecited states o. lo6 energy, such as are sometimes .ound in compleed transition2metal
ions (see Chapter -+7
%&1&1& Magneti# s;s#epti?ilit0: "erromagnetism an/ anti"erromagnetism
The Curie or Curie2Weiss 3eha/iour is typical o. simple paramagnetic su3stances 3ut
there are other .orms o. paramagnetism 6hich sho6 a more complicated dependence
upon temperature and applied Leld7 These more comple 3eha/iours arise 6here there is
some degree o. interaction 3et6een the permanent, indi/idual molecular or atomic mag2
netic moments, so that i. thermal motion is su.Lciently reduced this interaction causes
the indi/idual moments to orient themsel/es, one 6ith respect to the other7 A. the mutual
orientation o. the moments is parallel (Digure #27-a+, the 3ul4 magnetic moment 3ecomes
/ery large and the material is said to 3e .erromagnetic7 A. the mutual orientation is antipar2
allel (Digure #27-3+, the material is anti.erromagnetic7 An each case there is a transition
temperature 3elo6 6hich the mutual interaction o. the magnetic moments is dominant and
Curie2Weiss 3eha/iour is replaced 3y .erro2 or anti.erro2magnetism7 This characteristic
temperature is 4no6n as the Curie temperature in the .ormer case and the ;ebel
(Louis ;ebel, #$0* I 2000+ temperature in the latter7
To o3tain 0uantitati/e relationships 3et6een o3ser/ed magnetic properties and molec2
ular parameters 6e must no6 deLne some o. the terms 6hich 6e shall use 6hen 6e
deri/e epressions .or the magnetic moments due to electronic or3ital motion and spinP
Lrst some deLnitions7
%&1&1' Magneti# Bel/s an/ /ipoles: some /eBnitions
A magnetic Leld ($+ is a /ector 0uantity and the direction o. the /ector, 3y deLnition, is
the direction in 6hich a hypothetical, isolated north pole 6ould mo/e under the inOuence
(a+
(3+
6ig;re %&1+ The relati/e orientations o. magnetic moments in .erromagnetic (a+ and anti.erro2
magnetic (3+ materials
##0 Some Special Topics
;
S
6ig;re %&1, The direction o. a magnetic Leld is the direction in 6hich a hypothetical, isolated
north pole 6ould mo/e
m
i
i
6ig;re %&1- A magnetic dipole, T, is a /ector representing the magnetic Leld due to a current
Oo6ing in a small loop7 (The current is a Oo6 o. positi/e charge+
o. the Leld7 Thus, the Leld can 3e represented 3y lines o. .orce 6hich carry arro6s
indicating its direction (Digure #27%+7
The deLnition o. a magnetic dipole (T+ is discussed in Bo #2727 At is a /ector .ormed
3y a current (i+ circulating in a small loop (area A+ (Digure #27$+ and its magnitude is
gi/en 3y1
T = iA !#2.2.5"
The /ector T is perpendicular to the plane o. the current loop and points in the direction
in 6hich a right2handed scre6 ad/ances 6hen turned in the direction o. the current Oo67
The units o. T are JT

#
or Am
2
7
An Bo #27, the Lange/in relationship 3et6een the measura3le, macroscopic property
(H + o. a su3stance and the magnetic moment (T+ o. the molecules composing that su32
stance is deri/ed7 We must no6 o3tain epressions .or T in terms o. the or3ital motion and
spin o. the electrons so as to esta3lish the /ital, 0uantitati/e lin4 3et6een the macroscopic
o3ser/a3le, suscepti3ility, and atomic and molecular electronic structure7
%&1&1( T$e magneti# e""e#t o" ele#troni# or?ital motion
We are interested in the magnetic Lelds, 6hich are created 3y the or3ital motion and spin
o. the electron, and the 6ay in 6hich these Lelds interact 6ith applied magnetic Lelds7 As
6e 4no6 .rom Section 27-, the Bohr theory o. the hydrogen atom is not a .ully Oedged
0uantum2mechanical theory7 ;e/ertheless, 6e can gain much insight into our present
pro3lem 3y means o. that theory and 6e no6 use it to calculate the magnetic dipole
generated 3y an electron mo/ing in a circular Bohr or3it7 We ma4e use o. the result
.rom classical electromagnetic theory that the magnetic dipole, o.ten called magnetic
dipole moment (T+ 6hich arises .rom a current (i+ Oo6ing in a closed loop is gi/en 3y
'0uation (#27275+7 The /ector (T+ is perpendicular to the plane o. the current loop and its
direction is related to the direction o. the current as sho6n in Digure #27#0
]
7
]
By con/ention, the current in a circuit is ta4en to Oo6 .rom regions o. positi/e potential to regions o. negati/e potential7
When the current is 3eing carried 3y electrons they Oo6 in the opposite direction7
Cagnetism in Chemistry ###
N
L
R
m
+
F
7
6ig;re %&1%. The angular momentum (L+ and magnetic dipole moment (T+ due to a current (i+
produced 3y an or3iting positi/e charge (7 +
A. the current Oo6s .rom + to +y the magnetic dipole /ector points in the +K
direction o. a right2handed coordinate system7 Thus, i. the current is the result o. an
or3iting positi/e charge, the dipole moment /ector is parallel to the angular momentum
/ector, L, (Chapter *+ o. the or3iting charge7 A positi/e charge (7 + mo/ing 6ith /elocity
(v+ in a circular or3it (radius r +, produces a current (i+ (charge per second+ o.1
i = 7v,2(r !#2.2.?"
so that, since A = (r
2
1
T = 7vr,2 !#2.2.-"
The classical angular momentum, L, o. an or3iting particle o. mass m
p
is m
p
vr so that
6e can also 6rite the magnetic moment in terms o. the or3ital angular momentum, L,
and 6e Lnd that1
T
=
7 L,2m
p
!#2.2.%"
in 6hich the radius o. the or3it no longer .eatures so that the epression applies to an
or3it o. any radius7
9ere 6e are interested in the case o. an electron in a Bohr or3it to 6hich the a3o/e
epression applies i. 6e su3stitute e (the electronic charge+ .or 7 and m
e
(the electronic
mass+ .or m
p
7 The change o. the sign o. the charge means that the angular momentum
and magnetic moment are no6 anti2parallel (Digure #27##+ and1
T = eL,2m
e
!#2.2.$"
We no6 recall that Bohr 0uantised the angular momentum o. his allo6ed or3its, a
result 6hich arises naturally in the .ull 0uantum mechanical analysis o. SchroM dinger
6ho
.ound (Chapter *+ that the allo6ed /alues o. angular momentum (L

+ are gi/en, in units
o. h,2( , 3y the 0uantum num3er (l+ through the .ormula1
#
L

= {
l!l
+
#"
} 2
h,2( !#2.2.#0"
(L

is used to a/oid con.usion 6ith the 0uantum num3er L in .urther de/elopment+7
Thus, the possi3le /alues o. T are1
# #
T
= {
l!l
+
#"
} 2
eh,*( m
e
{
l!l
+
#"
} 2
T
B
(#2727##+
N
L
R

F
e
m
6ig;re %&1%% The angular momentum (L+ and the magnetic dipole moment (T+ due to an or3iting
electron
6here eh,*( m
e
! T
B
" is the /ohr magneton 6hich, in SA units, has the /alue $.2-*0%
#0

2*
JT

#
(A m
2
+7 At is the .undamental constant 6hich relates the magnetic dipole
generated 3y an or3iting electron to its 0uantised angular momentum7 Thus, the magnetic
moment is also 0uantised7 An a many2electron atom the total magnetic moment may 3e
calculated using the a3o/e .ormula 3ut replacing l 3y L, the 0uantum num3er .or the
total or3ital angular momentum1
# #
T
= {
L!L
+
#"
} 2
eh,*( m
e
{
L!L
+
#"
} 2
T
B
(#2727#2+
Though the theory @ust descri3ed is a simple one, the a3o/e result agrees eactly 6ith
that o3tained 3y a .ull 0uantum2mechanical treatment7
%&1&1) T$e #onse@;en#es o" #$emi#al ?on/ing
When atoms .orm co/alent chemical 3onds the .reedom o. mo/ement o. the electrons,
and hence their or3ital angular momenta, can 3e much reduced and this also reduces
the corresponding magnetic moments7 This 71enching o. the or3ital angular momentum
6hich results .rom 3onding is /ery di.Lcult to calculateP it has pro/ed con/enient to
allo6 .or this phenomenon 3y introducing a parameter, g
l
, 4no6n as the or3ital g+factor
6hich can 3e determined 3y eperiment and, in .a/oura3le cases, calculated7 With this
modiLcation '0uation (#2727##+ reads1
and in a .ree atom, g
l
= #.07
#
T
=
g
l
{
l!l
+
#"
} 2
T
B
!#2.2.#,"
We 4no6 .rom Chapter * that i. 6e select a particular direction in space, almost
in/aria3ly the K2direction, then the or3ital angular momentum /ector characterised 3y the
0uantum num3er l can ha/e 2l + # orientations 6ith respect to the chosen ais, each
characterised 3y a /alue o. the 0uantum num3er m
l
, 6hich ta4es all the integer /alues
.rom +l to l and gi/es the /alue o. the K2component o. the angular momentum (l
K
+
through the e0uation1
l
K
=
m
l
h,2( !#2.2.#*"
The corresponding e0uation .or the K2component o. the magnetic moment is1
T
K
= g
l
m
l
T
B
!#2.2.#5"
The positi/e (negati/e+ /alues o. m
l
6hich characterise electrons 6ith positi/e (nega2
ti/e+ K2components o. angular momentum correspond, in the simple /ie6 descri3ed a3o/e,
to electrons or3iting the nucleus in opposite directions7 The magnetic moments due to
pairs o. electrons occupying or3itals 6ith e0ual and opposite /alues o. m
l
, e7g7 a .ull
shell o. #0 d2electrons, cancel and such atoms can ha/e no or3ital magnetic moment7
The presence o. magnetism due to or3ital electronic motion is there.ore a characteristic
o. atoms 6ith incompletely Llled electron su32shells7
%&1&1* T$e magneti# e""e#t o" ele#tron spin
At seems 0uite o3/ious that an or3iting electron can produce a magnetic moment and, as
6e ha/e seen a3o/e, the magnitude o. the moment can 3e readily calculated using classical
physics7 Less o3/iously, the spin o. the electron also gi/es rise to a magnetic moment,
though this cannot 3e calculated using a classical approach7 Andeed, it 6as only 6hen
<irac introduced relati/ity into 0uantum mechanics that the eact 0uantitati/e description
o. a phenomenon 6hich had 3een 6ell 4no6n eperimentally .or a3out ,0 years 6as
.ound7 The application o. the relati/istic theory is /ery di.Lcult, especially .or systems
containing more than one electron7 Dortunately ho6e/er, 3oth theory and eperiment sho6
that an ecellent 0uantitati/e description o. the magnetic moment due to electron spin
may 3e o3tained 3y a simple etension o. the theory deri/ed .or the or3ital motion7 Thus,
the magnetic moment due to electron spin angular momentum and its K2component may
3e 6ritten1
and
#
T
=
g
s
{
s!s
+
#"
} 2
T
B
!#2.2.#?"
T
K
= g
s
m
s
T
B
!#2.2.#-"
The /alue o. the spin angular momentum is not changed 3y chemical 3onding7 9o62
e/er, 6e retain the g2.actor 3ecause 6e Lnd that the correct relati/istic treatment o. the
magnetic moment due to electron spin sho6s that spin angular momentum gi/es rise to a
magnetic moment 6hich, .or a .ree electron, is 27002,22 times larger than that produced
3y an or3ital angular momentum o. the same magnitude7 Thus, .or magnetic moments
due to spin the g2.actor is 27002,227 Dor most purposes, and certainly .or ours, it is 0uite
su.Lcient to set g
s
=
2.07 As in the case o. or3ital magnetic moments, the moment arising
.rom a num3er o. electrons can 3e o3tained using the a3o/e .ormulae and replacing s
and m
s
6ith S and 5
s
, the 0uantum num3ers .or the total spin and its K2component,
respecti/ely7 A. the electron spins are antiparallel, i7e7 i. they are paired and ha/e e0ual
and opposite m
s
/alues, then their spin magnetic moments cancel7 9erein lies the essence
o. one o. the simplest 3ut most important uses o. magnetic measurements in the elucida2
tion o. molecular electronic structure I magnetism is a sensiti/e indicator o. the
num3er o. unpaired electrons7
Where there are 3oth or3ital and spin contri3utions, the total magnetic moment is the
/ector sum o. the t6o7
2
2
2
2
2
2
2
%&1&1+ Magnetism in pra#ti#e
So .ar, so goodP 6e ha/e o3tained the 3asic .ormulae 6ith 6hich, in principle, the magnetic
moments o. atoms and molecules may 3e calculated7 =n.ortunately, their application is
made di.Lcult 3y the .act that magnetically interesting species ha/e ground electronic
states 6ith unLlled electron shells and are conse0uently multiply degenerate7 Dor eample,
the ground state o. an atom ha/ing a single d electron outside closed shells is
2
<, 6hich
is ten2.old degenerateP this degeneracy may 3e partially li.ted 3y spin2or3it coupling to
gi/e a .our2.old degenerate
2
<
,
state and a si2.old degenerate
2
<
5
7 An a transition2
metal
2 2
ion these degeneracies may 3e li.ted .urther 3y the crystal Leld o. the surrounding ligands
(see Chapter -+7 There.ore, the BoltKmann population o. the components o. the ground
state must 3e ta4en into account 6hen the magnetic properties o. the species are calculated
and .ormulae applica3le to general cases can only 3e gi/en 6hen accompanied 3y ca/eats
regarding the relati/e magnitudes o. any ground state splittings and ;-7 The pro3lem is
discussed in detail in 8an 8lec4Gs classic treatise7
##
We illustrate some aspects o. the
pro3lem here 3y eamining the magnetic properties o. an atom 6ith one d electron under
/arious conditions rele/ant to the discussion o. Section -7?7
Dirst, 6e consider a gas2phase atom or ion 6ith one d electron outside closed shells7 All
#0 or3itals a/aila3le to the electron ha/e 6ell deLned spin and or3ital angular momenta
and their magnetic properties are summarised in Ta3le #2757
The magnetisation, 5 , o. an assem3ly o. N d
#
atoms can no6 3e calculated, .or
a Ou density / , using the e0uations deri/ed in Bo #27,7 We multiply the magnetic
moment o. each state 3y its population, sum the result and di/ide 3y the total population7
As an eample o. the contri3utions to numerator and denominator, consider |+2 +
#
7
An the numerator, this state is entered as a magnetic moment o. , Bohr magnetons
multiplied 3y a population .actor o. ep (,/ H;- +7 The population .actor also appears
in the denominator7 States ha/ing magnetic moments o. Kero are also populated so they
appear in the denominator, though not in the numerator7 The complete epression is1
N
{
,!e
,

e
,
"
+
2!e
2

e
2
"
+
2!e


e

"
}
5 = NT =
{e
,
+ e

,
+ e
2
+ e

2
+ 2!e

+ e

" + 2e
0
}
(#2727#%+
Ta?le %&1) The magnetic moments (T in Bohr magnetons+ o. the states
o. a single d electron and their energies (E+ in a Ou density (/ +
|G
l

K
|G !h,2(" 2s
K
|G !h,2(" T,T
B
EHJ
| 2
#
2 # +, ,/
|
#

#

#

#
+
2

2/
|
2
+
#

2
+
#
+
#

#/
|
0

#

0

#
+
#

#/
|
#
+
#

#
+
# 0 0
| +
#

#
+
#

# 0 0
|0 +
#

2
0
+# # +#/
| + 2
#

2
+2 # # +#/
| + # +
#

2
+# +# 2 +2/
| + 2 +
#

2
+2 +# , +,/
2
C
a
g
n
e
t
i
c

m
o
m
e
n
t


(
B
o
h
r

m
a
g
n
e
t
o
n
s
+
6here / H;-7 The pairs o. eponential terms 6ith e0ual and opposite eponents can
3e ta4en together as sinh or cosh so the Lnal e0uation .or 5 is1
N {,sinh!," + 2sinh!2" + 2sinh!"}
5 =
{cosh!," + cosh!2" + 2cosh!" + #}
!#2.2.#$"
This .unction, 4no6n as a Brillouin .unction, is plotted in the .orm 5,N /ersus /,-
in Digure #27#2 (graph #+7 T6o aspects o. the graph deser/e comment7
Where /,- P #.0, i7e7 6here / is small and - is large, the graph is linear7 This
is the Curie region 6here H is proportional to #H- 7 We shall comment on it .urther
3elo67 As /,- increases, ho6e/er, cur/ature sets in and the graph 3ecomes horiKontal
at /,- %7 This is 4no6n as sat1ration P it arises 6hen the states are split so .ar apart
3y the Leld andHor the temperature is so lo6 that only the lo6est state is occupied7 Dor
d
#
this is |2
#
6ith a magnetic moment o. +,T
B
, as the asymptotic /alue o. the
graph conLrms7 'perimental measurements o. the magnetisation o. transition2metal and
rare2earth compounds sho6 ecellent 0uantitati/e agreement 6ith this theory7
#2
Cuch o. the eperimental data on magnetic properties in the literature has 3een mea2
sured at modest Lelds (P0.5- + and temperatures not .ar .rom 25

C, 6ith the result that

the determination o. magnetic suscepti3ilities and their use in in.erring electronic con2
Lgurations etc7 has usually 3een 3ased upon measurements made in the Curie region o.
the magnetisation cur/e7 An /ie6 o. the dependence o. suscepti3ility on temperature these
results are no6 o. limited /alue7 An Bo #27, the slope, C, o. the magnetisation cur/e in
,75
,70
#7 d
#
state o. a .ree atom
275
27 d
#
atom in a strong,
octahedral crystal .ield
270
#75
,7 d
#
state 6ith or3ital angular
momentum .ully 0uenched
#70
075
070
070 270 *70 ?70 %70 #070
BHT (TeslaH>el/in+
6ig;re %&1%& Brillouin .unctions .or a single d electron
2
this region is sho6n to 3e ;T
o
T
2
H,; and this relationship might 3e used to determine the
re0uired magnetic moment7 Alternati/ely, since #.0 in this region, 6e may epand
the eponential .unctions in '0uation (#2727#%+ to @ust t6o terms and e/aluate 5 , 6hich
6e then Lnd to 3e1
There.ore1
5 = NT = N !,0,#0" = ,N/ , ;- !#2.2.20"
H = 5T
o
,/ = ,N T
o
, ;- !#2.2.2#"
6hich sho6s the epected linear dependence o. H upon #H- 7 Drom Bo #27, 6e also ha/e1
H = N T
o
T
2
,,;- !#2.2.22"
and e0uating the t6o results 6e Lnd T = ,T
B
7 The moment is in Bohr magnetons 3ecause
these are the units o. T used in Ta3le #2757 ;ormally, 6e 6ould calculate T .or the .ree
d
#
atom directly using the 0uantum num3ers .or the angular momentum o. the
2
< state
and a .ormula ('0uation (#27272,++ deri/ed 3y 8an 8lec4
##
.or the case 6here multiplet
splittings are small compared 6ith ;-7 This certainly applies here since 6e are assuming
that spin2or3it coupling is Kero7 We also assume that g
l
=
# and g
s
=
21
#
T
=
Z
{
L!L
+
#"
} +
*
{
S!S
+
#"
}
\
2
T
B
!#2.2.2,"
With this .ormula, .or a
2
< state 6here L = 2 and S =
#
, 6e Lnd T = ,T
B
, in agree2
ment 6ith the result a3o/e7
When multiplet splittings are large compared 6ith ;-, 8an 8lec4
##
has sho6n that1
#
T
=
g
Q
{
Q !Q
+
#"
} 2
T
B
!#2.2.2*"
6here1
g
Q
= # + {Q !Q + #" + S!S + #" L!L + #"},2Q !Q + #" (#272725+
T6o other magnetisation cur/es .or a d
#
atom are sho6n in Digure #27#27 Graph 2 is
o3tained i. the atom is su3@ect to a strong, octahedral crystal Leld 6hen, 3ecause o. the
large crystal2Leld splitting, only the d
y
, d
K
and d
yK
or3itals are occupied (see pro3lem
*+7 Graph , sho6s the magnetisation o. a .ree d
#
atom 6hich has only spin angular
momentum, all or3ital angular momentum ha/ing 3een 0uenched7 This is a case 6hich
6e are unli4ely to meet eperimentally7
To see ho6 a Curie2Weiss dependence o. suscepti3ility on temperature might arise
6e can consider the case o. a d
#
ion in the Leld o. eight e0ual charges arranged at the
corners o. a tetragonal antiprism7 To picture such an arrangement, imagine Lrst that you
ha/e eight charges arranged at the corners o. a cu3e7 ;o6 grasp t6o opposite s0uare .aces
and pull them apart so that the remaining .our .aces are no6 rectangular7 The resulting
3ody is a tetragonal prism7 Dinally, to o3tain the tetragonal antiprism rotate one s0uare
.ace through $0

relati/e to the other7 This arrangement o. charges can 3e ad@usted to
gi/e a d2or3ital energy2le/el scheme such as in Digure #27#,, in 6hich E is an ar3itrary
energy7 The magnetic moments (T+ o. the d2electron states and their energies (E+ in such
a crystal Leld are listed in Ta3le #27?7 Setting = /,;- and y = E,;- and epanding
eponential .unctions o. and y to t6o terms only 6e Lnd1
T = {20!# y" + %!# 2y" + 2},{*!# y" + *!# 2y" + 2} (#27272?+
'nergy
2E k#,cW
#E
k2,cW
0
k0,cW
6ig;re %&1%' The energy le/els o. the d states o. a single d electron in a tetragonal antiprismatic
crystal Leld
Ta?le %&1* The magnetic moments (T in Bohr magnetons+ o.
the states o. a single d electron and their energies (E+ in a tetrag2
onal antiprismatic crystal Leld and a Ou density (/ +
|G
| + 2
+
#

2
!l

K
+ 2s
K
"|G !h,2("
+,
T,T
B
,
EHJ
E + ,/
| + 2
| 2
| 2

#

2
+
#

2

#

2
+#
#
,
#
+#
+,
E + #/
E #/
E ,/
| + #
| + #
+
#

2

#

2
+2
0
2
0
2E + 2/
2E
| #
+
#

2
0 0 2E
| #

#

2
2 +2
2E 2/
|0 +
#
2
|0
#
2


+#
#
#
+#
+#/
#/
Cultiplying out the numerator and denominator, neglecting terms in y 6hich are
second order, 6e o3tain1
5 = NT = N {#5,!5 ?y"} = {#5N/ , ;- },{5 ?E, ;- } (#27272-+
There.ore1
H = 5T
o
,/ = {#5N T
o
, ;- },{5 ?E, ;- }
and multiplying top and 3ottom 3y - H5 6e Lnd1
H = {,N T
o
,;} #,{- ?E,5;} !#2.2.2%"
6hich sho6s that H has a Curie2Weiss temperature dependence 6ith # = ?E,5;7
%&1&1, S0stems o" intera#ting mole#;lar magnets
An Section #27272 the phenomena o. .erromagnetism and anti.erromagnetism 6ere 3rieOy
mentioned7 These properties are the result o. interactions 3et6een molecular or atomic
magnets and interest in materials 6hich sho6 them has gro6n rapidly 3ecause o. their
technological applications7 9ere 6e can address only the most 3asic aspect o. this su32
@ectP the mechanism o. the interaction7 At should 3e clearly understood at the outset that
the interaction is not the magnetic dipole2dipole interaction o. the constituent molecular
magnets7 A much2simpliLed 3ut instructi/e calculation 6ill ma4e this clear7 Aron, a 6ell2
4no6n .erromagnetic material, has a 3ody2centred cu3ic (3cc+ lattice in 6hich e/ery atom
is 2.*%

#0

#0
m .rom its eight nearest neigh3ours7 The indi/idual magnetic moment o.
the iron atoms is 2722 T
B
and the Curie temperature (-
C
+ 3elo6 6hich the .erromagnetic
3eha/iour is o3ser/ed is #0*, >7 The energy o. interaction (E
int
+ o. t6o magnetic dipoles
(T
#
and T
2
+ distance R apart is1
E
int
= {T
0
,*( }{!T
#
T
2
",R
,
,!T
#
+"!T
2
+",R
5
} (#27272$+
A. the dipoles are orientated at $0

to +1
E
int
= {T
0
,*( }{!T
#
T
2
",R
,
} !#2.2.,0"
This interaction 6ill 3e a maimum i. T
#
is parallel to T
2
so that, .or the particular
case o. iron1
E
ma
= {!2.22 $.2- #0

2*
"
2
,!2.*% #0

#0
"
,
} #0

-
= 2-.-- #0

25
J
Such an interaction in a 3cc lattice 6ill gi/e rise to a 3and o. energy le/els, each le/el
corresponding to a di..erent relati/e orientation o. the magnetic moments, 6ith a spread
o. #? times the a3o/e Lgure, i7e7 **.*,

#0

2*
J (see Section #27,7#+7
]
;o6, consider
the population o. this 3and o. energy le/els at #00 >, .ar 3elo6 -
C
, 6here the iron
should 3e clearly .erromagnetic7 According to the BoltKmann la6, at #00 > .or e/ery
#00 iron atoms in the lo6est state in the 3and there 6ill 3e approimately $- in the
highest state7 And, o. course, all the intermediate le/els 6ill 3e correspondingly highly
populated7 There.ore, e/en at #00 > all relati/e orientations o. the magnetic moments o.
the iron atoms 6ill 3e approimately e0ually populated, there 6ill 3e no o/erall ordering
o. the moments and no .erromagnetism7 We should also note that i. there 6as signiLcant
ecess population in the lo6est state the iron 6ould 3e anti.erromagneticU Clearly, the
energy associated 6ith magnetic dipole2dipole interaction is se/eral orders o. magnitude
too small to 3e responsi3le .or maintaining magnetic order up to #0*, > and, .urthermore,
the order 6hich it 6ould produce i. it 6ere stronger 6ould not 3e a .erromagnetic one7
What, then, is the mechanism o. this strong interactionJ
Section ##757, contains an etensi/e discussion o. the reasons .or the di..erence in the
energies o. the t6o ecited states o. helium 6hich ha/e the same conLguration, #s
#
2s
#
, 3ut di..er in the relati/e orientations o. the electron spins7 The triplet 6ith parallel
spins is signiLcantly lo6er in energy than the singlet in 6hich the spins are paired7
An that case too, the di..erence in energy is not a conse0uence o. the direct magnetic
interaction
]
This is an o/er2estimate o. the 3and 6idth since it is not possi3le to ha/e an arrangement in 6hich the magnetic moments
o. the central iron atom and each o. its eight nearest neigh3ours are all parallel to each other and perpendicular to the line
@oining each pair7 9o6e/er, this is not important since 6e shall sho6 that the interaction is much too small any6ay7
e
2
,r
#2
|T |S
T|
Q
#s2s

@
#s2s
0
S|
0 Q
#s2s
+
@
#s2s
+
o. the electron spin magnetic moments 3ut arises in an indirect 6ay .rom the e..ects o.
inter2electronic repulsion, a /ery much more potent .orce7
An order to understand more clearly 6hy the interaction 3et6een the magnetic centres
has the characteristics o. a dipole2dipole interaction, e/en though it is not, 6e Lrst return to
the helium atom pro3lem, .ollo6ing /an 8lec47
##
The symmetric ( + and antisymmetric
(

+ spin .unctions .or the t6o electron are1

#
and

+
=


=
2
{
L!#"

K!2"
+
K!#"

L!2"
}
!#2.2.,#a"

#
2
{
L!#"

K!2"

K!#"

L!2"
}
!#2.2.,#3"
At is su.Lcient .or our present purpose to consider only the t6o spin .unctions a3o/e
and neglect the other t6o symmetric .unctions, L!#" L!2" and K!#" K!2"7
The corresponding space .unctions are1

#
and

+
=


=
2
{
$
#s
!#"

$
2s
!2"
+
$
2s
!#"

$
#s
!2"
}
!#2.2.,2a"

#
2
{
$
#s
!#"

$
2s
!2"

$
2s
!#"

$
#s
!2"
}
!#2.2.,23"
Because, according to !auli, a total 6a/e .unction must 3e antisymmetric 6ith respect
to the echange o. electrons # and 2, the spin and space .unctions must 3e com3ined as
.ollo6s to .orm the triplet (|T + and the singlet (|S + state 6a/e .unctions1
|S =
+


!#2.2.,,a"
and
|T =


+
!#2.2.,,3"
The energies o. the triplet and singlet states di..er 3ecause the inter2electronic repulsion
in the t6o states is di..erent7 We can epress this result in terms o. the matri o. the
operator .or inter2electronic repulsion, e
2
Hr
#2
1
!#2.2.,*"
Q
#s2s
and @
#s2s
are the Coulom3 and echange electron repulsion integrals respec2
ti/ely (Section ##757,+ and 6e recall that the operator e
2
Hr
#2
operates solely on the space
.unctions,
+
and

7
We no6 eamine the operation o. the spin operator S

#

S

2
on the spin .unctions,
+
and

7 Dirst 6e epress the operator in terms o. the components o. the /ectors S

#
and S

2
1
S

#

S

2
=
S

#K
S

2K
+
S

#
S

2
+
S

#y
S

2y
=
S

#K
S

2K
+
#
# 2 # 2
2
{
S

+
S


+
S

S

+
}
(#2727,5+
Bearing in mind that an operator 6ith su3script # (2+ operates only on electron # (2+, 6e
can ta3ulate the results o. the a3o/e spin2component operators on the t6o spin .unctions1
#
S
#
S
2
#
*
*
2
@
|L!#" K!2" |K!#" L!2"
S

#K
S

2K

# #
*
|
L!#"

K!2"

*
|
K!#"

L!2"

# #
2
S

#+
S

2
0
2
|
L!#"

K!2"

2



+
2
|
K!#"

L!2"

0
=sing the results in the a3o/e ta3le and '0uation (#2727,5+ 6e Lnd that S

#
S

2
|T
=
# ,
+
*
|
T

and S

#

S

2
|
S
=
*
|
S

and 6e can also epress this result as a matri1
S

#
S

2
|T |S
T| +
#
0
!#2.2.,?"

