Ana|ynca| Methods |n Chem|stry

(Cn-429)
ur. Maheswaran Shanmugam
Lmall: eswar[chem.llLb.ac.ln
hone: 7187
Ana|ynca| Methods |n Chem|stry
What we are go|ng to study?
Course deLalls:
1. LlecLron paramagneuc resonance
2. Super conducung CuanLum lnLerference uevlce (SCulu)
3. lnLroducuon Lo Cpucal meLhods
- uv-vlslble
- lnfra red
- lluorlmeLry
- ALomlc absorpuon
4. Scauerlng of 8adlauon
- nephelomeLry
- 1urbldlmeLry
- 8aman SpecLroscopy
3. LlecLro-analyucal meLhods
- Cycllc volLammeLry
- olarography
- AmperomeLry
- ConducLomeLry
6. 1hermogravlmeLry (1CA) and ulerenual Lhermal analysls (u1A)
7. Cas ChromaLography and hlgh performance llquld chromaLography (PLC)

- r|nc|p|e
- Instrumentanon
- Methods
- App||canons
1ext and keference books:


1. LlecLron paramagneuc 8esonance: A pracuuoner's Lool klL
- Marlna 8rusLolon and Lllo Clamell
2. LlecLron aramagneuc 8esonance by !ohn A Well and !ames 8. 8olLon

3. nM8, nC8, L8 and Mossbauer specLroscopy ln lnorganlc ChemlsLry by
8. v. arlsh
1ext 8ooks and keferences
L|ectron aramagennc kesonance (Lk)
WhaL ls an L8 specLrum?
lL ls usually a ploL of rsL derlvauve of absorpuon of mlcrowave frequency
radlauon agalnsL Lhe magneuc eld lnLenslLy.
LlecLron aramagneuc 8esonance
LlecLron Spln 8esonance or
LlecLro Magneuc 8esonance
ueLecLs Lhe unpalred elecLron ln Lhe
sample under lnvesugauon and lLs
elecLronlc sLrucLure around lL
Magneuc eld (C)
L|ectron aramagennc kesonance (Lk)
L8
Conunuous wave meLhod ulsed meLhod
Low lnLenslLy conunuous lrradlauon
(mlcrowave) of sample
ShorL pulses of hlgh power mlcrowave
radlauons are senL Lo Lhe sample and
Lhe sample response ls recorded ln Lhe
absence of radlauon.
What are the ma|n features of an Lk spectrum?
Maln parameLers and feaLures of L8 specLrum:
1. osluon of absorpuon: Magneuc eld value aL whlch Lhe absorpuon Lakes place
2. number, Separauon, relauve lnLenslLy of Lhe llnes
3. WldLh and Shape of Lhe llne
Structure of the spec|es under |nvesnganon
1he|r |nteracnon w|th env|ronment
Dynam|c process assoc|ated w|th |t.
Magnenc moment of an e|ectron
8epresenLauon of elecLron spln
angular momenLum vecLor
uenluve spln value of Lhe vecLor, S
z
= 1/2
1hese spln sLaLes are dler ln orlenLauon
of Lhe angular momenLum ln space buL
boLh spln sLaLe has same magnlLude of
angular momenLum.
Cr|g|n of Lk spectra_e|ectron sp|n |n a magnenc he|d(2eeman eect)
1he exlsLence of magneuc momenL assoclaLed wlLh Lhe elecLron spln responslble
for Lhe energy separauon beLween Lhe spln up and spln down
In the presence of magnenc he|d (8):
When 8 ls parallel Lo z axls, Lhen 5 wlll Lake Lhe value of 5
z
ln presence of Magneuc eld, Lhe degeneracy of Lhese sLaLes wlll be lled, based on
Lhe allgnmenL of Lhe momenLs wlLh Lhe exLernal magneuc eld, one sLaLe wlll ln
lower ln energy and Lhe oLher sLaLe wlll be hlgher ln energy
Pence Lhe spllmng of energy levels depends on sLrengLh of Lhe magneuc eld.
L
n
e
r
g
y
8 = 0
1hese Lwo energy levels are degeneraLe ln Lhe absence of magneuc eld
L|ectron sp|n |n a magnenc he|d (2eeman eect)
8 > 0
Spllmng of elecLronlc energy
l evel l n Lhe presence of
magneuc eld called Zeeman
spllmng or Zeeman LecL
L
n
e
r
g
y

M
s
x
8 = 0
Magneuc lleld (8)
!8
pp

h" = g#8
" = (g#/h)8 = 2.8024 x 8 MPz


for 8 = 3480 C " = 9.73 CPz (x-band)
for 8 = 420 C " = 1.2 CPz (L-band)
for 8 = 110 C " = 300 MPz (8adlofrequency)
L8 ls Lhe resonanL absorpuon of mlcrowave radlauon
by paramagneuc sysLems ln Lhe presence of an applled
magneuc eld
M
s
= +x
M
s
= -x
h Plancks constant 6.626196 x 10
-27
erg.sec
" frequency (GHz or MHz)
g g-factor (approximately 2.0023)
# Bohr magneton (9.2741 x 10
-21
erg.Gauss
-1
)
B magnetic field (Gauss or mT)
!L=h"=g#8
8 > 0
L|ectron sp|n |n a magnenc he|d (2eeman eect)
Macroscop|c co||ecnon of e|ectron sp|ns
! revlously whaL we have descrlbed Lhe slLuauon for an lsolaLed elecLron, however ln
a real sysLem Lhe elecLrons wlll be ln Lhe order of 10
10
or even more.
! 1here wlll be lnLeracuon beLween Lhe elecLron or wlLh envlronmenL
! noL only LhaL Lhe elecLron wlll be conned ln an orblLal of an aLom or a molecule
Lven for Lhe macroscoplc sysLem, ln Lhe absence of Magnenc he|d Lhese elecLrons wlll be
equally dlsLrlbuLed beLween Lhe spln up sLaLe and spln down sLaLe (due Lo degeneracy of
Lhese Lwo sLaLes (spln up ($) and spln down(#)))
ln Lhe presence of magneuc eld, dlsLrlbuuon of elecLron beLween Lhe spln down Lo
Lhe spln up sLaLes are declded by Lhe Lhermal equlllbrlum wlLh Lhe lamce or
envlronmenL.
1he rauo beLween Lhe number (n) of $ spln Lo Lhe # spln glven by 8olLzmanns
dlsLrlbuuon equauon
k
8
= 8olLzmann consLanL = 1.3806 % 10
-23
! k
1 = AbsoluLe LemperaLure of Lhe lamce.
Sp|n |amce re|axanon
1he equauon becomes
opulauon usually aL lower energy sLaLe wlll be hlgher, hence Lhe Lransluon from #
spln sLaLe Lo $ spln sLaLe occurs.
uue Lo conunuous lrradlauon of elecLromagneuc radlauon, lL ls posslble Lo have
equal dlsLrlbuuon of elecLron ln spln down (#) sLaLe as well as spln up sLaLe ($). ln
Lhls slLuauon, epr slgnal wlll saLuraLe or dlsappears.

Powever, ln reallLy even lf you run Lhe experlmenL conunuously for long ume,
saLurauon doesnL occur due Lo spln-lamce lnLeracuon. le. 1he absorbed energy
wlll be losL due Lo lnLeracuon wlLh envlronmenL or lamce.

1hls spln lamce relaxauon process occurs very rapldly whlch ls usually reporLed as
lnverse of Lhe characLerlsuc ume 1
1
Lhan Lhe sumulaLed emlsslon.
Schemanc representanon to exp|