S
|
0

,
Again 6e recall that, although 6e ha/e placed the sym3ol .or the complete 6a/e
.unction |T and |S at the head o. the columns and ro6s o. the matri, the matri
elements in this case are deri/ed solely .rom the spin .unctions7 The matrices #2727,* and
#2727,? can 3e lin4ed 6ith a matri ('0uation (#2727,-a++1
2@
#s2s
S

#
S

2
= e
2
,r
#2
Q
#s2s
+
#
or, in terms o. the complete matrices ('0uation (#2727,-3++1
#s2s
!#2.2.,-a"

@,2 0
0 ,@,2

Q @ 0 =
0 Q
+
@

Q + @,2 0 +
0

Q
+
@,2

(#2727,-3+
6here the su3scripts #s,2s on Q and @ ha/e 3een omitted to simpli.y the notation7 The
rules o. matri alge3ra re0uire that the e0uality holds .or e/ery set o. corresponding matri
elements, e7g7 .or (# #+, @,2 = Q @ Q + @,27 This result sho6s that the eigen/al2
ues o. the operator e
2
Hr
#2
, 6hich are the di..erent energies o. the parallel (symmetric
spin
.unction+ and anti2parallel (antisymmetric spin .unction+ electron pairings, plus a constant
term (Q + @,2+ are e0ual to the eigen/alues o. the operator 2 @ S

#
S

2
7
:emar4a3ly, the spin operator S

#
S

2
mimics the operator e
2
Hr
#2
, 6hich is in .act
responsi3le .or the
energy di..erence 3et6een the parallel and antiparallel coupling o. the magnetic moments,
and pro/ides a much simpler 6ay o. calculating the relative energies o. the coupled le/els
than 6ould other6ise 3e the case7 An important 0uestion remains7 The a3o/e analysis is
3ased on the /ery simple system o. @ust t6o electrons in the helium atomP does it apply
to other systems 6ith many more electronsJ <irac has sho6n that it does7 An a many2
electron molecule or crystal the spins o. any pair o. electrons, i and @, may 3e regarded as
3eing coupled together 3y an energy o. the .orm 2 @
i@
S

i
S

@
7 ;ote that the
su3scripts
on > relate to the spatial 6a/e .unctions o. the electrons i and @ so that the /alue o. the
coupling energy 6ill al6ays depend upon the distri3ution o. the electrons in/ol/ed7
%&1&1- A note o" warning
The readerGs attention is dra6n to some potential causes o. con.usion7 The sym3ol @
i@
has 3een used here in the epression .or the coupling .or the sa4e o. consistency 6ith the
2
2
2
2
2
2
2
discussion o. the helium atom in Chapter ##7 But in the magnetochemistry literature Q
is in/aria3ly used in this contet7 At is most important to note that the magnetochemistGs
Q is our @ and not the Coulom3 integral 6hich 6e ha/e called Q 7 =n.ortunately, there
is also a lac4 o. consistency in the .orm o. the coupling epression used in applicationsP
some authors neglect the .actor o. 2 andHor the negati/e sign7
%&1&1%. An appli#ation
As an eample o. the a3o/e theory 6e consider the case o. a triangular arrangement o.
three interacting centres (Digure #27#*+7 Systems o. this .orm, in 6hich the magnetism
deri/es .rom transition2metal ions lin4ed 3y their ligands, ha/e 3een etensi/ely studied7
An order to limit the siKe o. the pro3lem 6e consider the case 6here the magnetism at each
centre deri/es .rom one unpaired spin only, i7e7 S
K
=
#
7 The 9amiltonian operator is1
9

= 2{@
#2
S

#
S

2
+ @
2,
S

2
S

,
+ @
,#
S

,
S

#
} (#2727,%+
and 3y epressing S

#
S

2
in terms o. S

K
, S

+
and S

, as 6e ha/e done a3o/e, 6e o3tain

the %

% matri o. 9

as t6o # # and t6o , , matrices1

|LLL |KKK

LLL
|
#
!@
#2
+
@
2,
+
@
,#
"

KKK
|
#
!@
#2
+
@
2,
+
@
,#
"
2 2
|LLK |LK L |KLL
LLK |
#
!@
#2
+ @
2,
+ @
,#
" @
2,
@
,#
LK L| @
2,
#
!+@
#2
+ @
2,
@
,#
" @
#2

KLL
|
@
,#

@
#2
#
!
+
@
#2

@
2,
+
@
,#
"
|KK L |K LK |LKK
KK L|
#
!@
#2
+ @
2,
+ @
,#
" @
2,
@
,#
K LK | @
2,
#
!+@
2,
+ @
#2
@
,#
" @
#2

LKK
|
@
,#

@
#2
#
!
+
@
#2

@
2,
+
@
,#
"
When @
#2
= @
2,
= @
,#
@ these .our matrices gi/e .our2.old degenerate eigen2
/alues o. +, @,2 and , @,27 When @
#2
= @
2,
@ and @
,#
= .@ , 6here . is an
ar3itrary parameter, 6e Lnd t6o2.old degenerate eigen/alues o. !* .@",2 and ,.@,2
@
,#
#
@
#2
, 2
@
2,
6ig;re %&1%( Three interacting magnetic centres
'nergy
+, @H2
+(* .+@H2
+,.@H2
0 I I I I I I I I I I I I I I I I I I I
(2 + .+@H2
, @H2
. = #70 070 V . V #70
6ig;re %&1%) The energy le/els o. three interacting magnetic centres
and a .our2.old degenerate eigen/alue o. !2 + ."@ ,27 'nergy2le/el schemes .or . = #.0
and 0.0 P . P #.0 are illustrated in Digure #27#57
%&1' THE 8AN3 THE2RY 26 S25I3S
The electrical properties o. conductors, semiconductors and insulators are argua3ly the
material properties most important to modern technology7 The 3asic 0uantum2mechanical
description o. the electronic structures o. solids and the interpretation o. their properties
3y that means has played a /ital role in the de/elopment o. the technology7 This is a
3ranch o. solid state physics 6hich 6e can only touch upon here7 We shall emphasise
the elementary principles o. the 0uantum2mechanical description o. the 3onding in solids
and Lnd it to 3e a logical etension to inLnite arrays o. interacting atoms o. the concepts
and methods already descri3ed in our treatment o. discrete molecules7 We approach the
pro3lem .rom t6o di..erent /ie6points7
%&1'1% T$e tig$t ?in/ing approximation
Consider the sodium atomP the ionisation energy o. the ,s electron is only 57#* e87
To remo/e the net electron 527*, e8 are re0uired 6hich, e/en allo6ing .or the .act
that this is the remo/al o. an electron .rom ;a
+
, sho6s ho6 high the energy o. the
,s electron is compared 6ith the 2p electron, i7e7 the ,s electron is much less tightly
3ound to its atomic core than the 2p electron7 At is clear .rom these Lgures that the
unpaired ,s electron must play an important role in the 3onding in sodium metal and,
although 6e shall Lnd that the unoccupied ,p or3itals are also in/ol/ed, the concept o. the
interaction o. the singly occupied ,s or3itals pro/ides our starting point7 We no6 recall
the molecular or3ital theory o. the hydrogen molecule (Section ?75+, 6here t6o hydrogen
#s A"s o. energy E
#s
com3ine to .orm a 3onding and an anti3onding C" o. energy
E
#s
+
K and E
#s

K respecti/ely7 K is the interaction 3et6een pairs o. ad@acent or3itals
The Band Theory o. Solids #2,
and is a negati/e 0uantity7 A. 6e ma4e the reasona3le assumption that the interaction o.
t6o sodium atoms is conLned to the interaction o. their t6o ,s A"s 6e can dra6 an
energy2le/el diagram o. eactly the same type .or ;a
2
7 We no6 as4 6hat 6ould 3e
the result o. adding .urther sodium atoms to .orm linear ;a
,
;a
*
. . . ;a
;
molecules,
6ith
K = 0 only 3et6een ad@acent atoms7 This is a pro3lem .or 6hich there is an alge3raic
solutionP the energies are gi/en 3y the .ormula1
E
m
= E
,s
+ 2K cosZm(,!; + #"\ m = # 2 , . . . ; (#27,7#+
6here m is a 0uantum num3er characterising the energy le/el and E
m
increases 6ith
increasing m7 The e0uation a3o/e applies to a linear chain o. car3on 2p
K
A"s such as
6e ha/e in the 9uM c4el theory and the interaction (K + has eactly the same meaning
here as it did in Section #27#7 An the limit o. a /ery large /alue o. ; 6e Lnd the lo6est
and highest energy le/els, E
#
and E
;
, at1
E
#
= E
,s
+ 2K cosZ(,!; + #"\ E
,s
+ 2K cosZ0\ = E
,s
+ 2K
E
;
= E
,s
+ 2K cosZ;(,!; + #"\ E
,s
+ 2K cosZ( \ = E
,s
2K (#27,72+
All the other ;22 energy le/els must Lt in 3et6een these t6o outer limits7 They .orm a
*and o. closely spaced le/els7 The etension o. this concept to a three2dimensional array
o. sodium atoms is 0uite straight.or6ard7 An a ro6 o. sodium atoms each atom has t6o
nearest neigh3ours and the 6idth o. the 3and is 2 2K = *K P as a3o/e7 Dor a simple
cu3ic lattice each atom has si nearest neigh3ours, t6o along each o. the three Cartesian
aes, and the total spread o. the 3and is ? 2K = #2K 7 An .act, at normal temperatures
and pressures sodium metal has a 3ody2centred cu3ic lattice 6ith eight nearest2neigh3our
atoms and the spread o. the 3and is #?K 7 The su3@ect is clearly eplained 3y >ittel7
#,
A
#2mm cu3e o. sodium contains a3out #0
20
atoms, each o. 6hich pro/ides one ,s A", so
that the num3er o. energy le/els in the 3and, 6hich eperiment sho6s to 3e approimately
*.%

#0

#$
J .rom top to 3ottom, is etremely large and they .orm, to all intents and
purposes, an energy continuum7 A. this 6as the only contri3ution to the 3onding in sodium
metal 6e 6ould no6 place the ; electrons .rom ; sodium atoms in the lo6er ;H2 or3itals
o. the 3and and our description o. the 3onding 6ould 3e complete7 But the ,s or3itals
are not the only ones 6hich o/erlap as the sodium atoms approach each other as a more
detailed study re/eals7
An approimate calculated 3and structure .or sodium metal as a .unction o. interatomic
distance (r + is sho6n in Digure #27#?7 As r is reduced, the unoccupied ,p or3itals interact
Lrst and a 3and 3egins to .ormP the highest and lo6est le/els o. the 3and are indicated 3y
dotted and solid lines respecti/ely7 But since sodium has no ,p electrons the .ormation o.
this 3and generates no 3onding7 9o6e/er, as r is reduced .urther the ,p 3and 3roadens
and the ,s or3itals, 6hich ha/e one electron per atom, 3egin to interact and 3onding
commences7 At r *5 nm the highest le/el o. the ,s 3and crosses the lo6est le/el o.
the ,p 3and and the e0uili3rium /alue o. r !r
o
" .ollo6s at ,- nm7 At r
o
the lo6er part
o. the ,p 3and is lo6 enough to 3e populated 3y some o. the electrons .rom the ,s 3and
and the ;aI;a 3onds .ormed ha/e 3oth ,p and ,s character, i7e7 they are hy3rid 3onds
(Section ?7#5+7 There is no signiLcant interaction o. the 2p or3itals at r
o
, and, a fortiori,
o. the 2s and #s, 6hich is 6hy they ha/e not 3een included in the diagram7
As 6ith sodium, in general a num3er o. di..erent atomic or3itals may 3e epected to 3e
in/ol/ed in metal 3onding7 An a typical Lrst2ro6 transition metal, .or eample, *s, *p and
,d A"s contri3ute to 3and .ormation and 3onding7 'ach type o. or3ital 6ill .orm a 3and
'
n
e
r
g
y

(
a
r
3
i
t
r
a
r
y

u
n
i
t
s
+
#2* Some Special Topics
The 3and structure o. sodium metal
25
20
,p
#5
,s
#0
2p
5
0
0 25
r
0
50 -5 #00 #25
Anteratomic distance (nm+
6ig;re %&1%* The 3and structure o. sodium metal
6ith its energetic centre at roughly the energy o. the corresponding A" in the isolated
atom, and an idealised 3and structure might appear as represented in Digure #27#-(a+7
9o6e/er, 6e need to add more in.ormation to this 3are picture7 An the Lrst instance
6e must indicate on our diagram the occupation o. the energy le/els 3y electrons7 We
sho6 this (Digure #27#-(3++ 3y shading the 3ands, or parts o. 3ands, 6hich are Llled 6ith
electrons7 The energy at the 3order 3et6een occupied and unoccupied le/els is 4no6n as
the Dermi le/el, a.ter 'nrico Dermi 6hose name 6e ha/e already encountered7
We must also recognise that the 6idth o. a 3and, i7e7 the energy separation 3et6een the
highest and lo6est energy le/el, depends upon the interaction (K +, 6hich 6ill not 3e the
same .or the three types o. A"s7 The most important .actors determining the magnitude
o. K are1
The interatomic distanceP the greater the distance the smaller the interaction and the
narro6er the 3and7
The closeness 6ith 6hich the electron is 3ound to the atomP the more tightly the electron
is conLned to the atom the smaller the interaction and the narro6er the 3and7
Dinally, no indication o. the num3er o. le/els at any particular energy is gi/en in
Digures #27#-(a+ and #27#-(3+7 Generally, the num3er o. le/els at the etremes o. the
3and energy 6ill 3e lo67 As 6e mo/e to6ards the centre o. the 3and the num3er o.
'nergy
d23and
p23and
empty 3and
Dermi le/el
partially .illed 3and
*p23and
,d23and
s23and
.ull 3and
*s23and
<ensity o. states
(a+ (3+ (c+
6ig;re %&1%+ Band structure .or a typical Lrst2ro6 transition metal
le/els per energy unit, the density of states, 6ill increase7 Thus, the 3and structure o. a
typical transition metal might appear as in Digure #27#-(c+7
%&1'1& T$e ele#tronI gas F"ree9ele#tronG approximation
An alternati/e approach to a theoretical description o. the structure o. metals 6as sug2
gested 3y Arnold Sommer.eld (#%?% I #$5#+ in #$2%7 At is 3ased on a pertur3ed,
.ree2 electron model7 A. 6e again thin4 o. sodium as our eample 6e can imagine that the
,s electrons, one .rom each atom, are e..ecti/ely detached .rom their atomic cores and
.orm a sea or gas o. mo3ile electrons .ree to roam, almost at 6ill, through the metal7
They are not completely .ree 3ecause they mo/e in the periodic potential Leld o. the
positi/ely charged cores, 6hich ma4es important modiLcations to their energies and 6a/e
.unctions7 Dor the sa4e o. simplicity 6e shall consider a one2dimensional model
de/eloping .urther the description o. an electron in a linear 3o 6e initiated in Sections
,7? and ,7-7
We Lrst ma4e some modiLcations to the 6a/e .unctions descri3ed there7 We noted
that it 6as only possi3le to ha/e electrons mo/ing .reely in one dimension i. there 6ere
no 3oundaries to restrict the motion and that, under those conditions, the 6a/e .unctions
6ere eigen.unctions o. 3oth the operator .or linear momentum and o. the 9amiltonian7
!airs o. 6a/e .unctions that ha/e e0ual energies and correspond to electrons mo/ing
in the positi/e and negati/e 2direction 6ith e0ual and opposite linear momenta can 3e
identiLed7 9o6e/er, 6e did not normalise these 6a/e .unctions, and 6e must address
that pro3lem here7 Also, 3ecause 6e are interested in the e..ect upon the electrons o. the
periodic Leld o. the atomic cores, 6e need to choose a .orm o. our co2ordinate that
reOects the arrangement o. the cores7 "ur one2dimensional model consists o. a series o.
positi/ely charged atomic cores positioned at e0ual inter/als (a+ along the co2ordinate7
The potential energy o. a .ree electron (V + 6ill 3e lo6est 6hen it is at a core and

+;
S
+;
(3+
a
8 (a+
0p 2p *p ?p %p #0p

L
6ig;re %&1%, The core potential o. a linear array o. metal atoms (a+ Sta3le
+

+
and unsta3le

electron distri3utions (3+

highest 6hen it is mid6ay 3et6een them Digure #27#%(a+7 A suita3le alge3raic .orm .or
the potential is1
V = / cos!2;( HL" !#2.,.,"
6here L is a length 6hich contains ; cores (L = ;a+ and is assumed to 3e /ery much
larger than a, so that the energy le/els o. the system 6hen V = 0 are E
n
= n
2
h
2
,%m
e
L
2
and still /ery closely spaced7
Dollo6ing Section ,7-7#, 3ut epressing the co2ordinate in a manner compati3le 6ith
#27,7,, the pairs o. normalised 6a/e .unctions 6hich 6e shall use are1
#

n
=
!#,2L"
2
ep
{
in( ,L
}
!#2.,.*"
6here n is the 0uantum num3er and i =

!#" (Appendi %+7 The 6a/e .unctions are

normalised to unity and orthogonal 6ithin any section o. the system 3et6een L L and
L + L, 6here L is an ar3itrary point along the chain o. cores1

L+L
#

L+L
i( n,L
+i( n,L
LL

n

n
d
=
2 L
e


e d
LL
#

L
+
L
# d =
#
ZL + L L + L\ = #
=
2 L
L L
2 L
Since L is deLned as the length containing a speciLc num3er o. atomic cores, the
relati/e position 6ith respect to the cores o. the point L + L is eactly the same as that o.
L L, independent o. the /alue o. L7 There.ore, in choosing these limits 6e are simply
recognising the periodic nature o. the se0uence o. cores or latticeP i7e7 6e are using
%eriodic *o1ndary conditions7
We must no6 eamine the e..ect o. the potential (V + upon and the 6a/e .unctions
and energies o. the mo3ile electrons7 An order to approach the essentials o. the pro3lem
as directly as possi3le 6e esche6 a general analysis and concentrate upon a /ery special
case7 What is the e..ect o. this potential upon the 6a/e .unctions and energies o. a pair o.
electrons ha/ing e0ual 3ut opposite /alues o. n, i7e7 t6o electrons o. e0ual energy (linear
momentum+ mo/ing in opposite directions along J
We can /ie6 the mathematics either as an application o. degenerate pertur3ation theory
(Appendi *+ or as the construction o. t6o ne6 .unctions .rom a 3asis set o. the t6o

LL
/
/
.unctions (Appendi 2+1
and
#

+n
=
!#,2L"
2
ep
{+
in( ,L
}
#

n
=
!#,2L"
2
ep
{
in( ,L
}
!#2.,.5"
We re0uire the matri elements

n
|V

|

n
and 6e must remem3er that | implies
the comple con@ugate o. | 7 As an eample o. a diagonal element 6e ha/e1


+
n
|
V
|

+
n
=

/

L+L
e
i( n,L
cos

2;(
L

e
+i( n,L
d
2L
LL
/

L
+
L
# cos

2;(

d
=
2L
LL L
L+L
/ L

2;(

sin
=
2L

2;(
/
L

2;(L

LL
=
2;(

cos
L
sin 2;( = 0
The result o. Kero is scarcely surprising since 6e 4no6 that the 6a/e .unctions

n
descri3e electrons uni.ormly distri3uted along and there.ore su3@ect e0ually to the pos2
iti/e maima and negati/e minima o. the potential V 7 As an eample o. one o. the
o..2diagonal matri elements 6e e/aluate1

n
|
V
|

+
n
=

/

L+L
e
+i( n,L
cos

2;(

e
+i( n,L
d
2L
LL
L
/

L
+
L
e
+
i 2( n,L

cos

2;(

d
=
2L
LL
L
/

L
+
L

cos

2n(
+ i sin

2n(

cos

2;(

d
=
2L
L

L
L L L
/

L
+
L

cos

Zn + ;\2(

+ cos

Zn ;\2(

d
=
*L
LL
L L
i/

L
+
L

sin

Zn + ;\2(

sin

Zn

;\2(

d
*L
LL
L L
A. n = ; each o. the .our integrals a3o/e gi/es KeroU 9o6e/er, i. n = ; the integration
o. the Lrst and third terms is essentially unchanged and the .ourth goes to Kero e/en 3e.ore
the integration is per.ormed7 But the second term no6 3ecomes the integral o. cos!0" = #
and 6e ha/e1

/

L
+
L
cos!0" d
=

Z\
L+L
=

*L
LL
*L 2
Dor the pair o. 6a/e .unctions (

;
+ 6e can no6 epress the total energy, 4inetic
plus potential, in the .orm o. the 9amiltonian matri1
#
+; +;
9

|

+;
|

;

2 2 2

+;
|
; h ,%m
e
L /H2
2 2 2

;
|
/H2 ; h ,%m
e
L
By su3tracting E .rom each diagonal element and multiplying the resulting matri out
as a determinant (Appendi ?+ 6e o3tain the characteristic e0uation o. the matri1
!;
2
h
2
,%m
e
L
2
E"
2
/
2
,* = 0
.rom 6hich 6e Lnd the eigen/alues o. the total energy as ;
2
h
2
,%m
e
L
2
/H27 Since the
diagonal elements o. the a3o/e matri are e0ual, the t6o .unctions 6ill 3e e0ually in/ol/ed
in 3oth ne6 eigen.unctions 6hich, 6hen normalised, 6ill there.ore 3e o. the .orm1

#
and

+;
=

;
=
2
!
+;
+

;
"

#
2
!
+
;

;
" !#2.,.?"
We can Lnd 6hich o. our t6o energies 3elongs to 6hich eigen.unction simply 3y
e/aluating the integrals
+
;
|9

|
+
;
and

;
|9

|

;
using the matri elements
.rom the 2

2 matri o. 9

#
a3o/e7 Dor eample1


+;
|
9

|

+;
=
2


+;
+

;
|
9

|

+;
+

;

=
2
{
+;
|9

|
+;
+
;
|9

|
;
+
;
|9

|
+;
+
+;
|9

|
;
}
# 2 2
2 2 2 2 # # 2 2 2 #
=
2
{
; h ,%m
e
L
Similarly1
+
; h ,%m
e
L

2
/

2
/
} =
; h ,%m
e
L

2
/
2 2 2 #

;
|
9

|

;
=
; h ,%m
e
L
+
2
/
We see that the e..ect o. V has 3een to com3ine the 6a/e .unctions o. electrons
tra/elling 6ith e0ual /elocities in opposite directions in e0ual proportions, con/erting
running to stationary 6a/es7 The result o. the miing has 3een to raise the energy o.
one com3ination and to lo6er the energy o. the other7 The origin o. this e..ect o. the
introduction o. V is clear 6hen 6e eamine the .orms o. the ne6 6a/e .unctions1

#
#

+;
=
2
!
+;
+

;
"
=
!#,2L"
2
Zep
{+
i;( HL
} +
ep
{
i;( HL
}
\
#
=
!#,2L"
2
Zcos
{
;( HL
} +
i sin
{
;( HL
} +
cos
{
;( HL
}
i sin
{
;( HL
}
\
#
=
!#,2L"
2
Z2 cos
{
;( HL
}
\
The corresponding electron density is1

= !#,L"Z2 cos
2
{;( HL}\ = !#,L"Z# + cos{2;( HL}\
Similarly1

;
= !#,L"Z# cos{2;( HL}\
The argument o. the cosine in the epressions .or the electron density is eactly the
same as that in the potential V and the /ariation o. the density 6ith is there.ore /ery
similar to that o. V 7 Digure #27#%(3+ sho6s that
+;

+;
pea4s at the position o. the


!;#"
|
0 !;

#"
2
0 0

/H2 0


+;
|
0 0
2
/H2
0 0


;
|
0 0
/H2
2
0 0


+!;+#"
|
0
/H2
0 0
2
0


!;+#"
| /H2
0 0 0 0
2
2
2
cores 6here V is at its lo6est 6hilst the re/erse is true .or
;

;
7 This is the
reason
.or the energy di..erence o. / 3et6een the t6o .unctions7 The periodic potential o. the
cores has com3ined t6o tra/elling 6a/es 6ith 0uantum num3ers +; and ; to gi/e
t6o standing 6a/es o. di..erent energies and has created an energy gap, or 3and gap,
in the continuum (L is assumed to 3e /ery large+ o. energy le/els at that point7 A more
general analysis sho6s that 6e epect o..2diagonal matri elements o. V to occur 3et6een
all pairs o. 6a/e .unctions o. the .orm
m
and
n
i. n m = 2;, since such cases
6ill also gi/e rise to the integral o. cos!0" = #7 Thus, the matri o. |
+
;
and |

;
sho6n a3o/e is simply a part o. a much larger matri, in/ol/ing all the unpertur3ed states
(
n
+7 The .ollo6ing is a small section o. it, centred on the matri o. |
+;
and |
;
P

=
h
2
,%m
e
L
2
1
9

|

+!;#"
|

!;#"
|

+;
|

;
|

+!;+#"
|

!;+#"

2

+!;#"
|
!;

#" 0 0 0 0

/H2
;
;
!; + #"
!; + #"
We see that the matri is 3loc4ed out (Appendi ?+ into the single central 2 2 matri
and pairs o. identical 2 2 matrices o. the .orm1
9

|

+!;4"
|

!;+4"

2
and


+!;4"
|
!;

4"

/H2


!;+4"
|
/H2 !;
+
4"
9

|

!;4"
|

+!;+4"

2

!;4"
|
!;

4"

/H2


+!;+4"
|
/H2 !;
+
4" 7
The eigen/alues o. these matrices are easily .ound to 3e1
2 2 2 2 2
2 #,2
E
4
=
Z;
+ 4 \ Z*; 4 + / ,*\
An the cases 6here 4 = 0 the t6o .ree2electron .unctions, 6hich are mied, do not ha/e
eactly the same energy and so their displacement .rom their original positions 6ill 3e
smaller than the maimum o. /H27 The displacement 6ill decrease 6ith increasing 4 and
there 6ill no longer 3e e0ual miing o. the t6o 6a/e .unctions7 Thus, as 6e mo/e into
a 3and and a6ay .rom the 3and edges the standing 6a/es 6ith Kero electron momentum
gradually metamorphose into running 6a/es 6ith increasing electron momentum7
"ne can en/isage other /alues o. n and m .or 6hich n m = 2;, e7g7 !,; + 4"
!; + 4" = 2;7 But the energies o. the corresponding 6a/e .unctions 6ill 3e /ery di..erent
and to a good approimation the eistence o. o..2diagonal elements in the energy matri
'
n
e
r
g
y
; + 4
; + ,
V = 0
V 0
k4k
,
2
V = 0
(; + 4+
(; + ,+
; + 2
; + #
#
(; + 2+
0
(; + #+
;
;
; #
0
; 2
#
; ,
2
(; #+
(; 2+
(; ,+
,
6ig;re %&1%- The .ormation o. a 3and gap 3y a periodic potential, V
may 3e ignored7 The e..ect o. a periodic pertur3ation on the energy le/els o. a .ree
electron is illustrated in Digure #27#$7 The stac4s o. energy le/els at the sides o. the
diagram are those o. the unpertur3ed system (V
=
0+ immediately a3o/e and 3elo6 E
;
7
The degenerate pairs o. states are plotted separately according to the sign o. their linear
momentum7 The pertur3ed le/els (V = 0+ are plotted in the centre o. the diagram7 The
t6o 6ith 4 = 0 are singly degenerate, 3ut the remainder occur in degenerate pairs and are
represented 3y hea/ier lines7 ". the .our le/els characterised 3y a /alue o. |4| = 0, one
o. each degenerate pair arises .rom the V 2induced miing o.
+
!;
+
4"
and

!;

4"
and
the other t6o .rom the miing o.

!;
+
4"
and
+
!;

4"
7 The dashed lines, 6hich indicate
the connection 3et6een pertur3ed and unpertur3ed states, ha/e 3een limited to the case
o. |4| = # in the interests o. the clarity o. the Lgure7
Digure #27#$ is artiLcial in a num3er o. respects, most nota3ly in the large spacing
3et6een the le/els, 6hich in a realistic /ie6 6ould 3e much closer together7 But it does
sho6 ho6 the e..ect o. the potential V is to create a gap o. /, centred on E
;
, in the
energy le/els 6ith a conse0uent increase in the num3er o. le/els (density o. states+ in
the regions immediately outside the range E
;

/,27 This situation is unchanged and the
gap 6ill not decrease i. 6e no6 imagine the energy le/els to 3e such that there is no
discerni3le space 3et6een them 6hen V = 07
Dinally, 6e must note that in a real, three2dimensional metal the cores 6ill .orm periodic
potentials in many directions, and not necessarily along the three Cartesian co2ordinates,
and the 3and structure 3ecomes /ery complicated7 The treatment o. a real metal crystal
lattice re0uires more ad/anced theoretical methods7
%&1'1' Mole#;lar an/ ioni# soli/s
The tight23inding and .ree2electron descriptions o. solids seem to 3e naturally applica3le
to single crystals composed o. one type o. atom onlyP a crystal o. sodium (.ree2electron+
or o. diamond (tight23inding+ .or eample7 The di..ering physical properties o. these t6o
eamples can 3e related to the delocalised electrons in the sodium and the localised elec2
trons in diamond7 An the case o. molecular solids, ho6e/er, a distinction must 3e dra6n
3et6een the 3onding o. the atoms o. one molecule to those o. another, the intramolecular
3onding, and the intermolecular 3onding 6ithin each molecule7 Dor the lighter elements,
e7g7 solid hydrogen, phosphorus or 3enKene, 6here the intermolecular 3onds are .ar
stronger than the intramolecular, the 3and theory has little to o..er7 But as 6e ascend
the periodic ta3le the di..erence 3et6een the strengths o. the intra2 and inter2molecular
3onds decreases and 3and models 3ecome more applica3le7
Dor ionic solids too, the tight23inding /ersion o. the 3and theory is appropriate7 A. 6e
ta4e sodium chloride as our eample and assume that the trans.er o. one electron .rom
sodium to chlorine is complete, then the ,s and ,p or3itals o. the Cl

.orm ,s and ,p
3ands, 3oth o. 6hich 6ill 3e .ull 3ecause the chloride ion has a .ull complement o. ,s
and ,p electrons7 <etailed calculations sho6 that at the e0uili3rium internuclear distance
these t6o 3ands and the empty ;a
+
,s 3and are /ery narro6 and that the gap 3et6een
the highest Llled 3and, Cl

,p, and lo6est unLlled 3and, ;a
+
,s, is large, approimately
%2

#0
*
J mol

#
7 The narro6ness o. the 3ands conLrms the concept o. an ionic 3ond,
6hich is largely electrostatic in nature since it is atomic or3ital o/erlap, and co/alent
3onding, 6hich causes the energy spread o. a 3and7 The large gap 3et6een a .ull valence
*and, i7e7 a 3and .ormed .rom the /alence atomic or3itals o. the 3onded atoms, and the
empty 3and a3o/e it eplains 6hy sodium chloride is an insulator, vide infra7
%&1'1( Appli#ations
At is only .air to say that the simplicity o. the 3asic principles o. the a3o/e theoretical
descriptions 3elies the di.Lculty o. using them 0uantitati/ely7 Dor 0uantitati/e purposes
many more sophisticated interpretations o. the 3asic ideas ha/e 3een de/eloped7
#,I#5
7
But 6e might 3ear in mind here that it 6as in their introduction to a re/ie6 o. the
theory o. metals that Wigner and SeitK made the remar4s 0uoted in Section ?727 Dor our
present purposes, these theories are more important .or the light they shed on the reasons
underlying the general properties o. solids, and .or the 6ay in 6hich they sho6 ho6 the
3onding in discrete molecules and etended arrays o. atoms can 3e eplained 6ith the
same concepts7 The types o. solids to 6hich the a3o/e theories are most applica3le are
summarised in Ta3le #27-7
%&1'1) Metals< ins;lators an/ semi#on/;#tors
The /arying 3eha/iour o. solids 6ith respect to the conduction o. an electric current
is one o. their most 6ell24no6n and technologically important properties7 The range
Ta?le %&1+ Areas o. application o. the .ree2electron and tight23inding theories
Dree2electron approimation 6ith V /ery small A4ali metals
Dree2electron approimation 6ith larger V Solids 6ith s and p /alence electrons outside
closed shells
Tight23inding approimation Transition2metal d2electrons (hea/ier TCs+
8alence electrons o. non2metals (diamond+
Aonic solids
Ta?le %&1, The e..ect o. temperature on the electrical conducti/ity o. solids
Solid Conducti/ity, ^ !Sm

#
" '..ect o. temperature, -
Cetals and metallic alloys ^ = #0
?
#0
%
^ rises 6ith .alling - and may 3ecome
inLnite at /ery lo6 -
Semiconductors ^ = #0

-
#0
5
^ rises 6ith rising -
Ansulators ^
=
#0

20

#0

#0
^ rises 6ith rising -
o. conducti/ity (^ in S m

#
+ and the e..ect o. temperature upon it are summarised in
Ta3le #27%7
The 3and theory pro/ides a con/incing interpretation o. these data in terms o. the
occupation o. 3ands and the gap 3et6een .ull and empty 3ands (Digure #2720+7 The
running electron 6a/e .unctions immediately suggest a mechanism .or the trans.er o.
electrons .rom one end o. a solid to the other7 We must remem3er, though, that in e/ery
direction the 6a/e .unctions are paired so that, i. the 3and is .ull, transport o. electrons
in either direction is not possi3le, since there is no 6ay in 6hich an ecess o. electrons
tra/elling in a particular direction can 3e generated7 A solid in 6hich e/ery 3and is
either completely .ull or completely empty is there.ore an insulator (Digure #2720(a++7
But the gap 3et6een the .ull and empty 3ands must 3e large enough to pre/ent electrons
occupying the latter as a conse0uence o. the BoltKmann distri3ution, vide infra7
9o6e/er, i. a 3and is only partially occupied the application o. a /oltage to the
ends o. the metal creates a situation in 6hich the energies o. the electrons at the t6o
ends o. the metal are une0ual7 The electrons in the higher2energy or3itals @ust 3elo6
the Dermi le/el react to this situation 3y mo/ing to pre/iously unoccupied or3itals, @ust
a3o/e the Dermi le/el, 6here they can respond to the applied /oltage 3y mo/ing in
the appropriate direction7 Thus an ecess o. electrons mo/ing through the metal in the
direction o. the applied /oltage, i7e7 an electric current, is generated7 Conse0uently, 6e
see that an incompletely Llled 3and, 4no6n as a cond1ction *and, is re0uired .or metallic
electrical conducti/ity (Digure #2720(3++7 ;ote that in this case the siKe o. any 3and gap
is unimportant7
When the 3and gap o. a nominal insulator is so small that the BoltKmann distri3ution
places some electrons in the higher, empty 3and (Digure #2720(c++ there can 3e electrical
'nergy
<opant le/els
(a+
(3+
(c+
(d+
(e+
6ig;re %&1&. Schematic 3and structures .or1 a+ an insulator, 3+ a metal, c+ an intrinsic semicon2
ductor, d+ an n2type semiconductor and e+ a p2type semiconductor
conduction and this depends critically upon the population o. the higher 3and7 Such su32
stances are 4no6n as intrinsic semiconductorsP germanium and silicon are t6o important
eamples7 The conducti/ity o. an intrinsic semiconductor can 3e enhanced 3y the addition
o. /ery small 0uantities o. impurities, 6hich increase the num3er o. electrons in the con2
duction 3and7 Such a su3stance is 4no6n as an n2type etrinsic semiconductor 3ecause
the impurity adds negati/ely charged particles (electrons+ to the conduction 3and7
The A828 semiconductors in 6hich an element .rom group A8 o. the periodic ta3le,
e7g7 germanium (the host+, is doped 6ith an element .rom group 8, e7g7 antimany, .orm a
good eample7 The dopant atoms su3stitute host atoms in the crystal lattice, 6hich remains
unchanged 3ecause the 0uantity o. dopant is /ery small, o. the order o. # dopant atom to
#0
$
host atoms7 Since the dopant atoms are so .ar apart there is no interaction 3et6een
them and their electronic energy le/els are li4e those o. an isolated atom pertur3ed 3y the
host7 Thus, the dopant le/els are much narro6er than the representation in Digure #2720(d+
suggests7 But the important aspect o. the situation is that the /alence electrons o. the
dopant are higher in energy than those o. the host and lie @ust 3elo6 the /acant conduction
3andP they are thus a3le to contri3ute conducting electrons to that 3and7 The 3and structure
o. an etrinsic p2type semiconductor is sho6n in Digure #2720(e+7 An this case the dopant
is an element .rom an earlier group in the periodic ta3leP it has /acant electronic energy
le/els @ust a3o/e the .ull /alence 3and o. the pure semiconductor7 These /acant le/els
are a3le to accept some o. the electrons .rom the top o. the .ull 3and 3elo6 them lea/ing
/acancies, usually regarded as positi/e holes (hence p2type+, in it7 Again, 3ecause the 3and
is no6 no longer completely .ull, electrons are a3le to respond to an imposed /oltage and
the conducti/ity is increased7
The di..erent e..ects o. a change o. temperature on the conducti/ity o. a semiconductor
and a metal may 3e understood in the .ollo6ing 6ay7 Generally, the energies associated
6ith the mo/ement o. atoms or atomic cores, e7g7 /i3ration, are small compared 6ith
those o. electronic energy le/els7 9o6e/er, i. the temperature o. a semiconductor is
su.Lciently high it may 3e possi3le .or the BoltKmann distri3ution to ta4e some electrons
at the top o. a .ull /alence 3and a3o/e the 3and gap to a pre/iously empty conduction
3and7 "nce there they can mo/e in response to the applied /oltage and, as the temperature
is increased, the conducti/ity o. the semiconductor increases7 The e..ect o. temperature
on a metallic conductor arises in a di..erent manner7 Conducting electrons proceeding
through a metal must run the gauntlet o. the positi/e cores 6hich impede their motion7
As the temperature is raised the increasing mo/ement o. the cores ma4es this more
di.Lcult and the tra/elling electrons collide more .re0uently 6ith the cores, so reducing
the current7 This e..ect out6eighs the increase in conducti/ity that arises 3ecause the
electrons populate higher le/els o. the conduction 3and as a result o. the BoltKmann
distri3ution7 Con/ersely, as the temperature is reduced metallic conducti/ity increases
and at /ery lo6 temperatures, 20 > or lo6er, the resistance o. most metals and metallic
alloys .alls to KeroP they 3ecome superconductors7 This is surprising since 6e 4no6 that
/i3rational motion persists, e/en at a3solute Kero, gi/ing rise to the Kero2point energy7
Superconducti/ity there.ore re0uires a degree o. coupling 3et6een the motions o. the
electrons and the cores7 Theoreticians ha/e .ound that synchronous mo/ements o. the
cores com3ine to assist the passage o. pairs o. electrons through the lattice7 Where a
group o. positi/e cores ha/e 3een dra6n slightly closer together 3y the passage o. an
electron, the resulting region o. enhanced positi/e charge attracts a second electron to
.ollo6 the same path7
#,* Some Special Topics
%&1'1* 2pti#al properties o" soli/s
We are concerned here 6ith the optical properties o. pure solids, e7g7 metals or dia2
mondP the properties o. composite solids such as porcelain re0uire a consideration o. the
components o. the su3stance and the 6ay in 6hich those components interact7 The most
characteristic optical property o. the metals is their high reOecti/ity and opacity, 3oth o.
6hich arise directly .rom the presence o. the electrons, 6hich are highly mo3ile and not
conLned to speciLc interatomic regions as they are in molecules7 When the oscillating Leld
o. a light 6a/e stri4es a metal the mo3ile electrons respond 3y oscillating at the .re0uency
o. the incident light7 The mo/ing electrons produce an oscillating electric Leld and them2
sel/es 3ecome a light source o. the same .re0uency as the incident light7 We percei/e this
light emitted 3y the mo/ing electrons as a reOection .rom the metal sur.ace7 Being /ery
.ree, the electrons can respond to light o. a 3road range o. energies and light o. all /isi3le
.re0uencies is reOected7 Durthermore, since there are so many electrons no light 3eam can
penetrate .ar into a metal 6ithout 3eing reOectedP metals are there.ore opa0ue7 9o6e/er,
at high .re0uencies in the ultra/iolet range a limit is reached 6here the electrons can no
longer respond at the .re0uency o. the light7 At this 6a/elength the light passes through
the metal 6ithout interacting 6ith the electrons and the metal 3ecomes transparent7
A .e6 metals appear coloured7 The reddish hue o. copper (ZAr\,d
#0
*s
#
+, .or eample,
is a conse0uence o. the .act that electrons can 3e raised .rom the ,d /alence 3and to the
*s conduction 3and 3y light .rom the 3lue end o. the /isi3le spectrum7 This is a normal
a3sorption process o. the 4ind descri3ed in Chapters % and ##7 Thus, the light reOected
.rom the sur.ace o. a piece o. copper has less 3lue light than the incident light and the
metal there.ore appears red7 The same phenomenon is .ound 6ith most other metals 3ut
6e do not notice it 3ecause the light a3sor3ed lies outside the /isi3le range7
%&1'1+ Me#$ani#al properties o" soli/s
There are many other aspects o. the solid state I thermal conducti/ity, heat capacity,
mag2 netism I 6hich cannot e/en 3e touched upon here7 They lie more in the realm o.
solid state physics7
#,#*
9o6e/er, a .e6 3rie. comments on the mechanical properties o.
solids and their interpretation in terms o. the electronic structure may 3e in order7 The
3onds in metals, .or 6hich the primary 3onding .orces are a sea o. delocalised
electrons, are not directional7 Thus, 6hen metals are de.ormed their atoms are a3le to
.orm ne6 3onds 6ith their ne6 neigh3ours and metals can 3e easily de.ormed and
6ithstand considera3le distortion 3e.ore they rupture7 "n the other hand, solids such
as diamond 6ith highly directional co/alent 3onds are the hardest su3stances 6hich
6e 4no67 They are /ery di.Lcult to de.orm 3ut i. su.Lcient .orce to 3rea4 the 3onds is
applied they shatter7 Aonic solids are 3rittle7 The .orce re0uired to mo/e an ion 6ith respect
to its neigh3ours is .airly large, 3ut once the regular ionic array is disrupted the repulsion o.
ions o. li4e charge destroys the crystal7
%&1( 8I85I2RA!HY AN3 6URTHER REA3IN
#7 '7 9uM c4el, O. Physi;, +., 20*(#$,#+P +&, ,#0 (#$,#+P +*, ?2% (#$,2+P ,', ?,2
(#$,,+7
27 G7J7 9oi@tin4, Rec. -rav. Chim., ++, 555 (#$5%+7
Boes .or Chapter #2 #,5
,7 '7 9eil3ronner and J7;7 Currell, Q. Chem. Soc., 2?## (#$?2+7
*7 D7 >lages, Chem. /er., ,&, ,5% (#$*$+7
57 G7 >lopman, Q. Am. Chem. Soc., -., 22, (#$?%+7
?7 A7 Dleming, 9rontier 4r*itals and 4rganic Chemical Reactions, Wiley, ;e6 Ror4, #$-?7
-7 A7 Streit6ieser, 5olec1lar 4r*ital -heory for 4rganic Chemists, Wiley, ;e6 Ror4, #$?#7
%7 G7 Berthier, B7 !ullman and J7 !ontis, Q. Chim. Phys., (-, ,?- (#$52+7
$7 J7;7 Currell, S7D7A7 >ettle and J7C7 Tedder, Valence -heory, 2nd edn, Wiley, ;e6 Ror4, #$-07
#07 The units o. electrical and magnetic properties are o.ten con.using and di.Lcult to handle7 The
article 3y T7A7 &uic4enden and :7C7 Carshall, Q. Chem. Ed., (-, ##* (#$-2+, is /ery help.ul7
##7 J797 8an 8lec4, -he -heory of Electric and 5agnetic S1sce%ti*ilities, ".ord =ni/ersity !ress,
#$,27
#27 W7'7 9enry, Phys. Rev., ,,, 55$ (#$52+7
#,7 C7 >ittel, :ntrod1ction to Solid State Physics, -th edn, Wiley, ;e6 Ror4, #$$?7
#*7 ;7W7 Ashcro.t and ;7<7 Cermin, Solid State Physics, Saunders College !u3lishing, !hiladel2
phia, 200#7
#57 A7!7 Sutton, Electronic Str1ct1re of 5aterials, ".ord =ni/ersity !ress, #$$,7
82D %&1% T$e ent$alp0 o" #om?;stion an/ t$e /elo#alisation energ0 o" ?enMene
The enthalpies o. com3ustion o. car3on and hydrogen atoms are ###0 4J mol

#
and

,?# 4J mol

#
respecti/ely, so the com3ustion o. si moles o. car3on atoms and si
moles o. hydrogen atoms produces %%2? 4J o. energy7 The calculated energy e/ol/ed
in the com3ustion o. one mole o. Q>e4ulebG 3enKene is ,*5# 4J, considera3ly less
than that produced 3y the com3ustion o. the constituent atoms 3ecause more than
hal. o.
the energy released is used to 3rea4 the C
=
C, CIC and CI9 3onds7 The energy
released 3y the com3ustion o. one mole o. QrealG 3enKene is e/en less, indicating that
the 3enKene molecule is yet more sta3le than the >e4uleb structure implies (Digure
B#27#7#+7 The di..erence o. #*$ 4J mol

#
is the resonance or delocalisation energy7
'nergy (4J+
0 ? moles o. car3on dioide + , moles o. 6ater
,,02
,,5#
"ne mole o. [real[ 3enKene
#*$ 4J = <elocalisationHresonance energy o. # mole o. 3enKene
"ne mole o. [>e4ulp[ 3enKene
'nergy re0uired to 3rea4 , moles o. CgC 3onds,
, moles o. CIC 3onds and ? moles o. CI9 3onds
%%2?
? moles o. 9 atoms ) ? moles o. C atoms
6ig;re 8%&1%1% The enthalpies o. com3ustion o. one mole o. Q>e4ulebG and one mole o. QrealG
3enKene (not to scale+
#,? Some Special Topics
82D %&1& T$e orientation o" a magneti# /ipole in a magneti# Bel/
An Section #2727# 6e stated, 6ithout .urther @ustiLcation, that 6hen atomic or molec2
ular magnets are placed in a magnetic Leld they align their magnetic dipoles 6ith the
applied Leld, there3y increasing B7 This statement may appear counter2intuiti/e, espe2
cially so 6hen one considers the case 6ith 6hich it has a great deal in common I the
orientation o. molecules 6ith a permanent dipole moment in an electric Leld7 An that
case the orientation o. lo6est energy is 6here the molecules align themsel/es so that
their positi/e ends point to6ards the negati/e pole o. the applied Leld and their neg2
ati/e ends to6ards the positi/e pole, there3y opposing and reducing that Leld7 The
origin o. this apparent dilemma lies in the .act that isolated positi/e and negati/e
charges are real entities, 6hereas isolated north and south poles are Lgments o. our
imagination7 A. 6e ta4e a 3ar magnet and sa6 it in hal. 6e o3tain t6o 3ar magnets,
each 6ith a north and south pole, and 6e 4no6 that this remains true e/en 6hen 6e
continue the process until our remaining magnets are indi/idual atoms or molecules7
But 3odies o. atomic or macroscopic siKe, charged 6ith an electrical charge o. one
sign only, can 3e readily generated in the la3oratory7 There.ore, 6hen 6e calculate
the energy o. a magnetic dipole in a magnetic Leld 6e ha/e to consider the eact
.orm o. the dipole care.ully7
Since there are no such things as isolated north and south magnetic poles 6e
cannot represent a magnetic dipole in an applied magnetic Leld simply 3y replacing
the positi/e and negati/e signs o. the corresponding electric dipole I electric
Leld pro3lem 3y ; and S respecti/ely7 An .act, the origin o. all magnetism is the
circulation o. electric charge and the only true representation o. a magnetic dipole is
the magnetic Leld produced 3y a current Oo6ing around a small loop7 The energy o.
the resulting magnetic dipole 6ith respect to its orientation in an applied Leld must
3e determined 3y calculating the .orces eerted 3y the Leld on the current2carrying
components o. the loop7
A plan /ie6 o. a rectangular loop (area A+ perpendicular to the plane (K+ o. the
paper and carrying a Oo6 o. positi/e charge (i+ 6hich enters the paper at + and
emerges again at is sho6n in Digure B#2727#7 The magnetic moment (T+ produced
3y the current is perpendicular to the plane o. the loop (compare Digure #27#0+ and
ma4es an angle o. # 6ith the direction (K+ o. an applied Leld 3B47 Since the currents
on opposite sides o. the loop Oo6 in opposite directions there is no net .orce on the
loop, i. the Leld is uni.orm7 But DlemingGs le.t2hand rule tells us that there are .orces
3;4, as indicated in the Lgure, acting on the ascending and decending conductors o.
the loop 6hich are parallel to y7 The loop is there.ore su3@ect to a tor0ue ([ +, 6hich
tends to align the moment (T+ 6ith the Leld 3B47 At is not di.Lcult to sho6
#2
that1
[ = iA/ sin # = T/ sin #
or in /ector notation1
[ = T B
The corresponding .orces acting on the t6o horiKontal components o. the loop
are /ertical and opposed and produce no tor0ue7 At is clear .rom the Lgure that the
tor0ue acts in such a 6ay as to align T and B and 6e see that the presence o. the
;
m
B +
S
0
;
i
B o
;
6ig;re 8%&1&1% The .orces on a current loop in a magnetic Leld
paramagnetic atom or molecule does indeed enhance the applied Leld, 6hich 6as the
main o3@ecti/e o. this discussion7
We can also o3tain an epression .or the potential energy (E+ 3ecause in order to
increase the energy 3y dE 6e must per.orm 6or4 (dW + against the tor0ue and1
dE = dW = [ d# = T/ sin # d#
Antegration gi/es1
E = T/ cos # + constant
Since 6e are interested here only in relati/e energies 6e set the constant to Kero
so that1
E = T/ cos # or E = T B
Dinally, 6e should note that although 6e ha/e considered only the case o. a
rectangular loop, the result applies to a loop o. any shape and the magnetic moment
is al6ays iA, 6here i is the current and A the area o. the loop7
RE6ERENCES
#7 :7!7 Deynman, :7B7 Leighton and C7 Sands, -he 9eynman Lect1res on Physics, Addison2
Wesley !u3lishing Co7, London, #$?*7
27 A7S7 Grant and W7:7 !hillips, Electromagnetism, 2nd edn, Wiley, Chichester, #$$07
82D %&1' T$e #onne#tion ?etween experimental magneti# s;s#epti?ilit0 an/
atomi#Nmole#;lar magneti# moment I a #lassi#al treatment
An order to measure the macroscopic magnetic suscepti3ility o. a su3stance, and to
deri/e in.ormation a3out its electronic structure .rom such a measurement, 6e must
normally study the interaction o. the su3stance 6ith an imposed magnetic Leld7 The
potential energy (E+ o. a magnetic dipole !T" su3@ected to a magnetic Leld 3$4
(Digure B#27,7#+ is gi/en (Bo #272+ 3y the e0uation1
E = T/ cos # = T B
m
;
$
S
0
6ig;re 8%&1'1% The energy o. a magnetic dipole (T+ in a magnetic Leld ($+
6here / is the magnetic Ou density at the position o. the dipole and # is the angle
3et6een the magnetic Leld and the dipole7 This important result assumes that the
applied Leld 3$4 and the resultant Ou density 3B4 are parallel7
When a sample su3stance that consists o. molecules each ha/ing a magnetic dipole
moment !T" is placed in a magnetic Leld the molecules 6ill 3e su3@ect to t6o .orcesP
the tendency .or the indi/idual molecular dipoles to orientate themsel/es along the
direction o. the magnetic Leld and the opposing thermal motion7 The measured macro2
scopic magnetic properties o. the material 6ill depend upon the resulting distri3ution
o. orientations7
The .raction o. dipoles (d;+ lying at an angle 3et6een # and # + d# is e0ual to
the .raction o. the sur.ace o. a sphere o. unit radius 6hich lies 6ithin the same range
o. # 7 This is a 3and o. radius sin # , i7e7 length 2( sin# , and 6idth d# running
around the sur.ace o. the sphere, (Digure B#27,72+7
<ipoles orientated at di..erent /alues o. # ha/e di..erent potential energies and the
.raction o. molecules 6ith dipoles lying at an angle 3et6een # and # + d# is deter2
mined 3y the BoltKmann population appropriate to that particular energy7 The dipoles
6ith this orientation ha/e energy !/T cos #" so that their .ractional population (d;
#
+
depends upon the BoltKmann .actor (ep {/T cos #, ;- }+ and the orientational .actor
({2( sin # }+1
d;
#

ep
{
/T cos #, ;-
} {
2( sin #
}
d#
Dield $
d0
#
sin 0
0
Area o. element
=2p sin0 d0
6ig;re 8%&1'1& The area element .or magnetic dipoles lying at an angle 3et6een # and
# + d# to the magnetic Leld
+#
+#
6here ; is BoltKmannGs constant and - is the a3solute temperature7 We can replace
the proportionality sign 6ith a constant (A+, 6hich depends upon the num3er o.
molecules in the sample, and the relati/e areas o. the 3and and the sphere1
d;
#
= A ep{/T cos #, ;- } {2( sin # } d#
Since the contri3ution to the macroscopic dipole moment o. each mem3er o. this group
o. molecules is T cos # their contri3ution (d5
#
+ to the total macroscopic magnetic
moment !5 " 6ill 3e1
dC
#
= A ep{/T cos #, ;- } {2( sin # } {T cos # } d#
5 can no6 3e o3tained 3y integrating this epression o/er all possi3le molecular
orientations, i7e7 .rom 0 to ( 7 To determine the a/erage /alue o. T!T
a/
" 6e di/ide 3y
the total num3er o. molecules, 6hich 6e can Lnd 3y integrating the epression .or
d;
#
o/er the same range o. # 1

(
T
a/
=
A ep{/T cos #,4- } {2( sin # } {T cos # } d#
0

(
A ep{/T cos #,4- } {2( sin # }
d#
0

(
T ep{/T cos #, ;- } sin # cos # d#
0
=

(
0
ep{/T cos #, ;- } sin # d#
These integrals can 3e simpliLed 3y 6riting s = /T, ;- , t = cos # (6hence
sin # d# = dt+ and replacing the integration limits accordingly to gi/e1

#
T
a/
=
T
+#

#
+#
t ep{st} dt
ep{st} dt
TZep{st} !st #",s
2
\

#
=
Zep{st},s\

#

ep
{
s
} +
ep
{
s
}
#

#

coth{s}
=
T
ep
{
s
}
ep
{
s
}

s
=
T
s
This e0uation 6as Lrst deri/ed 3y !aul Lange/in (#%-2 I #$*?+ and carries
his name7 An order to apply it, important and readily @ustiLed approimations are
usually
made7 Since T is o. the order o. #0

2,
A m
2
, s
=
/T, ;-

2.5

#0

,
in a magnetic
Leld o. one Tesla and the epansion o. the eponential .unctions (see Bo ,7#+ can
3e truncated a.ter terms in s
,
gi/ing1

ep
{
s
} +
ep
{
s
}
#


2
+
s
2
#

2
+
s
2
#

T
a/
=
T
ep{s} ep{s}

s

T
2s + s
,
,,

s
=
T
2s!# + s
2
,?"

s

#
2
2
#

s s
,

BT
2

T
2s

!2
+
s "!#

s ,?"

s
=
T
,

#2

,;-
e..
=
An the third step 6e ha/e used the .act that !# + s
2
,?"

#
!# s
2
,?" i. s is small7
Thus1
T
a/
= /T
2
,,;-
and .or an assem3ly o. ; molecules per unit /olume1
5 = ;T
a/
= ;/T
2
,,;-
There.ore1
H = 5,8 = ;/T
2
,,;- 8
and since / = T
o
!8 + 5", 6hen 5 is small 6e ha/e1
H = ;T
o
T
2
,,;- {;T
o
T
B
2
,,;- }T
2
(B#27,7#+
The identity in '0uation (B#27,7#+ deLnes the /ohr magneton n1m*er !T
e..
",
6hich is ta4en to 3e positi/e7 At is the e..ecti/e magnetic moment measured in Bohr
magnetons7 Comparing the result 6ith CurieGs e0uation, H = C, - , 6e o3tain an
epression .or C1
C
=
;T
o
T
2
,,; or
{
;T
o
T
2
,,;
}
T
2
(B#27,72+
B e..
We ha/e deri/ed a classical epression .or the magnetic moment (5 + induced in a
collection o. ; dipoles 3y the application o. a magnetic Leld (8 +7 This is the macro2
scopic, eperimental side o. the pro3lem, a relationship 3et6een the suscepti3ility
!H ", 6hich 6e can measure, and a property (T or T
e..
+ o. the indi/idual molecule,
6hich 6e 6ould li4e to 4no67 ;ote that the suscepti3ility is deLned in terms o. the
applied magnetic Leld !8 ", as it must 3e since the applied magnetic Leld is something
that 6e can measure7 But our dipole !T" interacts 6ith the resulting Ou density !/ ",
6hich 6e cannot measure directly7 But the approimation /
=
T
o
8 is a good one
6hen 5 is small7
We no6 turn to the microscopic, 0uantum2mechanical aspect o. the pro3lem7 9o6
do the indi/idual electronic states o. a single atomicHmolecular magnet contri3ute
to the total T .or that entityJ The important .actors are the magnetic moment o.
each state, 6hich depends upon the or3ital and spin angular momentum, and the
energy o. the state, 6hich determines its population through the BoltKmann distri2
3ution7 Let these t6o .actors .or any state i 3e T
i
and E
i
respecti/elyP the means
o. calculating them are descri3ed in the main 3ody o. the tet7 We set i = # .or
the state 6hich has the lo6est energy in the applied Leld and epress the popula2
tions (;
i
+ o. all other states in terms o. the population ;
#
7 According to
BoltKmann 6e ha/e1
;
i
= ;
#
ep{!E
#
E
i
", ;- } ;
#
e
!E
#

E
i
", ;-
The total magnetic moment !T
t
" .or the molecule or atom is1
T
t

T
i
;
i
i
!ro3lems .or Chapter #2 #*#

L #.000K 070 070 07-0-
07-0-
L + 0.,##K
07%#5 0725*
07,?% 07,?%
L + 2.#-0K 072%2 07?#2 0752, 0752,
= =
c
To o3tain the a/erage moment !T
a/
" the a3o/e epression .or the total must 3e
di/ided 3y the total population1
T
a/
=

T
i
;
i
i

;
i
i
;
#

T
i
e
!E
#

E
i
", ;-
i
;
#

e
!E
#

E
i
", ;-
i
;
#
e
E
#
, ;-

T
i
e

E
i
,;-
i
;
#
e
E
#
, ;-

e

E
i
,;-
i
Cancelling out the .actors multiplying 3oth series, the epression .or T
simpliLes to1
T
=
i
T
i
e
E
i
,;-
(B#27,7,+

e

E
i
,;-
i
Applications o. '0uations (B#27,7#+, (B#27,72+ and (B#27,7,+ can 3e .ound in
Chapter #27
!R285EMS 62R CHA!TER %&
#7 81Fc;el or*itals for methylenecyclo%ro%ene !C
_
8
_
". The molecule has the car3on2
atom s4eleton 3elo61
*
c
c c
2 #
,
Dollo6ing the method descri3ed in Section #27#7*, set up the secular e0uations .or the
( 2electron system and sho6 that the molecular or3ital energies are gi/en 3y the roots
o. the e0uation1
6here = !L E",K 7

*

*
2
+
2
+
#
=
0
The e/aluation o. the 9uM c4el energies and atomic or3ital coe.Lcients is rather
tediousP they are .ound to 3e1
'nergy Coe.Lcients
L #.*%#K 0750? 07-*$ 07,02 07,02
<ra6 an energy2le/el diagram .or the molecule and calculate the ( 2electron charge
densities on each atom and the 3ond orders .or all 3onds .or the neutral molecule7
ZAns1 &
#
=
#.*%%, &
2
=
0.%--, &
,
=
&
*
=
0.%#%, !
#2
=
0.-5%, !
,*
=
0.%#%, !
2,
=
!
2*
=
0.*5,7\
What 6ould 3e the distri3ution o. positi/e or negati/e charge in the ions ZC
*
9
*
\
+
and ZC
*
9
*
\

J
Colecule ( 2Bond order Bond length
a
(pm+
'thane #5,7*
BenKene #,$7-
'thene #,,7$
'thyne #207*
27 C`C *ond lengths and *ond orders. Complete the .ollo6ing ta3le1
a
:nteratomic Eistances S1%%lement, Special !u3lication ;o7 #%,
The Chemical Society, London, #$?57
Z9ints .or determining 3ond order1 'thane has no ( 3ond, ethene has one and ethyne
t6o7 The 3ond order o. 3enKene can 3e calculated .rom the molecular or3ital coe.L2
cients gi/en in Digure ##757\
!lot a graph o. 3ond order /ersus 3ond length and use it to estimate the lengths
o. the t6o CIC 3onds in 3utadiene .or 6hich the 3ond order data can 3e .ound in
Ta3le #27*7 Compare your results 6ith the eperimental /alues o. r
#

2
= #,,.- pm
and r
2

,
= #*%., pm7 The prediction is not /ery goodP suggest 6hy7
,7 81Fc;el or*itals for methanal !8
J
C
=
4".
The hetero2atom, oygen, can 3e incorporated into the 9uM c4el scheme using the
pro2
cedure descri3ed at the end o. Section #27#7?7 Dorm the t6o secular e0uations .or
methanal 6ith h
"
= #.2 and 4
"
= 2.0 and sho6 that the energy le/els are gi/en 3y
the roots o. the polynomial
2
+ #.2 * = 07 Calculate the energies and coe.LcientsP
you should Lnd1
E = L #.*%%K C
C
= +0.%02 C
"
= 0.5$-
E = L + 2.?%%K C
C
= +0.5$- C
"
= +0.%02
Calculate the ( 2electron charge densities and 3ond orders .or the neutral molecule7
Z&
C
= 0.-#,, &
"
= #.2%?, !
C"
= 0.$5%\7 ;ote ho6 the larger /alue o. L assumed .or
oygen dra6s charge to that end o. the molecule7
*7 Construct a ta3le li4e Ta3le #275 .or a single d electron in a strong octahedral crystal
Leld7 Assume that spin2or3it coupling is Kero and that, 3ecause o. the large Leld, only
the or3itals d
y
, d
K
and d
yK
are occupied7 The atomic or3itals ha/ing m
l
=
# (i7e7 d
K
and d
yK
+ are not mied 3y the Leld (Chapter -+ and can 3e used in the .orm
|
m
l
, m
s

in the calculation7 The d
y
ho6e/er must 3e used in the calculation in the .orm1

|
d
y


#
= {
i, 2
}{|
2

#
| +
2

#
}
and
2 2 2

d
y


#
| = {
i, 2
}{
2

#
| +
2

#
|}
2 2 2
Sho6 that1
2 ep!2" 2 ep!2" + ep!" ep!" 2 sinh!2" + sinh!"
T
=
ep!2" + ep!2" + ep!" + ep!" + 2 ep!0"
=
cosh!2" + cosh!" + #
6here = /, ;- 7
=se a spreadsheet or other plotting program to dra6 the magnetisation cur/e li4e
graph 2 in Digure #27#27
57 Calculate the magnetic energy le/els o. a system consisting o. t6o interacting metal
#
ions one o. 6hich has S
=
#
, 5
S
=
and the other has S
=
#, 5
S
=
0,

#7 =se the
2
coupling 9amiltonian operator
(9

2
= 2>'

#
'

2
+ and proceed as in Section #2727#07
Rou 6ill Lnd that your result has much in common 6ith the energy le/els o. a single
p electron, in 6hich spin and or3ital magnetic moments are coupled 3y the spin2or3it
coupling7 ZThe u3i0uity o. phenomena 3ased on angular momentum is such that the
same pro3lems occur again and again7\
?7 Sho6 that the 6a/e .unctions (
m
+ deLned 3y '0uation (#27,7*+ are orthogonal to
each other, i7e7 sho6 that
m
|
n
= 0.0 i. m = n7
-7 <eri/e an epression .or the general matri element
m
|V

|
n
6here V

is the
potential deLned 3y '0uation(#27,7,+ and
m
are the 6a/e .unctions deLned 3y
'0uation (#27,7*+7
Appendi #
6;n/amental Constants
an/ Atomi# Units
6;n/amental #onstants
%
Constant 8alue in
SA units
8alue in
other units
c /acuum /elocity o. light 2.$$-$2 #0
%
m s
#
2.$$-$2 #0
#0
cm s
#
e elementary charge #.?02#% #0
#$
C *.%0,2# #0
#0
esu
; BoltKmannGs constant #.,%0?? #0
2,
J >
#
#.,%0?? #0
#?
erg deg
#
h !lanc4Gs constant ?.?2?0% #0
,*
J s ?.?2?0% #0
2-
erg s
h` !lanc4Gs constantH2( #.05*5- #0
,*
J s #.05*5- #0
2-
erg s
N
A
A/ogadroGs constant ?.022#* #0
2,
mol
#
?
0
permitti/ity o. .ree %.%5*#$ #0
#2
J
#
space C
2
m
#
(D m
#
+
T
0
permea3ility o. .ree *( #0
-
J s
2
C
2
m
#
space (; A
2
+
m
%
rest mass o. proton #.?-2?2 #0
2-
4g
T
/
Bohr magneton $.2-*02 #0
2*
A m
2
$.2-*02 #0
2#
erg
gauss
#
T
N
nuclear magneton 5.050-$ #0
2-
A m
2
5.050-$ #0
2*
erg
gauss
#
Atomi# ;nits
The metre, 4ilogram, etc7 are not /ery con/enient units 6ith 6hich to measure atomic and
molecular 0uantitiesP they are too large7 At is easier to 6or4 6ith units 6hich are directly
related to the .undamental physical 0uantities such as electronic charge and mass7 Such
a system is in 6idespread use and the units are 4no6n as atomic 1nits7
Apart .rom the con/enience associated 6ith the appropriate siKes o. the atomic units,
the system has another, e0ually important ad/antage7 A result epressed in terms o. the
.undamental physical constants is al6ays correct alge3raically and can 3e easily 3rought
up to date numerically 6hene/er a more accurate determination o. any o. the physical
Appendi #
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
2
*02 Dundamental Constants and Atomic =nits
constants is made7 The .ollo6ing atomic units occur most 6idely, a .ull list is gi/en 3y
Cills et al7
#
The atomic unit o. mass is the rest mass o. the electronP m
e
= $.#0$5? #0
,#
4g7 The unit o. charge is the elementary chargeP e = #.?02#$ #0
#$
C7
The atomic unit o. length is the Bohr radius or 3ohr (a
o
+, the radius o. the or3it o.
lo6est energy o. the electron o. the hydrogen atom in the Bohr theory7 The eact /alue
o. this 0uantity depends upon the mass o. the nucleus (see Section 575+7 There.ore, the
radius is deLned .or a nucleus o. inLnite massP a
0
= ?
0
h
2
,m
e
e
2
= 5.2$#-- #0
##
m7
The atomic unit o. energy is the 9artreeP E
8
= h
2
,*(
2
m
e
a
0
2
= *.,5$-5 #0
#%
J7
The 9artree is e0ual to the coulom3ic repulsion energy o. t6o elementary charges one
3ohr apart or t6ice the ionisation energy o. the hydrogen atom (assuming an inLnite
nuclear mass+7
The atomic unit o. action is !lanc4Gs constant di/ided 3y 2( 7 At has no special name
and is /ery .re0uently denoted 3y dra6ing a 3ar through the h .or !lanc4Gs constant1
h,2( h` = #.05*5$ #0
,*
J s7
The atomic unit o. time has no special nameP it is h` ,E
8
= 2.*#%%% #0
#-
s7
The atomic unit o. /elocity has no special nameP it may 3e epressed as a
0
E
8
,h
`
=
2.#%-?$ #0
?
m s
#
7
An atomic units, the SchroM dinger e0uation .or an electron mo/ing in a potential V
can 3e 6ritten1
+ 2!E V " =
0
RE6ERENCE
#7 A7 Cills, T7 C/itasq, >7 9omann, ;7 >allay and >7 >uchitsu, 31antities Units and Sym*ols in
Physical Chemistry, 2nd edn, Anternational =nion o. !ure and Applied Chemistry, #$$,7
*0* The 8ariation Cethod and the Secular '0uations
T$e Variation Met$o/
an/ t$e Se#;lar E@;ations
The num3er o. pro3lems .or 6hich 6e can sol/e the SchroM dinger e0uation directly
is small7 At is there.ore /ery .ortunate that the hydrogen atom is one o. this type,
since the solutions o3tained .orm the starting point o. all our 0uantum2mechanical
models o. atomic structure and .or many descriptions o. molecular structure7 An the great
ma@ority o. cases, ho6e/er, a direct solution o. SchroM dingerGs e0uation is not possi3le
and 6e must adopt other methods7 This appendi descri3es one such approach7 As a
preliminary 6e need a proo. o. the /ariation theorem7
T$e Aariation t$eorem
Gi/en any approimate 6a/e.unction $, 6hich satisLes the 3oundary conditions o. the
pro3lem, the epectation /alue !
$
, o. the o3ser/a3le ! calculated .rom $ 6ith the operator
!

6ill al6ays 3e greater than or e0ual to the lo6est eact eigen/alue o. !

7
Proof
Suppose that 6e ha/e an operator
!

the eact eigen/alues and eigen.unctions o. 6hich

are p
0
p
#
p
2
. . . and G
0
G
#
G
2
. . . respecti/ely7 Then1
!

|G
i
= p
i
|G
i
!A2.#"
and the |G
i
can al6ays 3e chosen to 3e orthogonal and normalised so that1
G
i
|G
@
= )
i@
!A2.2"
Suppose no6 that 6e ha/e a 6a/e .unction |$ , 6hich is not one o. the |G
i
, then the
epectation /alue !
$
o.
!

calculated .or the .unction |$ is gi/en (Section ,7$+ 3y1

$
|
!
|
$

-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
!
$
=

$|$
!A2.,"

C

C

i
The .unctions G
i
.orm a complete set and any .unction $ that satisLes the 3oundary
conditions o. the pro3lem can 3e 6ritten in terms o. them1
|$ =

C
i
|G
i
!A2.*"
i
ZT6o /ectors at right2angles .orm a complete set and any other /ector in the same
plane can 3e 6ritten in terms o. them\7
We can al6ays normalise |$ so that1
$|$ =

i

C
@
G
i
|G
@
= #
@
;ote that the sums o/er i and @ in the a3o/e epression are independent o. each other
so that i. the are n .unctions G
i
there are n
2
terms in total7
;o6, 3ecause o. '0uation (A272+1
i
C
i
= # !A2.5"
i
'panding $ in '0uation (A27,+ using '0uation (A27*+ 6e ha/e1
i

@
C
@

G
i
|
!

|
G
@
!
$
=
=sing '0uation (A27#+ gi/es1
i
C

4
l
C
l
G
4
|G
l

!A2.?"
i

@
C
@
p
@

G
i
|
G
@
!
$
=
i
C

4
l
C
l
G
4
|G
l

With the help o. '0uations (A272+ and (A275+ 6e Lnd1
!
$
=

C

C
i
p C

C
4
=
C

C
i
p !A2.-"
i i 4 i i
i 4 i
Su3tracting the lo6est eigen/alue (p
0
+ .rom 3oth sides o. '0uation (A27-+ 6e o3tain1
!
$

p
0
=

C

C
i
p

p
=
C

C
i
!p

p "
i i 0 i i 0
i i
6here 6e may ta4e p
0
into the 3rac4et 3ecause o. '0uation (A275+7
But, p
i

p
0
, 3y deLnition and C
i

C
i
must al6ays 3e positi/e (Appendi %+, there.ore1
!
$
p
0
0 or !
$
p
0
&7'7<7
%pplication of the 9ariation &ethod
Suppose that 6e ha/e a set o. n 3asis .unctions |a 7 They might 3e atomic electronic states
characterised 3y |L 5
L
S 5
S
, spin .unctions |L!#"K !2"L!," in an ;C: pro3lem or
The 8ariation Cethod and the Secular '0uations #*$

a

a
Gi
S
atomic or3itals |2p

. . . etc7 in the molecular or3ital theory7 We 6ish to Lnd linear
com3inations o. these 3asis .unctions1
n
|G =

C
Ga
|a
a=#
6hich are eigen.unctions (or as near to eigen.unctions as is possi3le 6ithin the limitations
o. the 3asis+ o. some operator,
!

say7 The coe.Lcients C

Ga
are simply num3ers 6hich
may 3e real, pure imaginary or comple7 An 6hat .ollo6s 6e shall assume that they are
real7 Adeally, the .unction |G must 3e such that1
!

|G = !
G
|G
The operator may represent any measura3le property ! and applications in 6hich
it is energy are especially common7 !
G
is the eigen/alue o.
!

corresponding to the
eigen.unction
|
G

7 We 4no6 .rom the /ariation theorem that the epectation /alue o. !

6ith the .unction

|
G

!
G
, 6ill al6ays 3e greater than the lo6est eigen/alue o. !

,
or
e0ual to it i. 6e Lnd the eact eigen.unction7 We use this as a criterion .or determining
the /alues o. the coe.Lcients C
Ga
3y Lnding the condition that the epectation /alue shall
3e a minimum7 We choose to minimise the epectation /alue rather than the eigen/alue
3ecause 6e cannot 3e sure, a %riori, that our set o. 3asis .unctions 6ill allo6 us to Lnd
an eigen.unction o. our pro3lemP they may not .orm a complete set .or eample7
The epectation /alue o.
!

6ith the .unction

|
G

, !
G
, is (Section ,7$+1
G
|
!
|
G

a CGa 3 CG3

a
|
!
|
3

a
C
Ga 3
C
G3
!
a3
!
G
=

G |G
=
a
C
Ga
3
C
G3
a|3


a
C
Ga
3
C
G3
S
a3
!
a3
and S
a3
are simply a33re/iations .or matri elements, a|!

|* , and o/erlap integrals,
a|3 , 6hich 6e must 4no6 or 3e a3le to calculate7 There.ore1
!
G

C
Ga

C
G3
S
a3
=

C
Ga

C
G3
!
a3
a 3 a 3
But, according to the /ariation theorem, the lo6est /alue o. !
G
6e can o3tain is the
3est, so 6e loo4 .or the set o. coe.Lcients 6hich gi/e lo6est point in the sur.ace o. the
plot o. !
G
against the un4no6n coe.Lcients C7 Dirstly 6e di..erentiate 3oth sides o. the
a3o/e e0uation 6ith respect to a particular C, C
Gi
say7 We must remem3er that !
G
is
itsel. a .unction o. C
Gi
, though !
a3
and S
a3
are not7 Thus, on the le.t2hand side 6e ha/e
a product to di..erentiate1
D !
G
D C
Gi

C
Ga

C
G3
S
a3
+
!
G

D {

C
Ga
3
C
G3
S
a3
} D {

= C
Ga

3
C
C
G3
!
a3
}
a 3
D C
Gi
D
Gi
Dor a minimum in P
G
, D P
G
,D C
Gi
is Kero and 6e ha/e1
!
G

D {

a
C
Ga

3
C
G3
S
a3
}
D C
Gi
=
D {

a
C
Ga

3
C
G3
!
a3
}
D C
Gi
To carry out the di..erentiations 6e epress the dou3le sum as three terms, paying
particular attention to terms in/ol/ing C
Gi
1

C
Ga

C
G3
S
a3
=

C
Ga

C
G3
S
a3
+
2C
Gi

C
G3
S
i3
+
C
2
ii
#50 The 8ariation Cethod and the Secular '0uations
a 3 a=i 3=i 3=i
!!
#2
!
G
S
#2
" !!
#,
!
G
S
#,
"

!!
22

!
G
S
22
" !!
2,

!
G
S
2,
"


a




Where 6e ha/e assumed that S
a3
= S
3a
and that all the coe.Lcients C are real7 A. 6e
6ish to recognise the .act that the coe.Lcients C and the o/erlap integrals S may 3e
comple or pure imaginary 6e ha/e to proceed slightly di..erently at this point, 3ut 6e
shall not ta4e that course7
The di..erentiation is no6 straight.or6ard and 6e Lnd1
D
{

C
Ga

3
C
G3
S
a3
}
0 2

C S 2C S 2

C S
D C
Gi
= +
3=i
G3 i3
+
Gi ii
=
G3 i3
3
The other side o. the e0uation gi/es a result o. eactly the same .orm and 6e ha/e1
2P
G


C
G3
S
i3
=
2

C
G3
P
i3


C
G3
!P
i3

P
G
S
i3
"
=
0
3 3 3
We o3tain one such e0uation .or e/ery C
Gi
, i7e7 .or e/ery 3asis .unction, |i 7 These are
the sec1lar e71ations7 Thus, .or the epectation /alue !
G
6e ha/e .or i = # 2 , . . . 1
C
G #
!P
##
!
G
S
##
" + C
G 2
!!
#2
!
G
S
#2
" + + C
G n
!!
#n
!
G
S
#n
" = 0
C
G #
!!
2#
!
G
S
2#
" + C
G 2
!!
22
!
G
S
22
" + + C
G n
!!
2n
!
G
S
2n
" = 0
1 1 1
1 1 1
C
G #
!!
n#
!
G
S
n#
" + C
G 2
!!
n2
!
G
S
n2
" + + C
G n
!!
nn
!
G
S
nn
" = 0
These are sim1ltaneo1s homogeneo1s e0uations in 6hich the un4no6ns are the coe.2
Lcients C7 They are satisLed 3y the trivial solution C
G#
= C
G2
. . . = C
Gn
= 0.0 3ut,
clearly, 6e are not interested in that7 The condition that they ha/e a non+trivial solution
is that the determinant 3elo6 is e0ual to Kero1
!!
##
!
G
S
##
"

!!
2#
!
G
S
2#
"
!!
#n
!
G
S
#n
"


!!
2n
!
G
S
2n
"


1 1 1 1
1 1 1 1

= 0




!!
n#

!
G
S
n#
" !!
n2

!
G
S
n2
" !!
n,

!
G
S
n,
"

!!
nn

!
G
S
nn
"

Since all the !
a3
and S
a3
are 4no6n, 6e can epand the determinant and o3tain a
polynomial o. order n in !
G
7 We re0uire the lo6est root7 We also ma4e use o. higher
roots, as 6ill 3e descri3ed 3elo67
9a/ing .ound the re0uired /alue o. !
G
, 6e can enter it in the secular e0uations and
sol/e them .or the coe.Lcients C7 The .act that the solution gi/es only the ratios o.
the coe.Lcients and not their a3solute /alues (3ecause the e0uations are homogeneous+,
presents no great pro3lem since 6e also ha/e the re0uirement that the eigen.unctions 3e
normalised 6hich gi/es us one .urther e0uation1

C
Ga

C
G3
S
a3
= #.0
a 3
An the de/elopment so .ar 6e ha/e made no particular assumptions a3out the 3asis
.unctions |a , so i. they are not orthogonal to each other terms in S
a3
appear o.. the
!
2#
!!
22
!
G
" !
2,
!
2n
1 1 1 1




C
2
diagonal and this raises etra, 3ut not insurmounta3le, pro3lems7 Dortunately, 6e can
usually Lnd a set o. orthogonal and normalised 3asis .unctions so that S
a3
= )
a3
and 6e
then ha/e only diagonal terms in S7 The secular e0uations 3ecome1
C
G #
!!
##
!
G
" + C
G 2
!
#2
+ C
G ,
!
#,
+ + C
G n
!
#n
= 0
C
G #
!
2#
+ C
G 2
!!
22
!
G
" + C
G ,
!
2,
+ + C
G n
!
2n
= 0
1 1 1 1
1 1 1 1
C
G #
!
n#
+ C
G 2
!
n2
+ C
G ,
!
n,
+ + C
G n
!!
nn
!
G
" = 0
The condition .or a non2tri/ial solution o. the e0uations1

!!
##
!
G
" !
#2
!
#,
!
#n









= 0

!
n#
!
n2
!
n,
!!
nn
!
G
"

is o. eactly the same .orm as the procedure .or etracting the eigen/alues !
G
o. the
matri .ormed o. the elements !
a3
3y e/aluating the characteristic e0uation o. the matriP
an nth order polynomial in !
G
(Appendi ,+7 This illustrates the connection 3et6een the
t6o approaches to the pro3lem7 Since the 3asis states are orthonormal the normalisation
re0uirement reduces to1
Ga
= #.0
a
"ur purpose has 3een to Lnd the lo6est /alue o. !
G
, 3ut 6hat o. the other /alues
6hich the method ine/ita3ly producesJ We can distinguish t6o cases7
Case I. An some pro3lems, especially in angular momentum, 6e ha/e a complete set
o. 3asis states |a 7 Dor eample, i. 6e are calculating the spin2or3it coupling o. a single
p electron then there are only si states characterised 3y |l m
l
s m
s
(three /alues o. m
l
and t6o /alues o. m
s
+7 =nder such circumstances the n /alues o. !
G
are the n eigen/alues
o. our pro3lem and the coe.Lcents C gi/e us the corresponding n eigen.unctions7 These
types o. pro3lem are also easy to handle 3ecause the 3asis states con.orm rigorously to
the condition S
a3
=
)
a3
7
Case J. A. the 3asis set is o. necessity incomplete, as in the LCA"2C" theory
.or eample 6here 6e can ne/er include all the A"s 6hich contri3ute to the C"s
(Section ?7#,+, then the higher /alues o. !
G
ha/e no .undamental signiLcance7 9o62
e/er, 6e al6ays regard them as approimations to the higher eigen/alues o. the system,
though 6e ha/e no 6ay o. 4no6ing ho6 accurate they are ecept 3y comparison 6ith
eperiment7 An the 9uM c4el theory (Section #27#+ 6e also ma4e the drastic
approimation
S
a3
=
)
a3
7 Though it is mani.estly untrue it simpliLes the pro3lem enormously7
E(a&ple: 8he hydrogen ato& in a &agnetic eld
The nucleus and the electron 6hich together .orm a hydrogen atom each ha/e a magnetic
moment 6hich is proportional to their spin angular momentum7 These magnetic momenta
,
2
#
interact 6ith each other, the Dermi contact interaction, and 6ith an applied magnetic
Leld, the Neeman e..ect7 The mutual magnetic interaction o. nucleus and electron is not
the classical dipole2dipole interaction 6hich a/erages to Kero in a .ree atom7 The Dermi
contact interaction represents the energy o. the nuclear moment in the magnetic Leld o.
the electron 6hen the electron is at the nucleus7 (Dor s or3itals the maimum electron
density is .ound at the nucleus, as an eamination o. atomic or3ital 6a/e .unctions 6ill
sho67+ The 9amiltonian operator .or the magnetic interactions o. a hydrogen atom in a
Ou density (/ + is1
9

= gT
B
/ S

N
g
;
T
;
/ :

N
+ aS

I

The Lrst t6o terms are the Neeman terms and the last the Dermi contact7 g and g
;
are
the electron and nuclear g2.actors, T
B
and T
;
are the Bohr and nuclear magnetons, I

and
S

are the operators .or the spin angular momenta o. the nucleus and electron and S

N
and
:

N
are the operators .or the K components o. those momenta7 a = !
2
"T
0
gT
B
g
;
T
;
|
!0"
|
2
6here T
0
is the /acuum permea3ility and |
!0"
|
2
is the electron density at the nucleus7
(See Section #272 .or more on magnetic properties7+ The scalar product (S

I

+ can 3e
6ritten in terms o. the Cartesian components o. the /ector operators (S

terms o. the corresponding raising and lo6ering operators (Section *7-+1

and I

+, or in
aS


I

=
a
{
S

(
:

x
+
S

y
:

y
+
S

B
:

B
} =
aS

B
:

B
+
!a,2"
{
S

+
:

+
S

+
}
"ur 3asis states are the spin states o. the hydrogen atom and they can 3e deLned 3y
6riting do6n all possi3le com3inations o. the K2components o. the nuclear and electron
spin, i7e7 |m
S
(electron+, m
:
(nucleus+ 7 Since m
S
and m
:
can each ta4e /alues o. +
#
and

2
6e ha/e the .our 3asis .unctions1
|
a
= | +
#

+
#


|
3
= | +
#


#


|
c
= |
#

+
#

and
|
d
= |
#


#
2 2 2 2 2 2 2 2
The indi/idual spin .unctions are orthonormal, i7e7
+
#
| +
#
=
#
|
#
=
#.0 and
# # # #
2 2 2 2
+
2
|
2
=
2
| +
2
=
07 Conse0uently, the .unctions
|
a
|
d

are also ortho2normal
so that .or the o/erlap o. any pair S
i@
=
)
i@
7
To set up the secular e0uations 6e re0uire all *

* terms o. the .orm

i
|
9

|
@

P t6o
eamples 6ill su.Lce to sho6 ho6 they are calculated1

3
|
9

|
3
= +
#


#
|
9

| +
#


#
2 2 2 2
# # # # #
= +
2


2
|
gT
B
BS

N

g
;
T
;
B

A
N
+
aS

N

A
N
+
2
a
{
S

+

A

+
S

A
+
}| +
2


2

Since S

and its components operate only on the electron, I

and its components
operate only on the nucleus and the other sym3ols are not operators, 6e can 6rite1

3
|
9

|
*
=
gT
B
B
+
#
|
S
N
| +
#

#
|
#

g
;
T
;
/
+
#
| +
#

#
|
:
O
|
#
2 2 2 2 2 2 2 2
+
a
+
#
|
S

O
| +
#

#
|
:

O
|
#
2 2 2 2
# # # # # # # # #
+
2
a
{ +
2
|
S

+
| +
2

2
|
:

|
2
+ +
2
|
S

| +
2

2
|
:

+
|
2
}
S

#
S

#
# # # #
:

#

2
*
# #
The results o. operating 6ith S

+
, S

and S

O
on
| +
2

and
|
2

are /ery simple
(Bo *7#+1
# #
| +
2
|
2

+
0
| +
2


|
2

0
S

O +
#
| +
#

#
|
#
2 2 2 2
and there are corresponding results .or :

+
, :

and :

O
, so that1
# # #
Similarly1

3
|
9

|
3
= +
2
gT
B
/
+
2
g
;
T
;
/

*
a

3
|
9

|
c
=
gT
B
/
+
#
|
S
O
|
#

#
| +
#

g
;
T
;
/

#
| +
#
+
#
|
:
O
|
#
2 2 2 2 2 2 2 2
+
a
+
#
|
S
O
|
#

#
|
:
O
| +
#
2 2 2 2
+
!a,2"
{ +
#
|
S
| |
:
| + + + |
S
# # #
| | | + }
2
+
2 2

2 2

2 2
+
2
The Lrst three terms are Kero, on account o. the orthogonality o. the indi/idual spin
.unctions, and so is the .ourth 3ecause o. the properties o. the raising and lo6ering
operators7 "nly the term in S

+
:

is non2Kero so that1
3|9

|c = a,2
Thus, setting
e
= gT
B
/ and
;
= g
;
T
;
/ , 6e Lnd the secular e0uations1
C
#
!
#

e

#

;
+
a,*

E"
+
C
2
0
+
C
,
0
+
C
*
0
=
0
2 2
C
#
0
+
C
2
!
#

e +
#

;
a,*

E"
+
C
,
!a,2"
+
C
*
0
=
0
2 2
C
#
0
+
C
2
!a,2"
+
C
,
!

#

e

#

;

a,*

E"
+
C
*
0
=
0
2 2
C
#
0
+
C
2
0
+
C
,
0
+
C
*
!

#

e
+
#

;
+
a,*

E"
=
0
2 2
The Lrst secular e0uation contains only C
#
and is there.ore independent o. the others,
so that 6e ha/e1
# # # #
2

e

2

;
+
a,*

E
=
0

E
=
2

e

2

;
+
a,* and C
#
=
#.0
# #
Similarly, the last e0uation gi/es E
=
2

e
+
2

;
+
a,* and C
*
=
#.07
The secular determinant .or e0uations 2 and , is1

2
E a,* E +a,2


=
0

+
a,2

#
E

a,*

E

Where < =
e
+
;
7 Cultiplying the determinant out, 6e Lnd that the 0uadratic
e0uation .or E is1
E
2
+
!a,2"E

#
<
2

,!a,*"
2
=
0
2
gi/ing
#
E
=
a,*

#
{
a
2
+
E
2
} 2
Gi/en numerical /alues o. a and <, it is 0uite simple to etract the t6o coe.Lcients,
C
2
and C
,
, corresponding to these t6o energies, 3ut it is tedious and not 6orth6hile to
o3tain alge3raic epressions .or them7 9o6e/er, the case o. Kero magnetic Leld is o.
interest and merits .urther discussion7
An the a3sence o. a magnetic Leld < =
e
+
;
= 0 and 6e Lnd three degenerate
energy le/els o. a,* and one o. ,a,*7 The separation 3et6een these t6o states o. the
hydrogen atom, 6hich correspond to the t6o possi3le relati/e orientations o. the nuclear
and electronic magnetic moment, is #,*20 C9K7 At is the .re0uency 6hich has 3een
scanned 6ith the intention o. detecting intelligent li.e in the galay (Section *7$+7 To
o3tain the coe.Lcients C
2
and C
,
.or the Kero2Leld case 6e su3stitute the t6o energies
3ac4 into the secular e0uations7 When E = a,* 6e ha/e1
C
2
!a,* a,*" + C
,
!a,2" = 0 aC
2
,2 = aC
,
,2
and
C
2
!a,2" + C
,
!a,* a,*" = 0 aC
2
,2 = aC
,
,2
.rom 6hich it is clear that C
2
= C
,
and, since C
2
2
+ C
,
2
= #.0, their a3solute /alues are1

When E = ,a,* 6e ha/e1

C
2
=
C
,
=
#, 2
and
gi/ing
C
2
!a,* + ,a,*" + C
,
!a,2" = 0 aC
2
,2 = aC
,
,2
C
2
!a,2" + C
,
!a,* + ,a,*" = 0 aC
2
,2 = aC
,
,2

C
2
=
C
,
=
#, 2
Thus, summarising our results .or the Kero2Leld case 6e ha/e1
The singlet

E
=
,a,*
s = {
#, 2
}{| +
#


#
|
#

+
#
}
The triplet
2 2 2 2
# #
E
= +
a,*
t+#
= |+
2

+
2

E
= +
a,*
t0 = {
#, 2
}{| +
#


#
+ |
#

+
#
}
2 2 2 2
# #
E
= +
a,*
t#
= |
2


2

2
,
2
,
2
2
Appendi ,
Energies an/ 4aAe 6;n#tions
?0 Matrix 3iagonalisation
To .ully understand this su3@ect the reader needs to 4no6 ho6 to multiply matrices and
to Lnd the in/erse o. a matri7
The determination o. eigen/alues and eigen.unctions 3y the solution o. secular e0ua2
tions (Appendi 2+ plays an important pedagogical role in 0uantum mechanics 3ut Lnds
/ery little application today7 The ad/ent o. the digital computer has made matri alge3ra
much more potent .or the .ormulation and solution o. practical pro3lems in 0uantum
mechanics7 We shall use the determination o. the 9uM c4el C"s .or the propyl
radical, C
,
9
5
, to compare the t6o methods7
The secular e0uations .or the ( 2electron system 3ased on three con@ugated car3on
atoms ha/ing A"s $
#
, $
2
and $
,
are (Section #27#+1
C
#
!L '" + C
2
K = 0
C
#
K + C
2
!L '" + C
,
K = 0
C
2
K + C
,
!L '" =
0
Their solution, 3y the method descri3ed in Section #27#, leads to the .ollo6ing energies
and 6a/e .unctionsP eigen/alues and eigen/ectors respecti/ely in matri terminology1
G
#
=
#
$
#
+ !#

2"$
2
+
#
$
,
'
#
= L +

2K
G
2
= !#,

2"$
#
+ 0$
2
!#

2"$
,
'
2
= L

G
,
=
#
$
#

!#,
2"$
2
+
#
$
,
'
,
= L 2K
Matrix elements
When using matri2alge3ra 6e Lrst set up a matri the elements o. 6hich are the possi3le
/alues, nine in this case, o. $
i
|9

|$
@
, 6here
9

is the 9amiltonian operator and the $

i
,
i = # ,, are 4no6n as the 3asis .unctions7 An the present case they are the three car3on
2p
K
atomic or3itals7 These are the 0uantities 6hich 6e Lrst denoted 3y 9
i@
in the 9uM c4el
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
#5? 'nergies and Wa/e Dunctions 3y Catri <iagonalisation
#
2
,
2
theory and then replaced 3y L and K in accordance 6ith 9uM c4elGs approimations7
We o3tain the 9amiltonian matri Z9\1
9

$
#
$
2
$
,
$
#
L K 0
$
2
K L K
$
,
0 K L
Z9\
;ote that, .ollo6ing 9uM c4elGs method, 6e set all o/erlap integrals to Kero7 A.
the 3asis .unctions are not orthogonal and there are o/erlap integrals then their
inclusion complicates the pro3lem, though it can also 3e handled per.ectly 6ell 6ith matri
methods7 9o6e/er, most chemical applications o. 0uantum mechanics, apart .rom those
arising .rom C" theory, start .rom a 3asis o. orthogonal .unctions and the pro3lems
associated 6ith o/erlap do not there.ore arise7 The present description o. the matri method
o. o3taining eigen/alues and eigen.unctions applies only to a set o. 3asis .unctions
6hich are either truly orthogonal or are assumed to 3e so7
An a computational solution o. our pro3lem 6e 6ould no6 insert appropriate numerical
/alues .or L and K and use a computer to diagonalise the resulting matri7 9o6e/er, in
order to understand the process o. diagonalisation 6e shall here proceed alge3raically7
We pose the 0uestion1 What 6ould the 9amiltonian matri loo4 li4e i. 6e used the three
.unctions G
i
rather than the $
i
to construct itJ To ans6er that 0uestion 6e e/aluate t6o
matri elements as eamples1
#

# #

#
G
#
|9

|G
#
=
2
$
#
+
!#,
2"$
2
+
2
$
,
|9

|
2
$
#
+
!#,
2"$
2
+
2
$
,

# # #
=
*
$
#
|9

|$
#
+
2
$
2
|9

|$
2
+
*
$
,
|9

|$
,

+ 2 !
#
" !#,

2" $
#
|9

|$
2
+ 2 !
#
" !#,

2" $
2
|9

|$
,
2 2
# # #

=
*
L +
2
L +
*
L +
!#,
2"K + !#, 2"K = L + 2K

G
#
|9

|G
2
=
2
$
#
+
!#,

2"$
2
+
#
$
,
|9

|
!#,

2"$
#
!#

2"$
,

= !#,2 2" $
#
|9

|$
#

!#,2
2" $
,
|9

|$
,
+
#
$
2
|9

|$
#

#
$
2
|9

|
$
,

= !#,2
2"L !#,

2 2
2"L +
#
K
#
K = 0
2 2
When 6e e/aluate the remaining elements 6e Lnd, as the reader can conLrm, that the
matri constructed using the three .unctions G
i
is the diagonal matri Z<\, in 6hich the
diagonal elements are the C" energies, or eigen/alues o. our pro3lem1
9

G
#
G
2
G
,
G
#
L +

2K 0 0
G
2
0 L 0
G
,
'nergies and Wa/e Dunctions 3y Catri <iagonalisation #5-

0 0 L

2K
Z<\
The process o. diagonalising a matri is the process o. .orming com3inations o. the
3asis .unctions such that all the o..2diagonal elements o. the matri constructed 6ith
the ne6 com3inations are Kero7 The diagonal elements are then the eigen/alues7 The
.ormation o. the com3inations is su3@ect to the re0uirement that each o. the original 3asis
# # #
i i
# # #
2

2
2 2

2
2

i
i

i
.unctions is completely Qused upG in the process7 Drom a purely mathematical /ie6point,
the procedure in/ol/es the construction o. a second matri Z8\ such that1
Z8\
#
Z9\ Z8\ =
Z<\
6here Z9\ is the 9amiltonian matri to 3e diagonalised, Z8\
#
is the in/erse o. Z8\ and
Z<\ is the resulting diagonal matri7 This .orm o. trans.ormation o. Z9\ to Z<\ is called a
similarity transformation7 The multiplications are, o. course, matri multiplications7 The
matri Z8\ is 3uilt up 3y an iterati/e process 6hich computers do /ery 6ell, and many
sophisticated su3routines are a/aila3le .or the purpose7 When the procedure is complete
the re0uired eigen/ectors, 6hich are the atomic or3ital coe.Lcients, C
i
in this particular
application, are the elements o. the matri Z8\7 Thus, diagonalisation is a process 6here3y
those com3inations o. the 3asis .unctions, $
i
, 6hich are eigen.unctions o. 9

associated eigen/alues, are .ound simultaneously7

:eaders 6ho are .amiliar 6ith matri operations may li4e to conLrm that i.1
and their
i
Z8\
=
i

0

i
then Z8\

#
=
i

i
0

i
#
i
2
i
# #
2
2
#
i
2
i
#
i
2
#
i
2
i
# #
2
2
#
i
2
i
#
i
2
(There is no error here7 An this particular case, as is o.ten .ound in applications o. 0uantum
mechanics, Z8\ = Z8\
#
7 Z8\ is called a 1nitary matri7+
and
i
L +

2K 0 0
i
Z8\
#
Z9\Z8\ = Z<\ =
i
0 L 0
i
0 0 L

2K
T$e #$ara#teristi# e@;ation o" a matrix
A .urther eample o. the underlying similarity 3et6een the use o. matri and determinantal
methods to Lnd eigen/alues is .ound in the characteristic e0uation o. a matri7 We return
to our 9uM c4el matri .or the propyl radical Z9\ and su3tract ' .rom each diagonal
element1
$
#
$
2
$
,
$
#
$
2
$
,
L '
K
0
K
L '
K
0
K
L '
A. 6e regard the ne6 matri as a determinant and multiply it out according to the rules
o. determinant alge3ra 6e o3tain a cu3ic e0uation in '1
{L '} {!L '"
2
K
2
} K {K!L '"} = 0
{L '} {!L '"
2
2K
2
} = 0
=
The polynomial 6e ha/e o3tained in ' is called the characteristic e71ation o. the
matri and its roots are the eigen/alues o. the matri, as 6e no6 conLrm7 The roots are1
L ' = 0 ' =
L
and
!L '"
2
2K
2
= 0 L '

2K or ' = L

2K
An principle, the eigen/alues o. any matri can 3e determined 3y Lnding the roots o.
the characteristic e0uation7 9o6e/er, apart .rom in the simplest cases, diagonalisation is
3y .ar the more e.Lcient method7
8lo#>e/9o;t matri#es
An 0uantum2mechanical calculations it is 0uite common to Lnd matrices 6here a diagonal
element has no o..2diagonal element associated 6ith it7 "ne may also Lnd smaller su32
matrices 6ithin a larger matri 6here there are no o..2diagonal elements connecting the
su32matri 6ith the remainder o. the matri1
i
a 0 0
i
i
3 0 0
i
i i
i i
i 0 0 c y i
0 0 y d
An the eample a3o/e, the t6o 2 2 su32matrices at top le.t and 3ottom right ha/e
no connections to each other through o..2diagonal elements7 Catrices o. this .orm are
said to 3e *loc;ed o1t and each 3loc4 is independent o. the others7 Thus the a3o/e matri is
actually t6o independent matrices1

a

3
and

c y

y d
each o. 6hich can 3e diagonalised separately7
eneral sol;tion o" a & X & eigenAal;e pro?lem
There is a general solution o. the 2 2 eigen/alue pro3lem 6hich 6e use se/eral
times in this 3oo47 Suppose that 6e ha/e to determine the eigen/alues and eigen/ectors o.
the .ollo6ing matri in 6hich the 3asis .unctions ($
a
and $
3
+ are normalised and
orthogonal1
$
a
$
3
$
a
A N
$
3
N B
We deLne1
#
=
#
!A + B" =
#
!A B" and = {
2
+
N
2
}
2
2 2
6here .or 6e ta4e the root 6hich has the same sign as N7
We also deLne an angle (# + such that1
# #
cos # = |{! + ",2 }
2
| and sin # = |{! ",2 }
2
|
6here 6e ta4e the positi/e s0uare root in each case7
The eigen/alues ('+ and their normalised, orthogonal eigen/ectors ( + are no6
gi/en 3y1
'
#
= +
#
= cos # $
a
+ sin # $
3
'
2
=
2
= sin # $
a
+ cos # $
3
A. N R 0 then R 0 and the lo6er eigen/alue has a node 6hile i. N P 0 P 0
and the higher eigen/alue has a node7 This is the case, .or eample, 6hen N represents the
3onding interaction 3et6een t6o atomic 6a/e .unctions ($
a
and $
3
+ and is there.ore a
negati/e 0uantity7 Then, is P0, '
#
is the lo6er energy and
#
is the 3onding molecular
or3ital7
2
is the anti3onding C"7
Appendi *
!ert;r?ation T$eor0
'act solution o. SchroM dingerGs e0uation is possi3le .or only a /ery small proportion
o. the pro3lems o. interest in the physical sciences7 Great importance there.ore attaches to
approimate methods o. solution and among these methods pertur3ation theory, 6hich
is also etensi/ely used in classical mechanics, occupies a /ery important place7 The
techni0ue can 3e applied 6here the 9amiltonian can 3e 6ritten as a sum o. t6o parts, a
simple part 6hich i. present alone 6ould generate a solu3le SchroM dinger e0uation, and
a second part consisting o. one or more relati/ely small additional terms7 The approimate
3eha/iour o. the system can then 3e o3tained 3y considering the solu3le part as gi/ing
the dominant 3eha/iour and treating the actual 3eha/iour as a relati/ely minor de/iation,
or %ert1r*ation, .rom this calcula3le 3eha/iour7 The pertur3ation can 3e estimated 3y
studying the small, complicating additional terms in the second part o. the 9amiltonian7
The analysis o. time2independent and time2dependent pertur3ations is di..erent and 6e
treat only the .ormer type o. pro3lem here7
Time9in/epen/ent pert;r?ation t$eor0
We ha/e a 9amiltonian operator o. the .orm1
9

= 9
!0"
+ 9


!A*7#"
6here the energy associated 6ith 9
!0"
is large compared 6ith that deri/ed .rom 9


7 An
order to .acilitate the alge3ra 6e 6rite '0uation (A*7#+ in the .orm1
9

= 9
!0"
+ <9


!A*72"
< is an ar3itrary parameter, 6hich 6e use to 4eep trac4 o. the order o. the pertur3ation,
i7e7 the degree to 6hich our approimate 9amiltonian (9
!0"
+ <9


+ approaches the
true 9amiltonian (9

+7 "nce it has per.ormed its la3elling duty < is simply set e0ual to
#7 We
see4 eigen.unctions
|
G
4

and energies E
4
6hich satis.y the SchroM dinger
e0uation1
9

|G
4
= !9
!0"
+ <9


"|G
4
= E
4
|G
4
!A*7,"
An addition to the assumption concerning the relati/e magnitudes o. the energies asso2
ciated 6ith 9
!0"
and 9


6e also assume the .ollo6ing1
i+
9

does not depend eplicitly on the time7

-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
#?2 !ertur3ation Theory
ii+ The complete set o. orthonormal eigen.unctions |G
n
!0"
and energies E
n
!0"
6hich
satis.y the SchroM dinger e0uation1
9
!0"
|G
n
!0"
= E
n
|G
n
!0"
!A*7*"
are 4no6n7
iii+ At is possi3le to epand the solutions o. the pertur3ed pro3lem as a po6er series in <1
|G
4
= |G
4
!0"
+ <|G
4
!#"
+ <
2
|G
4
!2"
+
E
4
= E
4
!0"
+ <E
4
!#"
+ <
2
E
4
!2"
+ (A*75+
|G
4
!#"
is the Crst order correction to |G
4
|G
4
!2"
is the second order correction, and
so on, and it is these .unctions, together 6ith the corresponding /alues o. E
4
!#"
, E
4
!2"
etc7, 6hich 6e 6ish to Lnd7 The 'pansion (A*75+ re0uires that the successi/e a3solute
/alues o. E
4
!n"
decrease rapidly and it should 3e noted that it is di.Lcult to esta3lish this,
a %riori, in any particular case7 There.ore, 6hen pertur3ation calculations are carried out
the /alues o. E
4
!n"
must al6ays 3e chec4ed to ensure that the re0uired decrease in their
a3solute /alues is in .act .ound7
A. 6e no6 su3stitute the 'pansions (A*75+ into the SchroM dinger '0uation (A*7,+
6e o3tain1
!9
!0"
+ <9


"!|G
4
!0"
+ <|G
4
!#"
+ <
2
|G
4
!2"
+ "
= !E
4
!0"
+ <E
4
!#"
+ <
2
E
4
!2"
+ . . ."!|G
4
!0"
+ <|G
4
!#"
+ <
2
|G
4
!2"
+ " (A*7?+
Since < is an ar3itrary parameter, the coe.Lcients o. the same po6er o. < on the t6o
sides o. '0uation (A*7?+ must 3e e0ual7 '0uating these coe.Lcients .or increasing po6ers
o. <, i7e7 orders o. pertur3ation, 6e Lnd1
<
0
9
!0"
|G
4
!0"
= E
4
!0"
|G
4
!0"

<
#
9
!0"
|G
4
!#"
+ 9


|G
4
!0"
= E
4
!0"
|G
4
!#"
+ E
4
!#"
|G
4
!0"

<
2
9
!0"
|G
4
!2"
+ 9


|G
4
!#"
= E
4
!0"
|G
4
!2"
+ E
4
!#"
|G
4
!#"
+ E
4
!2"
|G
4
!0"

etc7 (A*7-+
< has no6 ser/ed its purpose7 The Lrst o. these e0uations is simply '0uation (A*7*+, the
SchroM dinger e0uation .or the unpertur3ed system and it tells us 6hat 6e already
4ne6, namely that the Keroth approimations to |G
4
and E
4
are |G
4
!0"
and E
4
!0"
7
The second e0uation may 3e 6ritten1
!9
!0"
E
4
!0"
"|G
4
!#"
+ !9


E
4
!#"
"|G
4
!0"
= 0 !A*7%"
T6o possi3ilities are open to us here7 We may 3e a3le to sol/e this e0uation directly to
o3tain the re0uired corrections |G
4
!#"
and E
4
!#"
, 3ut this is rarely possi3le7 ;ormally 6e
proceed .urther 3y epressing the correction |G
4
!#"
in terms o. the complete set o. Keroth
order 6a/e .unctions, |G
n
!0"
, 6hich are assumed to 3e 4no6n (assumption (ii+ a3o/e+1
|
G
4
!#"
=
n
C
n
|
G
n
!0"

!A*7$"
We su3stitute this epansion into '0uation (A*7%+, multiply on the le.t 3y one o. the

G
n
!0"
|


G
@
!0"
|
say, and integrate o/er all space gi/ing1
G
@
!0"
|!9
!0"
E
4
!0"
"

C
n
|G
n
!0"
+ G
@
!0"
|!9


E
4
!#"
"|G
4
!0"
= 0
n
And using '0uation (A*7*+1


C
n
G
@
!0"
|!E
n
!0"
E
4
!0"
"|G
n
!0"
+ G
@
!0"
|!9


E
4
!#"
"|G
4
!0"
= 0
n


C
n
!E
n
!0"

E
4
!0"
"

G
@
!0"
|
G
n
!0"
+
G
@
!0"
|
!9



E
4
!#"
"
|
G
4
!0"
=
0. (A*7#0+
n
Because the .unctions |G
n
!0"
are orthonormal, o. the n terms in the sum only that
.or 6hich n = @ is non2Kero7 There.ore, 6hen @ = 4 the only term in the sum 6hich
remains has n = 4 and is Kero 3ecause the energy di..erence is Kero7 '0uation (A*7#0+
then reduces to1

G
4
!0"
|
9



E
4
!#"
|
G
4
!0"
=
0
or

G
4
!0"
|
9


|
G
4
!0"
=
E
4
!#"

G
4
!0"
|
G
4
!0"
=
E
4
!#"
.
This gi/es us the Lrst correction to the energy (E
4
!#"
+, in the .orm o. the matri element
o. the unpertur3ed 6a/e .unction
|
G
4
!0"

6ith the pertur3ation 9


1
E
4
!#"
= G
4
!0"
|9


|G
4
!0"
9
44
!A*7##"
6here 9
44
is simply a con/enient sym3ol .or the matri element7
A. @ = 4 in '0uation (A*7#0+, the only term in the sum o/er n 6hich can 3e non2Kero
is the one 6here n
=
@ 6hich gi/es us an epression .or all the coe.Lcients ecept C
4
1
C
@
!E
@
!0"
E
4
!0"
" G
@
!0"
|G
@
!0"
+ G
@
!0"
|!9


E
4
!#"
"|G
4
!0"
= 0
C
@
!E
@
!0"
E
4
!0"
" G
@
!0"
|G
@
!0"
+ G
@
!0"
|9


|G
4
!0"
E
4
!#"
G
@
!0"
|G
4
!0"
= 0
C
@
E
@
!0"
C
@
E
4
!0"
+ 9
@4
0 = 0
"r
C
@
=
9
@4
,!E
4
!0"

E
@
!0"
" !A*7#2"
The .orm o. '0uation (A*7#2+ raises t6o important points1
i+ A. there is degeneracy such that E
4
!0"
= E
@
!0"
the coe.Lcient 3ecomes inLnite and the
theory 3rea4s do6n7 We return to this point later7
ii+ The initial assumption that 9


, is small compared 6ith 9
!0"
implies that 9
@4
is
small compared 6ith E
4
!0"
and E
@
!0"
7 Thus, pro/ided that there is no degeneracy,
or near degeneracy, C
@
6ill 3e small and the pertur3ed 6a/e .unction 6ill not
di..er much .rom the unpertur3ed, 6hich is the 3asic premise o. the theory7
By means o. '0uation (A*7#2+ 6e can Lnd all the C
@
ecept C
4
6hich can 3e .ound
using the re0uirement that the 6a/e .unction, up to the order considered (po6er o. < = #
in this case+, shall 3e normalised7 According to '0uation (A*75+, our 6a/e .unction correct
to Lrst order is1
|
G
4
= |
G
4
!0"
+ |
G
4
!#"

so the condition .or normalisation is1
G
4
|G
4
= G
4
!0"
+ G
4
!#"
|G
4
!0"
+ G
4
!#"
= #.0 !A*7#,"
@
+

Drom '0uation (A*7$+ 6e ha/e1
|G
4
!#"
=
@=4
C
@
|G
@
!0"
+ C
4
|G
4
!0"
!A*7#*"
6here C
@
can 3e o3tained .rom '0uation (A*7#2+7 Thus the normalisation integral
('0uation (A*7#,++ 3ecomes1
G
4
!0"
+

C

G
@
!0"
|G
4
!0"
+

C
@
G
@
!0"
!A*7#5"
@=4 @=4
6here 6e ha/e, .or the moment, omitted the term C
4
|G
4
!0"
in |G
4
!#"
7
Since the
|
G
n
!0"

are orthonormal (A*7#5+ 3ecomes1

G
4
!0"
|
G
4
!0"

@=4
C
@

C
@
G
@
!0"
|G
@
!0"
= #.0 +

@=4
C
@

C
@
Thus, the normalisation integral ('0uation (A*7#5++ is e0ual to unity plus the term
2
@=4
C
@

C
@
6hich is o. the order o. < 3ecause C
@
is o. order < since it is a measure o.
the small miing o. |G
@
!0"
into |G
4
!0"
induced 3y the pertur3ation7 There.ore, the 6a/e
.unction |G
4
= |G
4
!0"
+ |G
4
!#"
is normalised to order < i. 6e neglect the term C
4
|G
4
!0"
,
i7e7 i. C
4
= 07 This is reasona3le, |G
4
!0"
cannot 3e corrected 3y adding a .urther small
contri3ution .rom the same .unction7
"ur 6a/e .unction, correct to Lrst order and normalised, is there.ore1

4 =

4
!0"
+


9
@4
!0"
!0"

@
!0"
!A*7#?"
@=4
E
4

E
@
To o3tain E
4
!2"
6e 6rite the third '0uation (A*7-+ as1
!9
!0"
E
4
!0"
"|G
4
!2"
+ !9


E
4
!#"
"|G
4
!#"
E
4
!2"
|G
4
!0"
= 0 !A*7#-"
and epand |G
4
!2"
in terms o. the |G
m
!0"
as 3e.ore1

|
G
4
!2"
=
m
B
m
|
G
m
!0"

!A*7#%"
Su3stituting '0uations (A*7$+ and (A*7#%+ into '0uation (A*7#-+, multiplying on the
le.t 3y G
@
!0"
| and integrating o/er all space, 6e o3tain1

G
@
!0"
|
9

!0"

E
4
!0"
|

B
m
G
m
!0"
+
G
@
!0"
|
9



E
4
!#"
|

C
n
G
n
!0"

m n
G
@
!0"
|E
4
!2"
|G
4
!0"
= 0


C
n

G
@
!0"
|
9


|
G
n
!0"

n n
C
n
E
4
!#"

G
@
!0"
|
G
n
!0"

E
4
!2"

G
@
!0"
|
G
4
!0"

+

B
m
G
@
!0"
|9
!0"
|G
m
!0"
m m
B
m
G
@
!0"
|E
4
!0"
|G
m
!0"
= 0 !A*.#$"
A. @ = 4 the last t6o terms o. '0uation (A*7#$+ cancel each other and 6e ha/e1

C
n
G
4
!0"
|9


|G
n
!0"
C
4
E
4
!#"
G
4
!0"
|G
4
!0"
E
4
!2"
G
4
!0"
|G
4
!0"
= 0
n
E
or
E
4
!2"
=

C
n
9
4n

C
4
E
4
!#"
=

C
n
9
4n
!A*720"
n
=sing '0uations (A*7##+ and (A*7#2+ gi/es1

9 9
n=4

!2"
4
=
n4
!0"
4n
!0"
!A*.2#"
n=4
E
4

E
@
We do not usually pursue pertur3ation theory to terms o. order higher than E
4
!#"
, E
4
!2"
and G
4
!#"
, 3ut such .ormulae are a/aila3le7 Ze7g7 J7"7 9irsch.elder, W7 Byers Bro6n and
S7T7 'pstein, Advances in 31ant1m Chemistry, %, 25? (#$?*+\7 The results o3tained here
are summarised in '0uations (A*722+ and (A*72,+7
'nergy correct to second order1
E
4
=
9
44
+


9
n4
9
4n
!A*.22"
!0" !0"
Wa/e .unction correct to Lrst order1
n=4
E
4

E
n

4 =

4
!0"
+


9
@4
!0"
!0"

@
!0"
!A*.2,"
@=4
E
4

E
@
T$e #ase o" /egenerate eigenAal;es in t$e ;npert;r?e/ sol;tion
Dormulae (A*722+ and (A*72,+ .ail 6hen there are degeneracies7 =nder such circum2
stances 6e adopt a /ariational approach and proceed as .ollo6s, 6e ha/e1
9

= 9
!0"
+ 9


(A*7#+
9

|G
4
= E
4
|G
4
(A*7,+
We epand |G
4
using '0uation (A*7$+, multiply on the le.t 3y G
@
!0"
| and integrate
o/er all space gi/ing1
G
@
!0"
|9

|

C
n
G
n
!0"
E
4

C
n
G
@
!0"
|G
n
!0"

n n
= C
n
{ G
@
!0"
|9

|G
n
!0"
E
4
G
@
!0"
|G
n
!0"
}
n


C
n
{9
@n
E
4
)
@n
} (A*72*+
n
9ere, 9
@n
is a matri element o. the .ull 9amiltonian and )
@n
!the >ronec4er delta" =
# i. @ = n and 0 other6ise7 There is an e0uation o. the .orm o. '0uation (A*72*+ .or
each degenerate 6a/e .unction

G
@
!0"
|
, so that 6e o3tain a set o. linear, homogeneous
e0uations 6hich are 4no6n as the secular e0uations7 Cethods o. sol/ing secular e0uations
are descri3ed in Appendices 2 and ,7
Example
Consider the pro3lem o. a particle conLned 6ithin a one2dimensional 3o o. length L 3y
inLnite potential 6alls at = 0 and = L7 The solutions o. the SchroM dinger e0uation .or
2
L
L
0
the unpertur3ed pro3lem1
9
!0"
|G
n
!0"
= E
n
!0"
|G
n
!0"
!A*.*"
are (Section ,7?+ I eigen/alues1 E
n
!0"
= n
2
h
2
,%mL
2
and eigen.unctions1 G
n
!0"
=

(2HL+
sin (n( HL+, 6here h is !lanc4Gs constant, m the mass o. the particle and n = #
the 0uantum num3er7 These results apply 6here the particle has only 4inetic energy7 The
pertur3ation 6hich 6e shall apply is an electrostatic Leld such that the potential energy
o. the particle (8+ increases linearly .rom /H2 at = 0 to +/H2 at = L7 This potential
.orms our pertur3ing 9amiltonian, 6hich 6e can 6rite as1
9


= /!
#
L",L = /,L /,2
An order to apply pertur3ation theory using '0uations (A*722+ and (A*72,+ 6e re0uire
matri elements o. the .orm1
G
@
!0"
|9


|G
4
!0"
9
@4
and it is con/enient to e/aluate and ta3ulate these7 An general 6e ha/e1
9
@4
= G
@
!0"
|/,L /,2|G
4
!0"
= G
@
!0"
|/,L|G
4
!0"
G
@
!0"
|/,2|G
4
!0"

= !/,L" G
@
!0"
||G
4
!0"
!/,2" G
@
!0"
|G
4
!0"

Since the eigen.unctions are orthonormal, the last term contri3utes a constant energy
o. /H2 to all diagonal elements and Kero to all o..2diagonal elements7 To e/aluate the
contri3ution o. the Lrst term 6e 6rite out its .ull alge3raic .orm and consider Lrst the
diagonal elements1
2 /

L
2

4( /

L

24(

/
G
4
|
8
|
G
4
=
L

L
sin
0
L
dx
=
L
2


cos
L
d
=
2
Thus, the t6o contri3utions to the diagonal elements cancel and all 9
44
= 07
When 6e consider the o..2diagonal elements 6e Lnd1
2 /

L

@(

4(


G
@
|
8
|
G
4
=
L

L
sin
0
L



sin
L
dx
/
=
L
2

L

cos
0

!@ 4"(
L
cos

!@ ) 4"(

dx
L

L
2
cos

!@ 4"(

+
L
sin

!@

4"(

=
!@

4"
2
(
2
L !@

4"( L
0

L
2
cos

!@ + 4"(

+
L
sin

!@
+
4"(


!@
+
4"
2
(
2
L !@
+
4"( L
0
At is necessary to consider 6hether (@ + 4+ and (@ 4+ are odd or e/en7 When (@ + 4+
and (@ 4+ are e/en, inserting the limits o. 0 and L sho6s that in this case the integral
is Kero and there are there.ore no o..2diagonal matri elements 6hen @ and 4 themsel/es
are either 3oth e/en or 3oth odd7 Another 6ay o. saying this is to say that there are
no o..2diagonal elements 3et6een states o. the same parity and 6e shall return to this
important point 3elo67 Where (@ + 4+ and (@ 4+ are odd, i7e7 6here @ and 4 themsel/es

G
@
!0"
|
9


|
G
4
!0"

# 2 , * 5
@ = # 0
#.--% /,(
2
0
0.#*2 /,(
2
0
@ = 2

#.--% /,(
2
0

#.$20 /,(
2
0

0.#%# /,(
2
@ = , 0

#.$20 /,(
2
0

#.$5$ /,(
2
0
@ = *

0.#*2 /,(
2
0

#.$5$ /,(
2
0

#.$-5 /,(
2
@ = 5 0

0.#%# /,(
2
0

#.$-5 /,(
2
0
2
are o. di..erent parities, 6e Lnd on inserting limits that1
2/

*@4
G
@
|
8
|
G
4
=
(
2

!@
2
4 "
2
Anserting appropriate /alues .or @ and 4 and adding the constant contri3ution o. /H2
to each diagonal element, 6e can ta3ulate the matri elements .or the lo6er 0uantum
num3ers1
4 =
At is interesting to note ho6 rapidly the magnitude o. the o..2diagonal matri elements
decreases as the di..erence 3et6een @ and 4 increasesP !(
2
,/"9
#4
= #.--%, 0.#*2,
0.0,$, 0.0#? .or 4 = 2, *, ? and % respecti/ely7 The matri elements .or @ 4 = #
decrease slo6ly to a limiting /alue o. 2.0/,(
2
.or large /alues o. @ and 47
The a3sence o. o..2diagonal matri elements 3et6een eigen.unctions o. the same parity
eempliLes a 0uantum2mechanical principle that is o. particular importance7 An order that
an integral such as G
@
!0"
|9


|G
4
!0"
3e non2Kero, the symmetry o. each component o. the
integral G
@
!0"
| 9


and |G
4
!0"
must 3e such that their product is o. the highest possi3le
symmetry7 An the language o. group theory 6e say that the integral must 3elong to
the totally symmetric representation o. the symmetry group o. the pro3lem7 The only
symmetry property 6hich 6e ha/e recognised here is that o. parityP the phases o. the
6a/e .unctions can either change sign (odd+ or 3e unchanged (e/en+ on in/ersion in the
centre o. the 3o7 '/en .unctions ha/e the highest symmetry, so in order to ha/e a Lnite
/alue the integral G
@
!0"
|9


|G
4
!0"
must 3e e/en7 The phases o. the 6a/e .unctions |G
4
!0"
(Digure ,7?+ determine that the .unctions are e/en 6hen 4 is e/en and odd 6hen 4 is odd7
And the potential is odd since it changes sign at the centre point o. the 3o7 There.ore,
6hen G
@
!0"
| and |G
4
!0"
are o. the same parity the integral as a 6hole is odd and must
there.ore 3e Kero as the a3o/e numerical results sho67 But 6hen G
@
!0"
| and |G
4
!0"
are
o. opposite parity the integral as a 6hole is e/en and a Lnite result is possi3le7
We are no6 in a position to apply pertur3ation theory to a pro3lem7 An Bo ,7* 6e
interpreted the electronic spectra o. the cyanine dyes in terms o. the energies o. an
electron in a one2dimensional 3o7 We .ound there that the eperimental data ga/e a
/alue o. ,#, #0

20
J .or h
2
,%ml
2
, 6here l is the length o. an indi/idual 3ond in the
cyanine chain7 Dor our eample 6e consider a chain o. #? 3onds .or 6hich, since L = #?l,
h
2
,%mL
2
= !,#,,#?
2
" #0

20
J = #.22, #0

20
J7 Thus, the lo6er energy /alues .or
this molecule are1
E
#
!0"
= h
2
,%mL
2
= #.22, #0

20
J E
2
!0"
= *h
2
,%mL
2
= *.%$# #0

20
J E
,
!0"
= $h
2
,%mL
2
= ##.00* #0

20
J
|
G
2
= |
G
!0"
+
@
Suppose, .or the sa4e o. this eample, that / = 2.0 #0

20
J and 6e 6ish to determine
the ne6 E
2
and |G
2
6hich result .rom this pertur3ation7 According to '0uation (A*722+1
9
@2
9
2@
E
2 =
9
22 +

!0" !0"
@=2
E
4

E
4
9
22
= 0.0 and the largest term in the summation is 6hen @ = # and .or that term in
the summation 6e Lnd1
'
!2"
!#.--% 2.0 #0

20
"
2
#2.?5 #0

20
0.0,5 #0

20
J
2 !@=#"
=
Dor @ = ,1
(
*
!,.??% #0

20
"
=
20 2
,5-.,
=
20
'
!2"
!#.$20 2.0 #0

" #*.-5 #0
0.025 #0

20
J
2 !@=,"
=
(
*
!?.##, #0

20
"
=
5$5.5
=
;ote ho6 interaction 6ith a state o. lo6er energy, |G
#
!0"
raises the energy o. |G
2
,
6hereas interaction 6ith a state o. higher energy, |G
,
!0"
, depresses it7 The contri3utions
to the energy o. |G
2
.rom states o. energy higher than E
,
!0"
are negligi3le and 6e
Lnally ha/e1
E
2
= !*.%$# + 0.0,5 0.025" #0

20
J = *.$0# #0

20
J
Dor the corrections to the 6a/e .unction 6e use1

9
@2
2
!0" !0"
|
G
!0"

= |
G
!0"
@=2
E
2

E
@
#.--%

2.0

#0
20
!0"
#.$20

2.0

#0
20
!0"
2

,?.202 #0

20
|
G
#
+
?0.,,, #0

20
|
G
,

= |
G
!0" !0" !0"
2

0.0$%
|
G
#
+
0.0?*
|
G
,

Dinally, it is o. interest to consider the Lrst order correction to |G
#
!0"
6hich is readily
.ound to 3e1
|
G
#
= |
G
#
!0"
+
0.0$%
|
G
2
!0"

We note that the small admiture o. |G
2
!0"
has a positi/e coe.Lcient so that (see
Digure ,7?+ the amplitude o. the 6a/e .unction |G
#
!0"
in the region 3et6een = 0 and
L,2 is slightly increased 3y the pertur3ation 6hile 3et6een = L,2 and L it is reduced7
Since the electron density is proportional to the s0uare o. the 6a/e .unction, this means
that the pertur3ation increases the electron density in the lo6er hal. o. the 3o and
decreases it at the upper end7 This is @ust 6hat 6e 6ould epect, since the pertur3ing
potential increases linearly 6ith and the electron 6ill respond to this 3y mo/ing to
lo6er /alues o. 7 An applying pertur3ation theory it is rather easy to ma4e tri/ial errors
o. sign and simple, 0ualitati/e considerations such as the a3o/e can 3e a use.ul aid to the
detection o. such errors7

Appendi 5
T$e Sp$eri#al Harmoni#s
an/ H0/rogen Atom 4aAe
6;n#tions
The .unctions o. # and $ 6hich .orm the solutions o. the angular part o. the hydrogen2atom
pro3lem are 6ell 4no6n7 They are .re0uently .ound as the solutions o. di..erential e0uations
arising .rom the theoretical analysis o. pro3lems ha/ing spherical symmetry, such as the
/i3ration o. a gas inside a sphere or the motion o. the 6ater on a Oooded planet7 They are
especially important in atomic physics 3ecause, since all atoms are spherically symmetrical,
the solutions o. SchroM dingerGs e0uation .or any atom can 3e .ormed .rom the same
angular .unctions as the hydrogen atomP the presence o. other electrons and the conse0uent
inter2 electronic repulsion changes the radial 3ut not the angular part o. the 6a/e .unction7
Durthermore, since com3inations o. atomic or3ital .unctions are .re0uently used to
construct or3itals .or molecules their use etends throughout theoretical chemistry7 We
shall not descri3e the etensi/e mathematics o. these .unctions, 3ut simply 6rite do6n
the lo6er mem3ers o. the group in a .orm 6hich is use.ul in chemical applications7
T$e expli#it normalise/ "orms o" t$e ";n#tion
&
!$" "or & g .< r%< r&
# #

0
!$"
=
!2( "

2

0
!$"
=
!2( "

2
# #

#
!$"
=
!2( "

2
ep!i$"
#c
!$"
=
!( "

2
cos!$"
# #

#
!$"
=
!2( "

2
ep!

i$"
#s
!$"
=
!( "

2
sin!$"
# #

2
!$"
=
!2( "

2
ep!2i$"
2c
!$"
=
!( "

2
cos!2$"
# #

2
!$"
=
!2( "

2
ep!

2i$"
2s
!$"
=
!( "

2
sin!2$"
The a3o/e .unctions are normalised in the sense that1

2(

m
!$"
m
!$" d$ = #.0
0
;ote that there is a choice o. .unction7 The .unctions on the le.t are eigen.unctions
o. 3oth the energy operator and the angular momentum operator7 Those on the right are
eigen.unctions o. the energy operator only7
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
#-0 The Spherical 9armonics and 9ydrogen Atom Wa/e Dunctions
#

#
#

#
+
2

2
#

#
#
2
2
2
2
T$e expli#it normalise/ "orms o" t$e ";n#tion
l<&
!# " "or l g .< % an/ &
l = 0 l = # l = 2
s2.unctions p2.unctions d2.unctions
#

# 2

00
= +
2

2
#0
= +
!,,2"

cos #
20
= +
2

!5,2"

!, cos # #"
#

,

sin #
= #5 sin # cos #
#+#
=
2
2+#
2
#

,

sin #
= + #5 sin # cos #
##
= +
2
2#
2

2+2
= +
*

#5

sin #

22
= +
*

#5

sin #
The a3o/e .unctions are normalised in the sense that1

(

lm
!# "
lm
!# " sin # d#
=
#.0
0
;ote that the /alue o. m is restricted to integers in the range +l to l7 The positi/e
signs ha/e 3een included to emphasise that there is a rather su3tle sign con/ention in use
here7 At 6ill not a..ect our use o. the .unctions in any 6ay, 3ut it is important 6hen they
are used in con@unction 6ith ad/anced /ector2coupling methods7
There are t6o use.ul recursion .ormulae .or the 7
and
#
sin #


l|m|#
!# "
=
Z!l
+ |
m
| +
#"!l
+ |
m
|
",!2l
+
,"!2l
+
#"\
2

l+#|m|
!# "
#

Z!l
|
m
| +
#"!l
|
m
|
",!2l
+
#"!2l

#"\
2

l#|m|
!# "
#
cos #


l|m|
!# "
=
Z!l
+ |
m
| +
#"!l
|
m
| +
#",!2l
+
2"!2l
+
#"\
2

l+#|m|
!# "
#
+
Z!l
+ |
m
|
"!l
|
m
|
",!2l
+
#"!2l

2"\
2

l#|m|
!# "
T$e sp$eri#al $armoni#s <
l<&
!# < $"
!roducts o. the .unctions
lm
!# " and
m
!$" are commonly 4no6n as the
spherical harmonics7 Some normalised eamples .ollo61
l = 0 s2.unctions R
00
= +
2

!#,( "
l = # p2.unctions l = 2 d2.unctions
R
#0
= +
2
!,,( "

cos # R
20
= +
*
!5,( "

!, cos # #"
# # 2
R
# #
=
#

!,,2(" sin # ep!i$" R

R
# #
= +
#

!,,2(" sin # ep!i$" R

2+#
2#
=
2
!#5,2(" sin # cos # ep!i$"
= +
2
!#5,2("

sin #

cos #

ep!

i$"
R
2+2
= +
*

!#5,2("

sin
R
22
= +
*

!#5,2("

sin
# ep!2i$"
# ep!2i$"
0

The Spherical 9armonics and 9ydrogen Atom Wa/e Dunctions *2-

T$e $0/rogen atom waAe ";n#tions
Although they are not spherical harmonics, the hydrogen atom radial .unctions (:
nl
(r++
and the complete hydrogen 6a/e .unctions (
nlm
+ are included here .or the sa4e o.
completeness7
8he nor&alised e(plicit for&s of the function R
n<l
3r4 for n g %= 2 and 6
2N
We deLne =
=
na

r
6here N is the nuclear charge in units o.
+
e and a
0
is the Bohr radius7
,
n
=
# l
=
0 R
#0
!r"
=
!N,a
0
"
2
2 ep!

=,2"
,
!N,a
0
"
2
n
=
2 l
=
0 R
20
!r"
=
!2 =" ep!=,2"
2 2
,
!N,a
0
"
2
n
=
2 l
=
# R
2#
!r"
=
= ep!=,2"
2 ?
,
!N,a
0
"
2
2
n
=
, l
=
0 R
,0
!r"
=
!? ?= = " ep!=,2"
$ ,
,
!N,a
0
"
2
n
=
, l
=
# R
,#
!r"
=
!* ="= ep!=,2"
$ ?
,
!N,a
0
"
2
2
n
=
, l
=
2 R
,2
!r"
=
=
$ ,0
ep!=,2"
All the a3o/e .unctions o. r, # and $ are all indi/idually normalised to unity and
mutually orthogonal1

2(

m
!$"
m

!$" d$ = )
mm

P
0

(

2
lm
!# "
l

m

!# " sin # d#
=
)
ll

)
mm

P
0 0
R
nl
R
n

l

r dr
=
)
nn

)
ll

There.ore, a complete hydrogen atom 6a/e .unction .ormed .rom a product o. three
o. them is also normalised to one7 See Appendi - concerning the /olume element in
polar co2ordinates7
'o&e co&plete nor&alised !a9e functions for the hydrogen ato&
#
#s
=
(
,
N

2
a
0
ep!=,2"
#-2 The Spherical 9armonics and 9ydrogen Atom Wa/e Dunctions
0
0
0
0
,
#

N

2

!2 =" ep!=,2"
2s
=
* 2(
a
, 5
#

N

2

#
cos # = ep!=,2" =

N

2
K ep!=,2"
2pK
=
* 2(
a
* 2(
a
0
=sing the .unctions
#
+
#
,
#

#
,
#c
!$" and
#s
!$", or simply 3y noting that
the three 2p or3itals must 3e eactly the same apart .rom their dependence upon , y
or K, 6e o3tain1
5
#

N

2

ep!=,2"
2p
=
* 2(
a
5
#

N

2

y ep!=,2"
2py
=
* 2(
a

g


Suppose that 6e ha/e a system in 6hich n atomic or molecular or3itals are each dou3ly
occupied 3y a total o. 2n electrons7 The 6a/e .unction .or the system might 3e thought
to 3e1
g $
#
L!#"$
#
K!2"$
2
L!,"$
2
K!*" . . . $
ns#
K!2n s 2"$
n
L!2n s #"$
n
K!2n"
But it is .undamental to 0uantum mechanics that electrons are indistinguisha3le and an
e0ually accepta3le 6a/e .unction could 3e o3tained 3y interchanging any t6o electrons,
e7g7 # and *, gi/ing1
g $
#
L!*"$
#
K!2"$
2
L!,"$
2
K!#" . . . $
ns#
K!2n s 2"$
n
L!2n s #"$
n
K!2n"
Andeed, any one o. the (2n+U permutations
]
o. electrons in or3itals is e0ually accepta3le
and all must 3e included in the complete description o. the system7 Durthermore, 6e 4no6
that the 6a/e .unctions descri3ing sets o. indistinguisha3le, .undamental particles must
ha/e a clear symmetry 6ith respect to interchange o. any t6o o. those particles (see
Sections ##7* and ##75 .or a .urther discussion o. this point+7 Dor electrons the 6a/e
.unction must change sign (3e antisymmetric+ 6hen a pair o. electrons are interchanged,
6hich is simply another 6ay o. stating the !auli principle7 John Clar4e Slater (#$00 I
#$-?+ pointed out that these re0uirements could 3e concisely .ulLlled 3y 6riting the total
6a/e .unction as a determinant o. the .orm1
$
#
L!#"$
#
L!2" . . . $
#
L!2n s #"$
#
L!2n"

$
#
K!#"$
#
K!2" . . . $
#
K!2n s #"$
#
K!2n"


$
2
L!#"$
2
L!2" . . . $
2
L!2n s #"$
2
L!2n"

#,
t
!2n"U


_ _ _ _

_ _ _ _

_ _ _ _

$
n
K!#"$
n
K!2" . . . $
n
K!2n s #"$
n
K!2n"

<eterminantal 6a/e .unctions such as are .re0uently represented 3y the leading
diagonal o. the complete determinant enclosed 3et6een t6o pairs o. /ertical 3ars1
g #,
t
!2n"U kk$# L!#"$# K!2"$2 L!,"$2 K!*" . . . $n
#
K!2n s 2"$ L!2n s #"$ K!2n"kk
s n n
The determinant includes all possi3le permutations o. electrons in or3itals and 6hen 6e
multiply it out according to the esta3lished rules o. determinantal alge3ra each constituent
]
(2n+U (spo4en Q2n .actorialG or Q.actorial 2nG+ g 2n X !2n s #" X !2n s 2" X _ _ _ X #7
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
*,0 Slater <eterminants
permutation is generated, 6ith the correct change o. sign .or interchange o. any t6o
electronsP e7g7

$
#
L!#"$
#
L!2"$
#
L!,"

g !#,
t
?"

$
#
K!#"$
#
K!2"$
#
K!,"


$
2
L!#"$
2
L!2"$
2
L!,"

u !#,
t
?"kk$
#
L!#"$
#
K!2"$
2
L!,"kk
"n multiplying the , X , determinant out 6e o3tain the total 6a/e .unction in the
eplicit .orm1
!#,
t
?" n$
#
L!#"$
#
K!2"$
2
L!," s $
#
L!#"$
#
K!,"$
2
L!2" ) $
#
L!2"$
#
K!,"$
2
L!#"
s $
#
L!2"$
#
K!#"$
2
L!," ) $
#
L!,"$
#
K!#"$
2
L!2" s $
#
L!,"$
#
K!2"$
2
L!#"T
The eample o. a three2electron 6a/e .unction alerts us to a .urther point a3out the
complete description o. many2electron systems7 Clearly, the .unction in 6hich the electron
in or3ital $
2
has K spin 6ould 3e e0ually accepta3le and the complete description o. the
system must there.ore 3e the normalised sum o. t6o Slater determinants1
g !#,
t
#2" nkk$
#
L!#"$
#
K!2"$
2
L!,"kk ) kk$
#
L!#"$
#
K!2"$
2
K!,"kkT
Appendi -
Sp$eri#al !olar Co9or/inates
We re0uire three co2ordinates to speci.y a position in space7 An the Cartesian system
6e choose three mutually perpendicular aes 6hich 6e normally designate , y and K7
9o6e/er, .or a spherically symmetrical pro3lem such as the hydrogen atom, the spherical
polar co2ordinate system is much more con/enient7
The relationships 3et6een the Cartesian and polar co2ordinate systems is sho6n in
Digure A-7#7 Consider the point !P its pro@ection onto the y2plane is p7 An the Cartesian
system the co2ordinates o. ! are , y and KP in the polar system they are r, # and $7 r
is the distance o. ! .rom the origin o. the co2ordinate system, "7 # is the angle 3et6een
"! and the K2ais7 $ is the angle 3et6een "p and the 2ais7 Since "p = r sin # , simple
trigonometry sho6s that the relationships 3et6een the t6o co2ordinate systems are1
= r sin # cos $ y = r sin # sin $ K = r cos
#
and
r
2
=
2
+ y
2
+ K
2
T$e Aol;me element in polar #o9or/inates
Cany 0uantum2mechanical calculations in/ol/e the e/aluation o. the integral o. a product
o. t6o or more 6a/e .unctions o/er the 6hole o. co2ordinate space7 Dor eample, the
N
!
0 r
"
R
.
p
F
6ig;re A+1% The relationships 3et6een Cartesian and spherical polar co2ordinates
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
*,2 Spherical !olar Co2ordinates
6a/e .unction (G + must 3e normalised, i7e7 6e must ha/e1

all space

d dy dK

all space

d/ = #.0
An Cartesian co2ordinates the /olume element, d dy dK d/ is an inLnitesimally small
cu3e 6ith sides d, dy and dK7 We o3tain it 3y mo/ing inLnitesimally small distances
along the , y and K aes in the /icinity o. a point such as ! in the Lgure a3o/e7 To
o3tain the /olume element in polar co2ordinates 6e ha/e to do the same thing, 3ut the
process and the result is not 0uite so simple1
#7 Dirst 6e mo/e a distance dr along "!7
27 When 6e change the angle # 3y d# , ! mo/es along an arc the length o. 6hich depends
not only upon d# 3ut also upon r, the distance o. ! .rom ", according to the .ormula1
arc = r d# , 6here d# is measured in radians7
,7 A mo/ement along the co2ordinate $ 3rings a3out a mo/ement o. p, the pro@ection o.
! in the y2plane7 As a3o/e, since the length o. "p is r sin # , p mo/es along an
arc o. length r sin # d$7
Thus, in polar co2ordinates, the sides o. our inLnitesimal /olume are dr, rd# and
r sin # d$, and the ne6 /olume element is r
2
sin # dr d# d$7 There.ore, the
normalisation
integral 3ecomes1

all space

d dy dK

all space

r
2
sin # dr d# d$ = #.0
The limits o. the three co2ordinates are1 0 r , 0 # ( and 0 $ 2( 7 An
order to ma4e clear 6hich integration limits 3elong to each /aria3le, multiple integrals
o. this sort are o.ten 6ritten1
(

r
2
dr

0 0
2(
sin # d#
0

d$
= #.0
Appendi %
N;m?ers: Real< Imaginar0
an/ Complex
Any num3er 6hich can 3e plotted as a point on a scale etending .rom to + is
4no6n as a real num3er7 :eal num3ers are di/ided into t6o types1 rational num3ers
can 3e epressed in the .orm pH0, 6here p and 0 are integers, and irrational num3ers,
6hich cannot 3e epressed in that .ormP e7g7 #.,-5 = ##,% is a rational num3er and
( = *!# #,, + #,5 #,- + " is an irrational num3er7
The s0uare root o. # is denoted 3y i7 This 0uantity cannot 3e epressed as a real
num3er and the product o. i and any real num3er is a num3er 6hich also cannot 3e placed
on the scale o. real num3ers7 At is 4no6n as an imaginary num3er7 ;o real num3er can
3e e0ual to an imaginary num3erP apart .rom Kero 6hich is .ound on 3oth scales at the
point 6here they cross (Digure A%7#+7 ;ote that i
2
=
#, i
,
=
i, i
*
= +
#, i
5
=
i, and
that these /alues recur in cycles .or higher po6ers o. i7
A com%lex num3er is the sum o. a real and an imaginary num3er 6ritten in the
.orm (a + i3+, 6here a and 3 are 3oth real num3ers7 At can 3e represented in a diagram
(Digure A%7#+ 6here the scale o. imaginary num3ers is plotted at right angles to the real
num3er scale7 This type o. representation o. comple num3ers is 4no6n as an Argand
diagram7 When t6o comple num3ers are added (su3tracted+ the real and imaginary parts
are added (su3tracted+ separately1
!a + i3" ! + iy" = a + i!3 y"
An an e0uation in/ol/ing comple num3ers, the real and imaginary parts on the t6o
sides o. the e0uation are separately e0ual7
imaginary ais
c
(cid+ o
3 o
(a + i3+
a
d
real ais
6ig;re A,1% The representation o. comple num3ers on an Argand diagram
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
2
2i
*,* ;um3ers1 :eal, Amaginary and Comple
The t6o comple num3ers, (a + i3+ and (a i3+, ha/e a special relationship and are
said to 3e the com%lex con&1gates o. each other7 When a comple num3er is multiplied
3y its comple con@ugate a positi/e real num3er is al6ays o3tained1
!a + i3"!a i3" = a
2
a3i + 3ai 3
2
i
2
= a
2
+ 3
2
6hich must 3e positi/e.
An 0uantum mechanics the comple con@ugate o. a comple 0uantity is usually indicated
3y an asteris4 so that !a + i3"

= !a i3" and it is especially important that the product
o. t6o such 0uantities al6ays gi/es a positi/e result7
A .raction ha/ing a comple num3er in the denominator can 3e simpliLed 3y multi2
plying the numerator and the denominator o. the .raction 3y the comple con@ugate o.
the denominator7
The Atalian mathematician Girolamo Cardano (#50# I #5-?+ appears to ha/e 3een the
Lrst to pu3lish (in #5*5+ mathematics in/ol/ing the s0uare roots o. negati/e num3ers
6hich he o3tained in the process o. sol/ing 0uadratic e0uations7 Dor many years mathe2
maticians regarded such entities as strange and useless7 An #-02, Gott.ried Wilhelm Lei3nitK
(#?*? I #-#?+, 6ho de/eloped calculus independently o. ;e6ton and 6hose notation 6e
use in modern mathematics, 6rote1 QThe <i/ine Spirit .ound a su3lime outlet in that
6onder o. Zmathematical\ analysis, that portent o. the ideal 6orld, that amphi3ian 3et6een
3eing and non23eing, 6hich 6e call the imaginary root o. negati/e unityG7 And indeed,
anyone might ha/e 3een ecused .or thin4ing that such an un6orldly concept 6ould ha/e
no application in science 3ut, on the contrary, it has pro/ed etremely /alua3le7 Comple
num3ers play a /ery important role in the theoretical models o. many phenomena including
alternating currents, di..usion and the re.raction o. light7 The mere eistence o. this 3rie.
account attests to their importance in 0uantum mechanics7
A particularly interesting and use.ul result is o3tained 6hen the argument o. the epo2
nential .unction contains i7 Drom Bo ,7# 6e ha/e1
ep!ia" = # + ia + !ia"
2
,2U + !ia"
,
,,U + !ia"
*
,*U +
6hich, using the properties o. the po6ers o. i noted a3o/e, and the series .or sine and
cosine gi/en in 3o *7#1
= # + ia !a"
2
,2U i!a"
,
,,U + !a"
*
,*U + = cos!a" + i sin!a"
Similarly1
ep!ia" = cos!a" i sin!a"
Alternati/ely, cos(a+ and sin(a+ can 3e epressed in terms o. the eponential .unctions1
cos!a" =
#
{ep!+ia" + ep!ia"}
sin!a" =
#
{ep!+ia" ep!ia"}
Appendi $
3ipole an/ Transition 3ipole
Moments
The dipole moment o. a molecule is an important 0uantity in its o6n right and the
transition dipole moment plays a central role in the description o. the transition pro3a3ility
in in.rared and electronic spectroscopy7 9ere 6e Lrst determine the 0uantum2mechanical
epression .or the dipole moment o. a molecule7 An order to 3e speciLc 6e shall ta4e
as our eample the lithium hydride molecule and 6e shall assume that its orientation in
space is Led so that the LiI9 3ond is aligned along the 2ais7 The situation might 3e
crudely represented as in the schematic representation o. the lithium hydride molecule
sho6n in Digure A$7#, in 6hich the 3lac4 dots represent the electrons and the open circles
the nuclei7
As an illustration o. the principles o. the procedure, consider Lrst the determination
o. the centre o. mass o. the molecule7 A. 6e neglect the mass o. the .our electrons and
consider only the nuclei then the co2ordinate o. the centre o. mass (
0
+ is gi/en 3y1
m
9

9 +
m
Li

Li

0
=
m
9
+ m
Li
!A$.#"
6here
9
and
Li
are the co2ordinates o. the hydrogen and lithium nuclei 6ith respect to
any co2ordinate origin 6hich 6e choose7 :earrangement o. '0uation (A$7#+ gi/es1
m
Li
!
0

Li
" = m
9
!
9

0
"
and i. 6e set the origin to 3e the centre o. mass, i7e7
0
= 0.0, then 6e o3tain the more
.amiliar relationship1
m
Li

Li
+
m
9

9
=
0
The centre o. charge can 3e determined in an eactly analogous 6ay, 3ut there are t6o
o3/ious di..erences7 Dirstly, since the charge on the electron is e0ual in magnitude to that
#+ ,+
2ais
6ig;re A-1% A schematic representation o. the lithium hydride molecule
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd

elec

o. the proton 6e cannot neglect it and, secondly, 6e must ta4e account o. the di..erent
signs o. the charges on the nuclei and the electrons7 An .act, 6e can determine a centre
o. positi/e and a centre o. negati/e charge7 A. these t6o centres are coincident then the
molecule has no dipole moment 3ut i. they are not coincident then the molecule has a
dipole moment (C+ and for a ne1tral molec1le1
C = & < !A$.2"
6here & is the sum o. either the electronic or the nuclear charges and < is the distance
3et6een the centres o. positi/e and negati/e charge7
The centre o. positi/e charge .or our lithium hydride molecule might 3e 6ritten1
+
,

Li
+
#

9
;
0
;

;
0
=
*
=
!A$.,"
*
6here 0
;
is the charge on nucleus (;+7 But this e0uation assumes that the nuclei are
stationary and 6e 4no6 that they are not7 9o6e/er, 3y using the /i3rational 6a/e .unction,
(G
/i3
+, 6hich descri3es the motions o. the nuclei in the /i3rational ground state, 6e can
replace '0uation (A$7,+ 3y the 0uantum2mechanically eact epression1


/i3
C

nuc

/i3
D /
0
=
*

/i3
|
C

nuc
|

/i3

!A$.*"
*
6here C

nuc
=
;
0
;
F
;
in 6hich the co2ordinate F
;
has 3een replaced 3y the operator
F
;
7 (We use F .or the co2ordinates o. the nuclei and .or those o. the electrons7+
The remar4s a3o/e are e/en more true 6ith regard to the determination o. the centre o.
negati/e charge 3ecause 6e certainly cannot consider the electrons to 3e localised point
charges7 But 6e do 4no6 that the distri3ution o. the electrons is gi/en 3y the product o.
a 6a/e .unction (G
elec
+ and its comple con@ugate !G

" so that1
0
=
6here C

elec
=
e
0
e

e
7

elec
C

elec

elec
D /
*

elec
|
C

elec
|

elec

!A$.5"
*
But '0uations (A$7*+ and (A$75+ are also o/ersimpliLed in that they assume that 6e
can use 6a/e .unctions .or the nuclei (G
/i3
+ and .or the electrons (G
elec
+ independently
o. each other7 But 6e 4no6 that they are inter2related 3ecause, .or eample, the strength
o. a 3ond, and hence the .orce constant and the /i3rational .re0uency, depend upon
the electron distri3ution in the molecule7 There.ore, 6e must 6rite our 6a/e .unctions
as .unctions o. 3oth the electronic and the nuclear co2ordinates and, according to Born
and "ppenheimer (Section ?7,+, it is a /ery good approimation to 6rite the total 6a/e
.unction as a simple product1
$
total
!,F" = G
elec
!,F" G
/i3
!F" !A$.?"
An '0uation (A$7?+ represents all the co2ordinates (not @ust the co2ordinates+ o. all
the electrons descri3ed 3y the electronic 6a/e .unction and F represents the co2ordinates
o. the nuclei7 At is there.ore a general epression that is not limited to diatomic molecules7
The presence o. 3oth electronic and nuclear co2ordinates .ollo6ing G
elec
reminds us o.
the .act that the electronic 6a/e .unction depends upon the positions o. the nuclei as
G
<ipole and Transition <ipole Coments *,-
6ell as upon those o. the electrons7 Thus, the .ull epression .or the molecular dipole
moment is1
C
=
*!F
+

"
=
$
total
!,F"
|
C
nuc
|
$
total
!,F"

$
total
!,F"
|
C
elec
|
$
total
!,F"
0 0
!A$.-"
This is the 0uantum2mechanical epression .or the dipole moment o. a molecule in the
state $
total
(,F+7 At can 3e 6ritten more concisely in the .orm1
C = $
total
!,F"|C

|$
total
!,F" !A$.%"
6here
C

=
4
0
4

4
and the sum runs o/er all particles, electrons and nuclei, 6ith appro2
priate changes o. the sign and magnitude o. 0
4
7
T$e transition /ipole moment
Dor the determination o. the pro3a3ility that a spectroscopic transition 3et6een an initial
state ($
i
total
+ and a Lnal state ($
.
total
+ (Section %7?+ 6ill 3e allo6ed 6e re0uire an
epression .or the transition dipole moment7 This is a generalisation o. '0uation (A$7%+ in
6hich the 6a/e .unction to the le.t o. the operator is replaced 3y one .or the ecited
molecular state ($
.
total
+7 The resulting integral represents the transitory dipole moment
generated 6hen the molecule changes its state, 6hich is the QhandleG 3y means o. 6hich the
oscillating electric Leld o. the radiation is a3le to couple 6ith the molecule7 That is I
dropping the (,F+ to simpli.y the notation I 6e re0uire1
/i3
|C

|G
i
/i3
!A$.$"
'0uation (A$7$+ is the 3asic .orm o. the epression .or a transition dipole moment7 An
order to apply it to =828AS and A: spectroscopies it is epedient to de/elop the .ormula
.urther7 This is done in Section %7-7
Sele#tion r;les
An other parts o. this 3oo4, nota3ly Chapters 5 and %, selection rules ha/e 3een discussed,
o.ten on the 3asis o. the conser/ation o. energy, angular momentum and parity7 This is not
the most common approach to the pro3lem7 At is more usual to start .rom '0uation (A$7$+,
6hich sho6s that the o3ser/ation o. a spectroscopic transition re0uires a non2Kero /alue .or
the transition moment integral (C
i.
+7 The .ulLlment o. that re0uirement is 3est in/estigated
3y considering the e2m radiation as a 6a/e rather than a particle and to in/o4e the po6er.ul
methods o. group theory7 Since group theory is not discussed here 6e shall not use it,
3ut the 3asic principles o. its application can 3e illustrated 3y deri/ing LaporteGs atomic
spectral selection rule (Section 57#072+7 The integral

$
.
total
|
C

|
$
i
total

consists o.
three
parts to each o. 6hich a parity can 3e assigned7 The operator (C

+ is a property o.
the
e2m radiation or photon and the parity o. the dipole photon is u (Section %75+7 The initial
and Lnal states can 3e o. either parity and i. they are 3oth g the o/erall parity o. the
integrand is g u g = u7 A. 3oth states are u the integrand is also u, 3ut i. the t6o
states are o. di..erent parity then the integrand is g7 The crucial argument no6 goes as
.ollo6s7 The .act that 6e can classi.y our operator and states and their product in terms
o. their parities means that they are composed o. pairs o. parts 6hich are exactly e71al
#%2 <ipole and Transition <ipole Coments
in magnit1de and o. the same sign i. the .unction is g 3ut o. o%%osite sign i. it is u7
The process o. integration is the summation o. these parts, so the integration o. a u
.unction is al6ays a sum o. e0ual and opposite parts 6hich has to gi/e Kero7 An the case
o. a g .unction, ho6e/er, a non2Kero result is epected, though a .ortuitous cancellation
o. oppositely signed contri3utions to the sum can al6ays occur7 Thus 6e deduce that
allo6ed electric dipole transitions in atomic spectroscopy are al6ays u g in accord
6ith LaporteGs rule7
Appendi #0
4aAe 6;n#tions "or t$e
'
6 States
o" /
&
;sing S$i"t 2perators
The use o. the lo6ering operators (L
j
s
and l
j
s
+ to determine the com3ination o.
microstates 6hich .orm the
,
D state o. the conLguration d
2
pro/ides a good eample o. the
application o. the raising and lo6ering or shi.t operators (Section *7-+7
Notation:
The re0uired
,
D states are completely descri3ed 3y the ;ets kL 5
L
S 5
S
7
9o6e/er, since 6e shall concentrate on the component o. the triplet 6hich has S g # and
5
S
g )#, it 6ill 3e con/enient to a33re/iate to kL 5
L
, i7e7 k, 5
L
# )# 3ecomes k
, 5
L
7
Similarly, to simpli.y the notation the microstates are 6ritten in the .orm km
l
r
!#"
m
l
r
!2" 6here the r superscripts indicate the m
s
/alue o. the electron7
A ta3le o. the microstates o. the electron conLguration d
2
is not an essential prere0uisite
.or this eercise, 3ut it does pro/ide a use.ul running chec47 Another use.ul chec4 is the
.act that each com3ination o. microstates, as it is .ound, is normalised7
8he &icrostates of the conguration d
&
)#
5
S
0 s#
)* k)2
)
!#" )2
s
!2"
), k)2
)
!#" )#
)
!2" k)2
)
!#" )#
s
!2" k)2
s
!#" )#
)
!2" k)2
s
!#" )#
s
!2"
)2 k)2
)
!#" 0
)
!2" k)2
)
!#" 0
s
!2" k)2
s
!#" 0
)
!2" k)2
s
!#" 0
s
!2"
5
L
k)#
)
!#" )#
s
!2"
)# k)#
)
!#" 0
)
!2"
k)2
)
!#" s#
)
!2"
k)#
)
!#" 0
s
!2" k)#
s
!#" 0
)
!2"
k)2
)
!#" s#
s
!2" k)2
s
!#" s#
)
!2"
k)#
s
!#" 0
s
!2"
k ) 2
s#
!#" s#
s
!2"
0 k)#
)
!#" s#
)
!2" k)#
)
!#" s#
s
!2" k)#
s
!#" s#
)
!2" k)#
s
!#" s#
s
!2"
k)2
)
!#" s2
)
!2" k)2
)
!#" s2
s
!2" k)2
s
!#" s2
)
!2" k)2
s
!#" s2
s
!2"
k0
)
!#" 0
s
!2"
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
L
j
t
t
g )
#
**0 Wa/e Dunctions .or the
,
D States o. d
2
using Shi.t "perators
plus the Qmirror imageG o. microstates ha/ing 5
L
/alues o. s#, s2, s, and s*7
Clearly, the component o. the
,
D 6hich has the highest K2component o. or3ital angular
momentum may 3e 6ritten in the t6o e0ui/alent notations1
k, , v k)2
)
!#" )#
)
!2" !A#0.#"
We no6 apply the lo6ering operator1
#
L
j
s
kL 5 g nL!L ) #" s 5!5 s #"T
2
kL 5 s #
!A#0.2"
to the le.t2hand side o. '0uation (#07#+ and the operator1
#
l
j
s
kl m g nl!l ) #" s m!m s #"T
2
kl m s #
!A#0.,"
to each electron on the right2hand side7 Since no con.usion can arise, su3scripts L and l
ha/e 3een dropped to simpli.y the notation7
We Lnd that1
6hile
s
k, , g ?k, 2 !A#0.*"
t

l
j
is
k)2
)
!#" )#
)
!2" g 2k)#
)
!#" )#
)
!2"
)
i
?k)2
)
!#" 0
)
!2" !A#0.5"
;ote that l
j
is
has to 3e applied to the t6o electrons, # and 2 (indeed 6ith
su3script i+, in turn and the results added7 But the Lrst term on the right is unaccepta3le,
3ecause 3oth electrons ha/e the same 0uantum num3ers, and it must there.ore 3e discarded7
The right2hand sides o. '0uations (A#07*+ and (A#075+ must 3e e0ual so that1
k, 2 g k)2
)
!#" 0
)
!2"
We proceed in eactly the same manner to o3tain k, # .rom k, 2 1
t
and
L
j
s
k, 2
g
!#0"k, #
t
so that1

l
j
is
k)2
)
!#" 0
)
!2" g 2k)#
)
!#" 0
)
!2"
)
i
?k)2
)
!#" s#
)
!2"
k, # g
!2,5"k)#
)
!#" 0
)
!2"
t
!,,5"k)2
)
!#" s#
)
!2"
;ote that the coe.Lcients o. the linear com3ination o. microstates are such that the
.unction is normalised7 This pro/ides a good chec4 .or errors7
Similarly, a.ter applying the lo6ering operators to 3oth sides o. the last e0uation
6e Lnd1
t
#2k, 0
t
!#2,5"k0
)
!#" 0
)
!2"
t
t
!#2,5"k)#
)
!#" s#
)
!2"
t
) !#2,5"k)#
)
!#" s#
)
!2" ) !#2,5"k)2
)
!#" s2
)
!2"
:e@ecting the Lrst term on the right 3ecause it contra/enes the !auli principle (3oth
electrons in the same or3ital, m
l
g 0, 6ith the same spin, m
s
g )
2
+ 6e ha/e1
k, 0 g !2,
t
5"k)#
)
!#" s#
)
!2" ) !#,
t
5"k)2
)
!#" s2
)
!2"
Wa/e Dunctions .or the
,
D States o. d
2
using Shi.t "perators **#
The process can 3e continued until the remaining three components o. the
,
D state
6ith 5
S
g )# ha/e 3een .ound7
A similar procedure using S
j
s
and sj
s
can 3e used to Lnd the components ha/ing
5
S
g 0 and s#7 As an illustration 6e do this .or the k, 0 # )# 6a/e .unction 6here
6e ha/e reintroduced the S and 5
S
0uantum num3ers7 Since 5
S
g S g # 6e Lnd1
t
6hile
S
j
s
k, 0 # )#
g
2k, 0 # 0

sj
is
n!2,
t
5"k)#
)
!#" s#
)
!2" ) !#,
t
5"k)2
)
!#" s2
)
!2" T
i
There.ore1
g !2,
t
5"nk)#
s
!#" s#
)
!2" ) k)#
)
!#" s#
s
!2" T
) !#,
t
5"nk)2
s
!#" s2
)
!2" ) k)2
)
!#" s2
s
!2" T
t
k, 0 # 0 g !2,5"nk)#
s
!#" s#
)
!2" ) k)#
)
!#" s#
s
!2" T
) !#,
t
#0"nk)2
s
!#" s2
)
!2" ) k)2
)
!#" s2
s
!2" T
Continuing, and noting that an electron spin denoted 3y a superscript I must 3e anni2
hilated 3y sj
s
, 6e Lnd1
k, 0 # s# g !2,
t
5"k)#
s
!#" s#
s
!2" ) !#,
t
5"k)2
s
!#" s2
s
!2"
The method descri3ed a3o/e is ideally suited to pro3lems in/ol/ing a small num3er
o. electrons, 3ut .or num3ers o. electrons larger than three the method is /ery tedious
to apply7 Dor these cases more direct approaches, 3ased on ad/anced angular momentum
theory, are a/aila3le7
calculation o. &.( see also lo6ering operator
/alues .or octahedral comple Iab anomalous Neeman e..ect #20
angular momentum '%, -,I$, anti3onding molecular or3ital(s+, hydrogen
In/ex
;ote1 Digures and Ta3les are indicated 3y italic %age n1m*ers, Boes 3y em?ol/ene/
n;m?ers, .ootnotes 3y su.L QnG
a* initio calculation o. A: spectra ,#? I #-
a* initio C" calculations #?-, ,#-
a* initio 8B calculations #?-
a3solute Kero (o. temperature+ * I 5
a3sor3ance 2*$, &)+
a3sorption coe.Lcient &)+
a3sorption spectroscopy, transitions in 22% I
$ a3sorpti/ity #*
al4ali metals, properties eplained #0-
allo6ed electronic transition 2,? I -
alternant hydrocar3ons ,?#
ammonia, 3ond angle Ib_, #?5
Amontons, Guillaume ,, *
angular correlation ,*#
angular .unctions (6a/e .unctions+ o. hydrogen
atom $$ I #00
polar diagrams #00 I
* angular integral(s+
/ector model -- I %
as /ector 0uantity -5 I ?
B components %#, %*
see also or3ital angular momentumP
spin angular momentumP total
angular momentum
angular momentum eigen.unctions, <irac
notation .or %2
angular momentum operator(s+
commutation rules ,+I-&
eigen.unctions cJ, 5*, %2
.or electron on ring 50, ?0
angular momentum 0uantum num3er -$, ###
anharmonic oscillator ,02
anharmonicity ,0$
anharmonicity constant ,0,
car3on dioide ,#* I
#5 annihilation operator -&
addition o. -$, 2*5
in classical mechanics -, I 5
conser/ation o. -5, -$, 22-, 2*,
deLnition -*
o. electron on ring 50 I
2 and energy '%
eamples %* I ?
and magnetic dipole moment ,?-
notation %2, %,
o3ser/ing transitions %#
o. photon ##5, 225
0uantum2mechanical
addition o. -$ I %0
conser/ation o. %0
la6s %#
selection rules ##5 I #?
-he 31ant1m in Chemistry :7 Grinter
2005 John Wiley & Sons, Ltd
molecule #*5 I ?
anti.erromagnetism ,?5, ,-*
Argand diagram _XX
aromatic hydrocar3ons
3onding in #?0
delocalisation energies ,5$ I ?0
( 2electron systems in *5, #?0, ,2$
see also 3enKene
aromaticity ** I ?
Arrhenius e0uation -
atom
BohrGs model 2* I ?
Lrst (Lucretius+ model 2
:uther.ordGs model 2*
atomic emission spectra 2, I
?
atomic nuclei, magnetic properties 2?2 I *
#%% Ande
atomic or3ital o/erlap #*? I $
) (delta+ o/erlap #*%
non23onding o/erlap #*% I $
( (pi+ o/erlap #*- I %
' (sigma+ o/erlap #*-
atomic or3itals
and electronic spectroscopy ,2%
linear com3ination o. 200, ,5,
atomic spectroscopy, selection rules in
##5 I #-, *,-, *,%
atomic transition pro3a3ilities %&)I-
atomic units *0# I 2
atomic 6a/e .unctions, classiLcation o. ##-
au.3au principle *?
applications #0-, #50
A/ogadro constant *0#
Balmer e0uation .or hydrogen atom emission
spectrum 25, '', %&%
SchroM dingerGs interpretation $-
Balmer series (hydrogen atom emission
spectrum o. hydrogen atom+ 25, $-, %&%,
%&&
3and gap(s+
.ormation 3y periodic potential Xab
insulators ,%%
semiconductors ,%% I $ 3and
theory o. solids ,-% I $0
electron I gas (.ree2electron+ approimation
,%#I?
applications Xad
tight 3inding approimation ,-% I
%# applications XaY, XaI, Xad
3arium,
#
S
0
2to2
#
!
#
transition ##%, IIW
3asis .unctions *0* I 5, *##
linear com3inations o. *05
Bec0uerel, J7 #%2
Beer I Lam3ert I Bouguer la6 2*$ I 50, &)*I
,
Beer la6 &)+
3ent molecules Ibb, #?-, Ibd
3enKene
Q3reathingG /i3ration ,0,
delocalisation energy, compared 6ith
enthalpy o. com3ustion ,5$ I ?0, XcW,
'-%
>e4uleb structures, enthalpiesHheats
o. com3ustion ,5$ I ?0, '-%
molecular or3itals ,*# I 2
( 2electron energy le/els ,*2 I *
( 2electron spectrum ,*# I
* protons &,%
3eryllium atom, electron repulsion integrals
%+)
Bethe, 9ans Al3recht #%2
3lac4 3ody, meaning o. term #*
3lac423ody radiation #, I #%
emission spectra I_
interpretation 3y !lanc4Gs hypothesis
#?I#%
!lanc4Gs hypothesis #5 I #?
:ayleigh I Jeans e0uation I_, #5
Ste.anGs la6 #,
3loc4ing out o. matrices ,%5, *#*
Bohr I 'instein condition (selection rule+ ##5,
22? I -, 2,2, 2*%
in ;C: spectroscopy 2?*, 2??
Bohr I 'instein e0uation 2*, %?, 22*, &),
Bohr magneton ,?%, *0#
Bohr magneton num3er '-*
Bohr model o. hydrogen atom 2* I ?, '.,
'%I', -%, 22,, 22?, ,??
Bohr radius *02
Bohr theory o. hydrogen atom structure 2* I
? eperimental agreement 2?, ''
.urther de/elopment o. 2?
BoltKmann, Lud6ig 'd6ard -, #,
BoltKmann constant #5, *0#
BoltKmann la6 2*%
3ond angles
car3on compounds #5?
hydrides Ib_, #?5
3ond order ,?#
3utadiene XbI
3ond pairs (o. electrons+ #?5
in /arious molecules Ibb ` Ibd
3onding models
hy3rid or3ital approach #5, I
?2 molecular or3ital theory #,$
/alence 3ond theory #,- I $
3onding molecular or3ital(s+, hydrogen
molecule #** I 5
Born I 9a3er cycle #,2
Born I "ppenheimer approimation #,? I
- applications 2,*, 2$-
3asis #,?, &)'
limitations #**
BornGs interpretation o. eigen.unctions *# I *,
5#
3oron isotopes, nuclear spin 0uantum num3ers
%*
Bouguer I Lam3ert la6 &)+
see also Beer I Lam3ert I Bouguer la6
BoyleGs la6 ,
*ra ` ;et notation &.), 2,0
see also 4ets
Brac4ett series (emission spectrum o. hydrogen
atom+ %&%
Q3reathingG /i3ration (o. 3enKene molecule+
,0,
3ridge analogy (marching soldiers+ 2,%
Brillouin .unctions ,-#
3romochloromethane
A: spectrum ,0? I -
sp hy3rid or3itals IcW, #?0
sp
2
hy3rid or3itals IcW, #?0
sp
,
hy3rid or3itals #5%, Ica
compared 6ith di3romomethane XYd
*23romo22,?2dimethylphenol, ;C: spectrum
Jba
Bunsen, :o3ert Wilhelm 2,
3utadiene
charge densities XbI
9uM c4el or3itals Xcb
( 2electron charge densities XbI
trans isomer Xc_
car3on
electron conLguration #5?
hy3ridisation o. atomic or3itals #5? I ?#
car3on I car3on atomic or3ital o/erlap
IbI car3on compounds, 3ond angles #5?
car3on dioide molecule
angle23ending /i3ration XIY, ,##
e..ect o. Coriolis interaction ,#5
asymmetric 3ond stretching /i3ration 2**,
XIY
e..ect o. Coriolis interaction ,#2 I #5
Cg" stretching /i3rations 2**, ,#0, XIY,
,#2
Coriolis interaction ,#2 I #?
e..ect o. Dermi resonance ,#0 I ##, XIb
geometry #??
symmetric stretching /i3ration 2**, ,#0,
XIY, ,#2
/i3rational spectrum ,0$ I ##
car3onyl compounds, correlation o. Cg" 3ond
order 6ith car3onyl stretching .re0uencies
XbX
Cardano, Girolamo *,*
Cartesian coordinates, relationship 6ith polar
coordinates _XI
centre o. charge, determination o. *,5 I
? characteristic e0uation o. matri *#, I
#*
charge correlation energy ,,$
listed .or #s
#
2s
#
states o. helium atom XXa
charge densities ,?#
3utadiene XbI
charge distri3ution #5,
charge trans.er comple, energy cur/es .or
XXJ
charge trans.er (CT+ spectra ,,0 I 2
charge trans.er to sol/ent (CTTS+ transitions
,,#
charge trans.er transitions #$? I -, ,,0 I
# charge unit *02
Charles, Jac0ues ,
chemical 3onding theory, 0uestions to 3e
ans6ered #,2
chemical shi.t (in ;C: spectroscopy+
2?-I-0
delta ()" scale 2?% I -0
listed .or /arious species JbW
chemically e0ui/alent protons &,%
circle, motion in '.I%
circularly polarised radiation 22#
le.t2handed (LC!+ 22#, 225
in ;C: spectrometer &,.
propagation o. JJI
right2handed (:C!+ 22#, 225
Clar, '7 ,**
classical mechanics
angular momentum in -, I
5 applica3ility #2
de/elopment o. $ I #2
.ailure #2 I #,
0uantisation in #% I
20
Cle3sch I Gordan coe.Lcients %0
Cle3sch I Gordan series -$, -&I', 22,
closed shells #0$
coloured complees, eplanations #%%, #$?
coloured metals, eplanation ,$0
com3ination 3ands (in A: spectroscopy+ ,0,
commutation o. operators '(, 5-I%, *,
angular momentum operators ,+I,
complete or3ital 6a/e .unctions #0*
comple con@ugates 5#, 2,0, *,*
comple num3ers *,, I *
Compton, Arthur 9olly, on scattering o.
F2rays 3y electrons 225, &).I%
Compton 6a/elength &)%
computational de/elopments #?- I
% conceptual .rame6or4s 2
Condon, 'd6ard =hler 2,?, &)'
see also Dranc4 I Condon principle
conduction 3and ,%%
conLguration interaction #*,
con@ugated polyenes, electronic spectra *)I+,
,2$
conser/ation o. energy ##5, 22-, &)%
conser/ation o. mass 22*
conser/ation o. momentum -5, -$, 22-, 2*,,
&)%
Coolidge, A7S7 #*,
Coriolis interaction ,## I #2
in car3on dioide molecule ,#2 I
#? and Dermi resonance ,#5 I #?
correlation diagram, .or d
2
energy le/els in
octahedral Leld IWI, #$2
cosine .unction *&
Coulom3 integral %+(, &.*, ,,-, ,-5
Coulom3ic attraction ,,#
Coulom3ic repulsion %+(, &.*, ,,-
Coulson, Charles Al.red #,2
coupling, o. angular momenta -$ I %0, aY
co/alency, and ligand Leld theory #$$ I 20,
co/alent chemical 3ond(s+ #,# I -$
magnetic moments a..ected 3y ,?%
co/alent molecules
spectra ,2$ I
,0
n(

transitions ,,0
(

(

transitions ,2$ I ,0
transition2metal complees #$? I -, ,,0
creation operator -&
see also raising operator
crystal Leld (CD+ theory #%2 I -
compared 6ith molecular or3ital theory
200
transition2metal complees #%- I $?
inter2electron repulsion in #%%, #$*
spin I or3it coupling in #$5 I ?
cu3ic symmetry, d2electron energy le/els Iaa
Curie constant ,?5, '-*
Curie la6 ,?*I5
Curie temperature ,?5
.or iron ,-*
Curie I Weiss la6 ,?5, ,-2
cyanine dyes, electronic spectra *)I+, *2,I*
) (delta+ o/erlap #*%
d
*
comple, in octahedral Leld #$-
d
2
conLguration
energy le/els .or 6ea4, strong and
intermediate octahedral Lelds #$# I
,
,
D states, application o. shi.t operators to
determine 6a/e .unctions .or **0 I
#
microstates *,$
strong2Leld coupling scheme in octahedral
Leld #$,I5
6ea42Leld coupling schemes in octahedral
Leld #%$I$#
dd transitions #$?
d2electron matri element #%*
d2.unctions *2?
d2or3itals #00
angular part o. 6a/e .unction #0, I *
radial part o. 6a/e .unction WW
#
< state (singlet <+ #0$
energies .or /arious atoms IIY
2
< state (dou3let <+ #0%
<a/isson, Clinton Joseph 2-
de Broglie, Louis 2? I %
degenerate eigen/alues, in unpertur3ed solution
*2#
degenerate energy le/els **
degrees o. .reedom 2$0
delocalisation energy (<L'+ ,5$
3enKene, compared 6ith enthalpy o.
com3ustion XcW, '-%
delocalised electrons, in hydrocar3ons #?0
density .unctional theory (<DT+ #?%, #%#
density o. states, transition metals ,%#
descripti/e models 2
diagonalisation o. matri *#2 I #,
diamagnetism ,?*
diamond
3and theory applied ,%-, Xad
mechanical properties ,$0
diatomic molecule
dum323ell model #%, 20, 2$#, JWJ
comparison 6ith real molecule ,02 I ,
rotation o. '%-I&.
/i3ration o. 2$#, JWJ, '%,I%-
Corse potential energy cur/e ,02, XYX
rotation o. 2$* I -
di3romomethane, A: spectrum, compared 6ith
di3romochloromethane XYd
<ic4inson, W7C7 2?-
dipole I dipole interaction, compared 6ith
electron I nucleus interaction 200n, 2-2
dipole moments *,5 I -
<irac, !aul *-, -%
notation .or angular momentum
eigen.unctions %2
dou3le2Keta .unctions %+'
dou3let states &,%I&
dum323ell oscillator #%
as model .or diatomic molecule #%, 20,
2$#, JWJ, '%,I&.
comparison 6ith real molecule ,02 I
, rotation o. '%-I&.
/i3ration o. 2$#, JWJ, '%,I%-
potential energy characteristics #$
<6ingeloo # galay %?
e..ecti/e nuclear charge %+&
eigen.unction(s+ 2$, ,$
BornGs interpretation *# I
* com3inations o. 5%
determination o.
3y matri alge3ra *## I #5
3y solution o. secular e0uations *0? I
#0 o. di..erent operators 52 I ,
and eperimental measurements 5, I
* o. hydrogen atom 2$
normalisation o. *?, *(
orthogonality *?, *)
physically accepta3le *, I *, *- I %
eigen/alue pro3lem, general solution o. 2 2
pro3lem *#* I #5
eigen/alue(s+ 2$, ,$
angular momentum o. electron on ring cI
and eperimental measurements 5,
o. hydrogen atom 2$, $? I -
'instein, Al3ert %, #,
on light20uanta (photons+ 2#, 22,, 22*,
22?
electromagnetic units (emu+ -, 2#? 3enKene X_d
ratio to electrostatic units -, 2#? electron /olt 2*%
on photoelectric e..ect 20, 2#, 22,
eperimental conLrmation 22, 22,
relati/ity theory #,
see also Bohr I 'instein777
'instein coe.Lcients 250, &),I-
electric current, units o. measurement -, 2#?
electric dipole interaction energy 2,*
electric dipole radiation 222
photons
angular momentum ##5, 225
selection rules 225 I ?
electric dipole transitions, conser/ation o.
angular momentum 2*2
electric 0uadrupole radiation 222
photons, selection rules 22?
electric 0uadrupole transitions ##?
conser/ation o. angular momentum 2*,
electrical anharmonicity ,0$
electrical conducti/ity, temperature e..ects
Xaa
electromagnetic radiation 2#? I #$
electric Leld component 2#- I
#$ .orms 222
magnetic Leld component 2#$
Ca6ellGs e0uations -, 2#?, 2#- I #$
see also light
electromagnetic spectrum JId, 222
electron paramagnetic resonance ('!:+
spectroscopy #$$, 2?#
electron repulsion energy
singlet state %+(, ,,-I%
triplet state %+(, ,,?I-
electron repulsion integrals &.)I*, ,,-
com3ination .or
,
! and
,
D states o. d
2
#$0, &.+I,
listed .or d or3itals
in comple .orms &%.
in real .orms &.-
electron on ring *0 I *
accepta3le eigen.unctions .or *# I
* angular momentum 50 I 2
calculation o. epectation /alue *+I,
energy le/els .or _c
9amiltonian operator .or *0 I #
9uM c4elGs rule .or aromatic hydrocar3ons
**I?
electron spin #05
magnetic properties a..ected 3y -%, ,?$
transition pro3a3ility a..ected 3y ,** I
?
electron spin correlation #-, I 5
electron spin 0uantum num3er -%
electron spin resonance ('S:+ spectroscopy,
interactions studied 2?#
electron transition density, (

(

transition in
electron
in BohrGs model o. atom 2*
charge on 22
magnetic properties JbJ
mass at rest *0#, *02
particle I 6a/e duality 2- I
%
pro3a3ility distri3ution .or *2, 5#
electron a.Lnity, in charge trans.er a3sorption
3and ,,#
electron conLguration(s+ #0%
car3on atom #5?
oygen molecule #?*
electron correlation #0? I
-
ecited helium atom ,*#
hydrogen molecule #*, I
5
electron g2.actor ##%, *0%
electron in linear 3o *? I
%
angular momentum eigen/alues cI
3oundary conditions *%
eigen.unctions .or *- I %
normalisation o. *(
orthogonality *)
9amiltonian operator .or *? I
- linear momentum *$ I 50
electron2mediated coupling 2-2
electron I neutron interaction %5 I -, 200n,
2-2 electron I nucleus attraction, in helium
atom
,,2
electronic energy le/els,
transition2metal complees
#%- I $?
electronic or3ital motion, magnetic e..ect o.
,
?
?
I
%
electronic spectroscopy
,2- I *% applications
,2%
and atomic or3itals ,2%
classiLcation o. spectra
*?, ,** and molecular
or3itals ,2% selection
rules ,** I %
timescales 2*?, J_b
transition2metal complees #$? I -
see also =8 I 8AS spectroscopy
electronic states o. atom #0- I ##
electronic transition dipole moment
2,? electronic transitions
allo6ed 2,? I -
compared 6ith A: and ;C: transitions
J
_
I
.or3idden 2,-
hydrogen atom (#s2p transition+ 2,% I $
electrostatic Leld due to ligands #%2
see also crystal Leld theory
electrostatic units (esu+ -, 2#?
ratio to electromagnetic units -,
2#? elementary charge (electronHproton+
*0#, *02 emission spectra 2, I ?
emissi/ity #,
energy
conser/ation o. ##5, 22-
units 2*%, *02
energy2con/ersion .actors J_W
energy le/el diagram(s+
atomic electronic spectroscopy, sodium <
lines 2*2 I ,
in.rared spectroscopy JWb
;C: spectroscopy, Lrst2order spectrum
Jdc
( 2electron energy le/els .or 3utadiene Xcd
three interacting magnetic centres Xda
energy operator
eigen.unctions o. cJ
.or electron in linear 3o *? I
- .or electron on ring *0 I #
eigen.unctions cJ
e0uili3rium internuclear distance #,,
hydrogen chloride '&&
e0ui/alent nuclei &,.I+
ethene IcW
3onding in #5%, #?0
electronic spectroscopy 2*, I *
9uM c4el or3itals
2*, ethyne IbY
3onding in #?0
echange integral %+), &.*, ,,-, ,-5
epectation /alue 5*
eperiment design 2 I ,
eperimental measurements
e..ect on system 55 I -
and eigen.unctionsHeigen/alues 5,
eponential .unction *&
etinction coe.Lcient &)+
see also a3sorption coe.Lcient
.2or3itals #00
angular part o. 6a/e .unction #0*
,
D state (triplet D+, o. d
2
in octahedral Leld
calculation o. matri elements o.
crystal2Leld 9amiltonian &.(I)
6ea42Leld coupling scheme #%$ I
$0 6ith
,
! state #$0 I #
Daraday, Cichael -, 2#?
Dermi contact interaction 200n, 2-2, *0%
Dermi le/el ,%0, XaI
Dermi resonance ,0$ I ##
and Coriolis interaction ,#5 I #?
Dermi resonance interaction term ,#0, ,#?
.erromagnetism ,?5, ,-*
Lne structure
A: spectra 2$-, ,00
;C: spectra 200
Lngerprint (in A: a3sorption spectrum+ ,0$
DiKeau, Armand 2#?
DlemingGs le.t2hand rule '-&
Doc4, 8ladimir A7 #0?
.or3idden electronic transition 2,-
.orce constant 2$#
angle23ending, .or small molecules XYb
3ond2stretching, .or small molecules XYb
Doucault, Jean 2#?
Dourier trans.orm A: spectroscopy 2**
Dourier trans.orm ;C: spectroscopy 2-%
Dranc4 I Condon principle 2,? I -, &)'I*
.ree induction decay (;C: spectroscopy+
2-%
.rontier or3itals see highest occupied molecular
or3italP lo6est unoccupied molecular
or3ital
.undamental constants (listed+ *0#
g2.actor see electron g2.actorP or3ital g2.actor
gas e0uations
pressure I /olume ,
pressure I /olume I temperature (.or QidealG
gases+ 5
temperature I /olume , I *, _
Gay2LussacGs la6 , I *
German nouns, construction o. 2$
Germer, Lester 9al3ert 2-
Gillespie, :7J7 #?*
QgoodG 0uantum num3ers %0, %#
Goudsmit, Samuel A3raham -%, #05, ##%,
#20
group theory #%2
gyroscope -5, 2?5
9a3er, DritK #,2
see also Born I 9a3er cycle
9amiltonian .ormulation #2
9amiltonian operator *0
.or crystal Leld #%%
calculation o. matri elements &.(I)
matri #%$
.or electron in 3o *? I -
.or electron on ring *0 I #
.or harmonic oscillator 2$,
.or hydrogen molecule #,* I ?
.or many2electron atom #05 I ?
.or nuclear spin system 2-,, &,&
.or rotation o. diatomic molecule '&%
.or /i3ration o. diatomic molecule '%-
harmonic oscillator 2$#
compared 6ith real diatomic molecule
02I,
eigen.unctions 2$*, JWc, ,#2, '&'I(
energy I distance cur/es IW, JWJ
0uantisation o. energy 2$, I *
0uantum mechanics Lrst applied 2$0
9artree I Doc4 .unctions #0?
9artree (unit o. energy+ *02
9eisen3erg, >arl Werner, matri mechanics
2?
9eisen3erg uncertainty principle 5? I -,
2*? e..ects 5%, 2$*
9eisen3erg uncertainty relationships 5?, *,
9eitler, Walter #,2, #,-
9eitler and LondonGs calculations .or energy o.
co/alent 3ond #,2, #,- I %
helium atom
ground state (#s
2
" conLguration, 6a/e
.unction ,,2 I ,, ,** I 5
#s
#
2s
#
conLguration ,,, I *#
electron repulsion in triplet and singlet
states ,,$ I *#
energies o. #s2s ecited states ,,5 I $
energies o. singlet and triplet states
,,%I$
magnetic interactions ,-5 I
? one2electron energies ,,5
I ? total 6a/e .unction ,,*
t6o2electron (repulsion+ energy ,,? I
%,
,-*I5
helium I helium 3ond #*?
9ermite polynomials '&'
9erschel, (Sir+ William 2#-
9ertK, 9einrich -, 20, 2#-
heteronuclear diatomic molecules, molecular
or3ital theory applied #5# I ,
high2spin complees #$-
highest occupied molecular or3ital (9"C"+
,5-
energy di..erence 3et6een 9"C" and
L=C", correlation 6ith spectral 3and
energies ,2$, ,5%, Xca
9o..man, :oald, etended 9uM c4el C" theory
20,
homonuclear diatomic molecules, molecular
or3ital theory applied #*$ I 5#
9oo4eGs la6 #%, 2$0 I
# hot 3ands ,02
9uM c4el molecular or3ital (9C"+ theory
,52I?,
applications o. 9C" coe.Lcients ,?# I
2 applications o. 9C" energies ,5- I
?0 assumptions ,5*
3asis ,52 I ,
delocalisation energies ,5$
determination o. 9C" energies ,5* I
5
9o..manGs etended /ersion 20,
9"C" and L=C" energies calculated
using ,2$, ,5-
L=C" I 9"C" energy di..erence ,5%
correlation 6ith energy o. %ara 3and o.
aromatic hydrocar3ons XcW
method ,5, I *
( 2electron energy calculations ,2$,
,5%I?0
( 2electron structure o. 3enKene ,*#
9uM c4el or3itals
3utadieneXcb
ethene 2*,
9uM c4elGs (*N + 2+ rule ** I ?
9und I Culli4en 3onding model #,$
and electronic spectroscopy ,2%
9und I Culli4en .unction #,$
9undGs rules ##0 I ##
applications #50, #5?, #$-, 2-,
3asis %+(
data illustrating IIY
9uygens, Christian 2#?
hy3rid atomic or3itals #5*
hy3rid or3itals, choice o. #?# I 2
hy3rid2or3ital 3onds, properties #?2
hy3ridisation #5, I ?2
o. car3on A"s #5? I ?0, IbI
choice o. hy3rid or3itals #?# I 2
!aulingGs approach #5, I 5
and /alence 3ond theory #5?
hydrides, 3ond angles Ib_, #?5
hydrocar3ons
molecular geometry
type # (al4anes+ #5?, #5- I
% type 2 (al4enes and aromatic
hydrocar3ons+ #5?, #5% I
?0 type , (al4ynes+ #5?, #?0
hydrogen #s atomic or3ital(s+
out2o.2phase com3ination o. #*,, #*5 I ?
parity operation on ##? I
#- polarisation o. #*0 I #
radial density .unction WW
hydrogen atom
BohrGs model 2* I ?, '., '%I', -%, 22,,
22?, ,??
characteristic emission (#*20 C9KH
072### m+ %?, *#0
eigen.unctions 2$
eigen/alues 2$, $? I -
electronic energy #,,
electronic transition (#s2p transition+
2,%I$
interactions in magnetic Leld *0- I
#0 mass 20, ,%
parallel2to2antiparallel transition %?
radial density .unctions WW
spectral series %&%I&
spin properties %5 I ?
transition dipole moment &)&I'
6a/e .unctions $- I #00, *2- I %
angular parts $$ I #0*, IY_
e..ect o. polarisation #*0 I #
9eitler I London (/alence 3ond+ approach
#,-I$
hydrogen atom (contin1ed +
9und I Culli4en (molecular or3ital+
approach #,$
impro/ements #*0 I
# nodes #0*, IY_
nuclear charge and #*0
radial parts $% I $, IY_
hydrogen atom emission spectrum 25, $-,
%&%I&
Lyman series $-, %&%, %&&
hydrogen chloride (
#
9I
,5
Cl+, /i3ration o.
'&%I'
hydrogen molecule
3inding energy #,, I *
9eitler and LondonGs calculations #,2,
#,-I%
3ond length 20, ,%
dissociation energy #,,
eperimental /alue #,,, IXa
/arious calculations IXa, #*,I*
energy terms
4inetic energy o. electrons #,*
4inetic energy o. nuclei #,*
potential energy due to interelectronic
repulsion #,5
potential energy due to internuclear
repulsion #,*
potential energy due to nucleus I
electron attraction #,*
energy /s internuclear distance IXb
e0uili3rium 3ond length #,,
eperimental /alue #,,, IXa
/arious calculations IXa, #*,I*
.re0uency o. oscillation 20, ,%
9amiltonian operator .or #,* I ?
molecular or3ital energy2le/el scheme .or
I_b
normalisation o. 6a/e .unctions .or
%*-I+.
0uantisation in 20
spin I spin coupling in 2-# I 2
hydrogen sulLde, 3ond angle Ib_, #?5
hydroyl radical
charge distri3ution in #5,
molecular or3ital energy2le/el scheme .or
IcJ
molecular or3ital theory applied #5# I ,
" I 9 3ond length
#5# hypothesis
meaning o. term ? I -
testing correctness ,
ideal gas constant 5
ideal gas la6 5
imaginary num3ers *$, *,,
inLnitesimal rotations theory -.
in.rared (A:+ spectroscopy 2%$ I ,2*
3asis 2$0
characteristic group .re0uencies ,0%
compared 6ith ;C: spectroscopy 2*0 I
# electric dipole interaction energy 2,*
eperimental aspects 2*0
selection rules 2**, 2$- I
,02
timescales 2*?, J_b
/i3rations o. polyatomic molecules
,05I%
in.rared transitions 2,5 I ?
compared 6ith =8 I 8ASHelectronic and
;C: transitions 2,% I *#
intensities ,0# I
2 insulators ,%%
e..ect o. temperature on electrical
conducti/ity Xaa
integration, o/er Qall spaceG 5*, *'
inter2electron repulsion
calculation .or some states o. d
2
&.)I,
in crystal Leld theory #%%, #$*
.or p
2
conLguration %&'I(
tripletHsinglet states %+(
inter2electronic spin I or3it coupling ##5
intermediate spin I or3it coupling ##, I
#* intermolecular charge trans.er ,,0 I #
intramolecular charge trans.er ,,0
in/erse distance, epressed in terms o.
spherical harmonics #%,
ionic contri3utions, in co/alent 3onding models
#*2
ionic solids
mechanical properties ,$0
tight23inding /ersion o. 3and theory used
,%-
ionisation o. atom $-
ionisation energy, in charge trans.er a3sorption
3and ,,#
A: spectra
a* initio calculations ,#? I #-
3romochloromethane compared 6ith
di3romomethane XYd
com3ination 3ands ,0,
Lngerprint ,0$
o/ertones ,0,
A: spectroscopy see in.rared (A:+ spectroscopy
iron
e..ecti/e nuclear charge .or occupied or3itals
%+&
.erromagnetism ,-*
irrational num3ers *,,
isochronous protons &,%
Jahn I Teller e..ect #$$
James, 97C7 #*,
Jeans, James 9op6ood #5
&& coupling ##2 I #,
>el/in scale (o. temperature+ *
>eplerGs la6s o. planetary motion #0 I
## 4eto I enol e0uili3rium 2*5, 2*-
4ets #%$, *,$
see also 3ra I 4et notation
4inetic energy operator ?0
4inetic theory o. gases -
>irchho.., Gusta/ -, #*, 2,, 2#?
l2type dou3ling ,#5
ladder operators %2 I
,
Lagrangian .ormulation #2
Landeb .ormula #20
Landeb inter/al rule #$5
Lange/in relationship ,??, '-)
Laporte (selection+ rule ##-, #$?, *,-
Larmor .re0uency 2?5, 2??
Larmor precession 2?5, Jbb
la6s
deduction .rom eperimentation 5 I
? meaning o. term ?
lead atom, eigenstates %&,
Lei3nitK, Gott.ried Wilhelm *,*
Lenard, !hilipp 'duard Anton 20
length units *02
Lennard2Jones, J7 %+)
Le6is, Gil3ert ;e6ton 22,
ligand Leld (LD+ theory #%#
and co/alency #$$ I 20,
historical de/elopment #%2
ligand2to2metal charge trans.er (LCCT+ #$?,
,,0
light
corpuscular model 2#?
'insteinGs 0uantum model 22, 22,
/elocity o. 22,, *0#
.actors a..ecting 2#?
as limiting /elocity #,
ratio o. electrostatic to electromagnetic
units -, 2#?
6a/e theory 2#?
limitations 2#, 22,
see also electromagnetic radiation
linear com3ination o. atomic or3itals (LCA"+
approach 200, ,5,
linear molecules #??, Ibb, Ibd
linear momentum
conser/ation o. &)%
deLnition -, I *
o. electron in linear 3o *$ I
50 o. photon 22* I 5
linear momentum operator *$, ?0
linearly polarised radiation 220
as sum o. le.t and right circularly polarised
radiation &,.
Linnett, J7W7 #?#
London, DritK #,2, #,-
see also 9eitler and LondonGs
calculations
lone pairs (o. electrons+ #?5
in coordination complees 202
in /arious molecules Ibb, Ibd
lone2pair electrons, n( transitions ,,0
lo62spin complees #$-
lo6ering operator %2 I ,, ,-, -.I%, -&
applications &+-, &,%, &,&, &,'
lo6est unoccupied molecular or3ital (L=C"+
,5-
energy di..erence 3et6een 9"C" and
L=C", correlation 6ith spectral 3and
energies ,2$, ,5%, Xca
LS coupling ### I #2
Lucretius 2
Lummer, "tto :ichard #*
Lyman series (emission spectrum o. hydrogen
atom+ $-, %&%, %&&
magnetic dipole
deLnition ,??, '-&
orientation in magnetic Leld '-&I'
magnetic dipole I dipole interaction ,-*
magnetic dipole interaction energy 2,*, ,-*
magnetic dipole radiation 222
photons, selection rules 225 I
? magnetic dipole transitions ##?
magnetic Leld ,?*, ,?5 I ?
polarised light a..ected 3y -, ##%, IIW
spectral lines a..ected 3y ##% I
20 magnetic interactions
helium ecited state ,-* I
? three2centre ,-- I %
magnetic moment(s+
.or atomic nuclei 2?2 I
, .ormulae .or #$- I %
listed .or /arious transition2metal ions IWa
and magnetic suscepti3ility ,?*, '-'I+
magnetic properties
atomic nuclei 2?2 I
* electrons JbJ
protons JbJ
magnetic suscepti3ility ,?* I 5
relationship 6ith atomicHmolecular magnetic
moment '-'I+
see also /olume magnetic suscepti3ility
magnetically e0ui/alent nuclei &,%
magnetisation ,?*
magnetism ,?, I -%
e..ect o. electron spin ,?$
.or d
2
conLguration *,$ ;ebel temperature ,?5
.or p
2
conLguration IYW ;e6tonGs corpuscular /ie6 o. light 2#?
magnetism (contin1ed +
origins '-&
practical applications ,-0 I ,
and spin angular momentum -%, ,?$
transition2metal complees #$- I $
see also nuclear magnetic resonance
(;C:+ spectroscopy
magnetogyric ratio 2?,
many2electron atom(s+ #05 I -
electronic structure ##2 0uantum
num3ers .or #0% selection rules
.or dipolar radiation
##5I#?
many2electron 6a/e .unctions ,,2 I ,
mass
conser/ation o. 22*
reduced 2$# I 2,
'%- unit *02
mathematical models 2
matri diagonalisation *#2 I #,
matri elements *## I
#, matri mechanics 2?
Ca6ellGs e0uations -, 2#?
mean /alue
o. energy #,-
o. o3ser/a3le 5,
measurement, e..ect on system 55 I -,
+. mechanical anharmonicity ,0$
mechanical properties, solids ,$0
metal2sur.ace selection rule 2** I 5, ,0?
metal2to2ligand charge trans.er (CLCT+
#$? I -,
,,0 metals
e..ect o. temperature on electrical
conducti/ity Xaa, ,%$
theory o.
.ree2electron approimation ,%# I ?
tight23inding approimation ,-% I
%#
Wigner and SeitKGs remar4s #,5, ,%-
methane
3onding in #5- I %
magnetically e0ui/alent protons &,%
microstates #0$
hydrogen molecule I_b
hydroyl radical IcJ
using sp hy3rid oygen or3itals Icc
lines @oining A"s and C"s #5,
nitrogen molecule IcY
octahedral C9
?
molecule (hypothetical+
JYJ
oygen molecule IcY
molecular or3ital (C"+ theory #,$
compared 6ith crystal Leld theory 200
compared 6ith 8B theory #5?, #?,
computational de/elopments #?-
heteronuclear diatomic molecules #5# I ,
homonuclear diatomic molecules #*$ I
5# uniLcation 6ith /alence 3ond theory
#*#I,
molecular or3ital (C"+ 6a/e .unctions,
normalisation o. %+.
molecular or3itals
3onding and anti3onding #*5 I
? and electronic spectroscopy
,2%
imaging o. #?%
molecular solids
mechanical properties ,$0
tight23inding /ersion o. 3and theory used
,%-
moment o. inertia 2$?
momentum see angular momentumP linear
momentum
Corse potential energy cur/e ,02, XYX
Culli4en, :o3ert Sanderson #,$, ,,#
see also 9und I Culli4en 3onding model
Culli4en population analysis #5,
Culli4en 6a/e .unctions ,,#
multiple 3onds, 8S'!: theory #?5 I -
n2type semiconductor Xaa, ,%$
natural phenomena, o3ser/ation o. # I 2
near2in.rared (;A:+ spectroscopy ,#-
near2in.rared spectrum JId
Lrst disco/ered 2#-
ne3ulae, emission spectra 2*,
as Slater determinants %&&, &.+
Cillennium Bridge, London 2,%
Cilli4an, :o3ert Andre6s 22
eperiments on 'insteinGs photon hypothesis
2,, 22,
models, categories 2
molecular geometry #?, I -
8S'!: model used #?* I
- molecular magnets
interactions ,-* I ?
orientation in magnetic Leld '-&I'
molecular or3ital energy2le/el schemes
;e6tonGs la6s o. motion ?, -, ## I
#2 nitrogen molecule
3onding in #50
molecular or3itals IcY
imaging o. highest occupied C" #?%
;C: tomography 2?-
;C: transitions 2?*
compared 6ith =8 I 8AS and A: transitions
2,% I *#, 2--
selection rule 2??, &+,I,.
non23onding (atomic or3ital+ o/erlap #*% I
$ normal mode o. /i3ration ,0*
normalisation
o. eigen.unctions *?, *'I*(, *25
o. 6a/e .unctions
in 9uM c4el C" calculation
,5? .or hydrogen molecule
%*-I+.
notation, angular momentum %,
nuclear charge
e..ecti/e %+&
in hydrogen molecule #*0
nuclear g2.actor *0%
nuclear magnetic resonance (;C:+ imaging,
medical applications 2?-
nuclear magnetic resonance (;C:+
spectroscopy 2?# I %-
A
2
spectrum 2-5 I ?
A
,
spectrum &,)I+
ABF spectrum &,)
AF spectrum 2-* I 5
chemical shi.t 2?- I
-0
delta ()" scale 2?% I -0
shielding constant 2-0
standard used 2?$
early disco/eries 2?#
e0ui/alent nuclei &,.I+
eperimental aspects 2*0, 2-0
Lrst order spectra 2-* I 5
.ree induction decay 2-%
.re0uency region 2?*
intensities o. ;C: spectral lines 2-? I
- interactions studied 2?#
magnetic dipole interaction energy 2,*
and 0uantum mechanics 2-- I
% relaation processes 2-?
second order spectra 2-5 I ?
signal saturation 2-?
timescales 2*?, J_b
nuclear magneton *0#
nuclear spin angular momentum 0uantum
num3er(s+ %,
3oron isotopes %*
nuclear spin I spin coupling 2-0 I ,
nuclear spin system, energy le/els 2-, I ?
;yholm, :7S7 #?*
o3ser/a3les ,%
o3ser/ation o. natural phenomena # I 2
prediction 3ased on 2
octahedral comple
angular integrals listed .or Iab
Brillouin .unctions .or single d electron
XdI, ,-2 octahedral
crystal Leld
calculation o. matri elements #%2 I -
results #%? I -
octahedral C9
?
molecule (hypothetical+ JYY
atomic or3ital o/erlap in JYI
molecular or3ital energy2le/el scheme
JYJ
molecular or3ital theory applied 200 I
2 octahedral species Ibb`d
octahedral symmetry, d2electron energy le/els
Iaa
one2dimensional 3o
electron in
accepta3le eigen.unctions *- I
% 3oundary conditions *%
9amiltonian operator .or *? I
- linear momentum *$ I 50
particle in *2# I 2
pertur3ation theory applied *22 I
* one2dimensional model
in 3and theory ,%# I ?
see also electron in linear 3o
one2electron atoms #0* I 5
selection rules .or dipolar radiation ##5
see also hydrogen atom
one2electron energies, ecited states o. helium
atom ,,5 I ?
operands, meaning o. term ''
operators ''I(, ,$
angular momentum operator 50, ?0
commutationHnon2commutation o. '(,
5-I%, *,
eigen.unctions o. di..erent 52 I
, 4inetic energy operator ?0
linear momentum operator *$, ?0
position operator 5$
potential energy operator 5$ I ?0
"ppenheimer, J7 :o3ert #,?
see also Born I
"ppenheimer
approimation
optical density &)+
see also a3sor3ance
optical properties, solids ,$0
or3ital angular momentum -? I %, ,+
causes -%
notation %,
or3ital angular momentum 0uantum num3er
o. rotating diatomic molecule %,
o. single electron %, I *, #0%
or3ital g2.actor ,?%
or3ital hy3ridisation #5, I
?2 or3ital o/erlap #*? I $
"rgel diagram IWI
see also Tana3e I Sugano diagram
orthogonality o. eigen.unctions *?, *'I)
oscillating electric Leld component o. light
2#-I#$
oscillating magnetic Leld component o. light
2#$
o/erlap integrals %*-
in 9uM c4el C" theory ,5?
o/ertones (in A: a3sorption spectra+ ,0,
oygen
Schumann I :unge 3ands &)*
sp hy3rid or3ital Ic_
oygen molecule
3onding in #50 I
#
electron conLguration #?*
( 3onding, in hydrocar3ons #?0
( 2electron spectra, 3enKene ,*# I *
( 2electron systems
in aromatic hydrocar3ons *5, ,*#
in con@ugated polyenes *)
( (pi+ o/erlap #*- I %
( (

transitions ,2$ I ,0
in 3enKene, electron transition density X_d
p
2
conLguration, terms determined .or
#0$I#0
p
2
electron conLguration
energies %&&I)
spin I or3it coupling in II_
terms determined .or #0$ I
#0 p2or3itals #00
angular part o. 6a/e .unction #0# I
, radial part o. 6a/e .unction WW
,
! state (triplet !+ ##0 I ###
energies .or /arious atoms IIY
6ea42Leld coupling scheme in octahedral
Leld #$0I#
5
! state (0uintet !+ #0%
p
2
2to2s
#
p
#
transition %&*I+
p2.unctions *2?
p2type semiconductor Xaa, ,%$
pairing energies #$-
paramagnetism ,?*
e..ect o. temperature ,?* I 5
temperature2independent ,?5
parity *2,
atomic or3itals ##? I #-
in crystal Leld theory #%*
photons 225
parity selection rule ##-, 225
!aschen series (emission spectrum o. hydrogen
atom+ %&%
!auli, Wol.gang -%, 2?#
!auli eclusion principle *5, -%, #05, #,%,
,,,
applications #0-, ##,, #50, **0
e..ects on /alence electron distri3ution
#?#I2, %+'
!auling, Linus Carl #5,, #%2
2,*2pentane dione, 4eto I enol e0uili3rium
2*5, 2*-
periodic 3oundary conditions *%, ,%2
periodic potential, 3and gap .ormed 3y ,%2 I
? periodic ta3le, 0uantum2mechanical /ie6
#0-, ##*
pertur3ation theory *#- I 2*
eamples o. ##2, ,%2, *2# I
*
!.und series (emission spectrum o. hydrogen
atom+ %&%
phase angle 2$#
photochemical reactions #*?, ,,%
photoelectric e..ect 20 I ,, 22,
'insteinGs theory 2#
eperimental conLrmation 22
photon counting *-
photon(s+ 2#, 22,
angular momentum ##5, 225
detection o. 2*2
energy 22*
linear momentum 22* I
5 mass 22*
parity 225
properties 22, I
?
release o. electrons caused 3y 20 I ,,
55
term Lrst used 22,
/elocity 22, I *
photosynthesis #*?
physical la6s 5 I ?
!lanc4, Ca %, #5
3lac423ody radiator hypothesis #,, #5 I
#?,
2*
!lanc4Gs constant #5, 2*, *0#
eperimental determination o. 22
plane polarised light 220
directional interaction ,0?
resolution into x and y components JJY
planetary motion #0 I ##
!latt, J7:7 *?, ,**
polar coordinates *,#
relationship 6ith Cartesian coordinates
_XI
SchroM dinger e0uation epressed in $- I
%,
,0,I*
/olume element in *,# I
2 polar diagrams
d2or3ital angular .unctions #0, I
* p2or3ital angular .unctions #0#
I , s2or3ital angular .unction #0#
polarisation
o. atomic or3itals #*0 I #
as o3ser/a3le property +.
polarised light 2#$ I 2#
circularly polarised light 22#
e..ect o. magnetic Leld -, ##%, IIW
linearly polarised light 220
and 0uantum mechanics *-I+%
polyatomic molecules, /i3rations ,0, I $
polynomial, roots o., .or 9uM c4el
molecular or3ital calculation ,55
!ople, J7A7 %+)
position operator 5$
postulate, meaning o. term ? I -
potential2energy cur/es, diatomic molecules
&)' I &))
potential2energy operator 5$ I ?0
!o6ell, 97C7 #?*
prediction, approaches to 2
principal 0uantum num3er $?
principle, meaning o. term ?
!ringsheim, 'rnst #*
pro3a3ility, determination in 0uantum
mechanics 2,2
!roctor, W7G7 2?-
progression (o. spectral 3ands+ 2,%
propyl radical, 9uM c4el matri .or *#2 I
#,
o. hydrogen atom WW
SlaterGs simpliLcation %+&
radiation I matter interaction 2#?
time2dependent interaction 2,0 I ,,
2??I-
time2independent interaction 2,0,
2,, I *5, 2$-
radio astronomy, hydrogen emission used %?
raising operator %2 I ,, ,-I-&
applications &+- I &,., &,&I'
:aman spectroscopy ,0$
car3on dioide /i3rational spectrum ,#0,
311
proteins, ;C: spectroscopy 2-0 rare earth coupling scheme #%%
proton rational num3ers *,,
magnetic properties JbJ
mass at rest *0#
proton ;C: transitions
compared 6ith electronic and in.rared
transitions J_I
see also nuclear magnetic resonance
(;C:+ spectroscopy
0uantaH0uantum, term Lrst coined #?
0uantisation o. energy #?
in classical mechanics #% I 20
0uantum electrodynamics (&'<+ -&, 2*-
0uantum mechanical harmonic oscillator
2$,I*
0uantisation o. energy 2$, I *
/i3rational eigen.unctions 2$*
Kero2point energy 2$*
0uantum mechanics
addition and conser/ation o. angular
momentum -$ I %0
applications ,- I -2
co/alent chemical 3ond #,# I -$
and ;C: spectroscopy 2-- I %
or3ital angular momentum in -? I
%
progression .rom classical mechanics
#,I,*
SchroM dinger method ,$ I *0
o. transition pro3a3ility 22- I ,,
0uantum num3er(s+ #?
.or many2electron atom #0%
o. single electron #0%
0uarter26a/e plate 22#
0uartet state &,%
0uenching #$%, ,?%
:acah parameters #$-, &.*
A parameter #$*, &.*
B parameter #$,, &.*
C parameter &.*
radial .unctions $% I $
:ayleigh I Jeans e0uation I_, #5
real num3ers, types *,,
reduced mass 2$# I 2, '%-
hydrogen chloride '&%
:egnault, Charles *
relati/istic mechanics #,
relaation processes, in ;C: spectroscopy
2-?, 2-%
resonance energy ,5$
see also delocalisation energy
resonance sta3ilisation, in charge trans.er
transitions ,,#
resonance structures #?,
3enKene IbX
car3onate anion IbX
cyanine dyes **
restoring .orce (in simple harmonic motion+
2$0
rigid rotator model 2$-
eigen.unctions 2$- rotational
motions 2$% I $ /i3rational
motions 2$$ I ,00
:itter, Johann Wilhelm 2#-
:osen, ;7 #*0 I #
rotation o. diatomic molecules '%-I&.
rotational constant 2$?
car3on dioide ,#* I #5
rotational selection rule 2$% I
$
semi2classical interpretation ,0#
:ussell I Saunders coupling ### I #2
:uther.ordGs model o. atom 2*
:y3erg, Johannes :o3ert, on Balmer e0uation
%&%
:y3erg constant %&%
/alues listed .or /arious atoms and ions
IYc
' 3onding, in hydrocar3ons #?0
' (sigma+ o/erlap #*-
s2.unctions *2?
s2or3itals #00
sp hy3rid or3itals IcW, #?0
sp
2
hy3rid or3itals IcW, #?0
sp
,
hy3rid or3itals #5%, Ica
see also harmonic oscillator
spin angular momentum -%, 2?#
simultaneous homogeneous e0uations *0? notation %,
s2or3itals (contin1ed +
angular part o. 6a/e .unction #0#
radial part o. 6a/e .unction WW
#
S states (singlet S+ ##0 I ##
energies .or /arious atoms IIY
saturation (magnetism+ ,-#
SCD (sel.2consistent Leld+ calculations #0?
SchroM dinger, 'r6in 2?, 2%
SchroM dinger e0uation 2% I
$ in atomic units *02
epression in polar coordinates $- I %,
,0,I*
angular .unctions $$ I #00,
,0* radial .unction $% I $, ,0*
solution o. *#, 5,, $?, #00, #,5
.or Corse potential energy cur/e ,02 I
, pertur3ation theory used *#- I 2*
.or polyatomic molecules ,0*
.or system under pertur3ation 22$
time2dependent e0uation 22%
time2independent e0uation 22%
SchroM dinger method in 0uantum mechanics
,$ I *0, $?
QseaG o. electrons ,%#
secular e0uations *0? I
-
.or 3utadiene ,55
.or propyl radical *##
see also /ariation theorem
SeitK, Drederic4 #,5, ,%-
selection rules ##5 I #-, #$?, 225 I -, *,- I
% electronic spectroscopy ,** I %
A: spectroscopy 2**, 2$- I ,02
;C: spectroscopy 2?* I -, &+,I,.
see also Bohr I 'instein
condition sel.2consistent Leld #0?
see also SCD calculations
semiconductors ,%% I $
e..ect o. temperature on electrical
conducti/ity Xaa, ,%$
S'TA (search .or etraterrestrial intelligence+
%?, *#0
shielding constant ('" in ;C: spectroscopy
2-0
shi.t operators %2 I ,
6a/e .unctions .or
,
D states o. d
2
*,$I*#
Sidg6ic4, ;787 #?*
similarity trans.ormation *#,
simple harmonic motion 2$0 I
,
space 6a/e .unctions %+'I(, ,,,, XXc
spin 6a/e .unctions %+', ,,*, XXc
total energies in #s
#
2s
#
helium atom
,,%I$
Slater determinant(s+ #%$, ,*%, *2$ I
,0 microstates as %&&, &.+
Slater rules .or calculation o. screening #-2
Slater2type or3itals (ST"s+ %+%I'
or3ital o/erlap .or IbI
sodium <2lines 22*, J_J
Neeman e..ect IJY, J_J
sodium metal
3and structure ,-$, XaY
3onding in ,-% I
$ solids
3and theory ,-% I %$
electrical conducti/ity ,%- I
$ mechanical properties ,$0
optical properties ,$0
Sommer.eld, Arnold 2?, ,%#
proo. o. normalisation and orthogonality
%+%
space .unctions %+'I(
space 0uantisation --
spectroscopic timescales 2*5 I
- spectroscopic transitions
comparison o. A:, ;C: and =8 I 8AS
transitions 2,% I *#
particle and 6a/e /ie6s 2*2 I 5
time2independent and time2dependent parts
o. 6a/e .unctions 22- I %, 2?? I -
spectroscopic units and notation 2*- I
$ spectroscopy 2#5 I 5$
deLnition 2#?
see also a3sorption777P atomic777P
electronic777P in.rared777P nuclear
magnetic resonance spectroscopy
spectrum
energyH.re0uencyH6a/elength ais, units used
2*%I$
intensityHa3sor3ance ais, units used
2*$I50
spherical harmonics *2?
applications #00, #%,, 2$-
spherical polar coordinates *,#
see also polar coordinates
sine .unction *&
singlet states %5, %+'
electron distri3utions .or ecited helium
atom ,,$ I *#
electron repulsion energy %+(, ,,-I%
li.etimes ,,%
o. nucleus 2?2
spin2.or3idden transitions #$-
spin .unctions %5, %+'
spin I or3it coupling (S"C+ %#, ### I #5
in crystal Leld theory #$5 I
? Lrst2order %&-
inter2electronic ##5
intermediate coupling ##, I
#* && coupling ##2 I #,
matri .or microstates o. p
2
conLguration
%&(I)
:ussell I Saunders (LS + coupling ### I
#2 and state energies II_
spin I or3it coupling constant #$5
spin I or3it coupling energy
### spin 0uantum num3er
o. nuclei %,, 2?2
o. single electron %, I *, #0%
spin I spin coupling, in ;C: spectra 2-0 I
, spin I spin coupling energy 2-2
spin states
hydrogen atom %5 I ?
single electron %*
t6o2electron system %5
spinning 3ulletsHpro@ectiles -5
s0uare planar molecules Ibb`d
Star4 e..ect 2$$
state energies, e..ect o. spin I or3it coupling
II_
Ste.an I BoltKmann constant #, I *
Ste.anGs radiation la6 #,
strong2Leld coupling scheme #%%
.or d
2
in octahedral Leld #$, I
5
Strutt, John William #5
sul.ur dioide, molecular geometry #?? I
- super2pairs (o. electrons+ #??
in /arious molecules Ibd
superconductors ,%$
superposition o. states 5$
sur.ace2adsor3ed species, DTA: spectroscopy
2**I5
symmetry species ,0*, ,0?
synchronised stepping .re0uency 2,%
T2shaped molecules Ibb
Tana3e I Sugano diagrams IWI, #$2I,
limitations #$,
temperature2independent paramagnetism (t7i7p7+
,?5
term energies ##0
term sym3ols #0%
assignment o. #0% I
#0
tetragonal antiprismatic crystal Leld
states o. single d electron
energy le/els XdX
magnetic moments ,-2 I ,, XdX
tetrahedral complees, dd transitions #$?
tetrahedral molecules #5- I %, Ibb`d
tetrahedral symmetry, d2electron energy le/els
Iaa
tetramethylsilane (TCS+, as standard in ;C:
spectroscopy 2?$
theory
at end2#$th century - I
% role in science # I ,
thermal radiation #,
thermodynamics, la6s o. ?
Thomson, George !aget 2-
three23ody pro3lem #0?
time, atomic unit o. *02
time2independent pertur3ation theory *#- I
2# tin atom, eigenstates %&,
total angular momentum -% I %#
transition dipole moment 2,* I %,
*,-
in hydrogen atom &)&I'
transition2metal complees
electronic energy le/els #%- I $?
electronic spectroscopy #$? I -,
,,0 magnetism #$- I $
transition metals
3and structure XaI
3onding in ,-$ I %#
density o. states ,%#
properties eplained #0-
transition moment (TC+ integral, e/aluation o.
%&*I+
transition moment operator %&)
transition pro3a3ility
e..ect o. electron spin ,** I ?
nuclear magnetic resonance &+,I-
0uantum mechanics 22- I ,,
conLrmation o. method 2,$
spatial aspects .or allo6ed electronic
transition ,*? I -
/i3rational .actor in ,*- I %
#,#,22trichloroethene
#
9 ;C: spectrum 2-0 I #, JdI
spin I spin coupling in 2-2 I ,
trigonal 3ipyramidal molecules Ibb ` Ibd
trigonal molecules Ibb ` Ibd
trigonal pyramidal molecules Ibb
triplet states %5, %+'
electron distri3utions .or ecited helium
atom ,,$ I *#
electron repulsion energy %+(, ,,?I-
li.etimes ,,%, ,*#
space 6a/e .unctions %+'I(, ,,,I*, XXc
spin 6a/e .unctions %+', ,,*, XXc
total energies in #s
#
2s
#
helium atom
,,%I$
t6o2electron repulsion integrals &.)I*
listed .or d or3itals
in comple .orms &%.
in real .orms &.-
Tycho Brahe #0
=hlen3ec4, George 'ugene -%, #05, ##%, #20
ultra/iolet catastrophe I_, #5
ultra/iolet spectrum JId
Lrst disco/ered 2#-
uncertainty principle 5? I -,
2*? e..ects 5%, --
uniLcation o. molecular or3ital and /alence
3ond models #*# I ,
unitary matri *#,
units J_a, *0#I2
con/ersion .actors J_W
=8 I 8AS spectroscopy
electric dipole interaction energy 2,*
eperimental aspects 2*0
terminology &)+
timescales 2*?, J_b
see also electronic spectroscopy
=8 I 8AS transitions, compared 6ith A: and
;C: transitions 2,% I *#
/acuum magnetic suscepti3ility ,?*
relationship 6ith magnetic moment ,??,
'-)
/alence 3and ,%-
/alence 3ond (8B+ theory #,- I $
compared 6ith C" theory #5?, #?,
computational de/elopments #?- I %
and hy3ridisation #5?
and resonance #?,
uniLcation 6ith molecular or3ital theory
#*#I,
/alence 3ond (8B+ 6a/e .unctions,
normalisation o. %*-
/alence electron distri3ution, e..ects o. !auli
eclusion principle #?# I
2 /alence electronsHor3itals #0-
/alence2shell electron2pair repulsion (8S'!:+
model #?* I -
Lrst de/eloped #?*
and multiple 3onds #?5 I -
6ater molecular shape considered #?5
8an de 9ulst, 9endric4 %?
8an der WaalsG gas e0uation 5
8an 8lec4, John 9as3rouc4 #%2, #$$, ,-5
/anadium(AAA+ heacyano comple ion,
spectrum #$* I 5
/ariation theorem *0, I #0
application o. *0* I -
eamples o. use #*0, #5#, ,5,, *0- I
#0 proo. *0, I *
/ector 0uantity -*
angular momentum as -* I
? /elocity, atomic unit o. *02
/elocity o. light 22,, *0#
.actors a..ecting 2#?
as limiting /elocity #,
ratio o. electrostatic to electromagnetic units
-, 2#?
/i3rational angular momentum, and Coriolis
interaction ,## I #?
/i3rational circular dichroism (8C<+ spectra
,#-
/i3rational selection rule 2$$ I ,00
semi2classical interpretation ,0#
/i3rations o. diatomic molecules 2$#, JWJ,
'%,I%-
/i3rations o. polyatomic molecules ,05 I %
angle 3ending mode ,05 I ?, XIY
asymmetric stretching mode ,05 I ?, XYd,
XIY
normal mode ,0*
roc4ing mode ,0-, XYd, ,0%
scissoring mode ,0-, XYd, ,0%
s4eletal /i3rations ,0$
symmetric stretching mode ,05 I ?, XYd,
XIY
6agging mode ,0-, XYd, ,0%
/i3ronic transition 2,?
/irial theorem $-
/olume magnetic suscepti3ility ,?*
and Bohr magneton num3er '-*
/ariation 6ith temperature ,?* I 5
8S'!: model see /alence2shell electron2pair
repulsion model
Wang, S7C7 #*0
6ater molecule
3ond angle #?*
/i3rations ,05 I ?
8S'!: model #?5
6a/e .unctions
o. hydrogen atom $- I #00
angular parts $$ I #0*,
IY_
9eitler I London (/alence 3ond+ approach
#,-I$
9und I Culli4en (molecular or3ital+
approach #,$
impro/ements #*0 I
#
nodes #0*, IY_
radial part $% I $, IY_
normalisation o.
in 9uM c4el C" calculation
,5? .or hydrogen molecule
%*-I+.
time2dependent part 22-
time2independent part 22- I
% 6a/e mechanics 2?, 2% I $, 50
6a/e num3er 2*%
6a/e theory o. light 2#?
limitations 2#, 22,
6ea42Leld coupling scheme #%%
.or d
2
(
,
D in octahedral Leld+ #%$ I
$0 .or d
2
(inclusion o.
,
!+ #$0I#
Wein3aum, S7 #*2
Weiss, !ierre ,?5
see also Curie I Weiss la6
Wigner, 'ugen !7 #,5, ,%-
Wilson, 'dgar Bright ,#?
6or4 .unction (o. sur.ace+ 2#
Roung, Thomas 2#?
Ru, D7C7 2?-
Neeman e..ect #05, ##- I 20, *0%
anomalous Neeman e..ect #20
normal Neeman e..ect ##% I
20 practical applications ##$ I
20
Kero o. energy, deLnition $?, #,,
Kero2point energy #?, *-, 5%, #,*, 2$*
With than;s to Pa1l Nash for creation of this index.
)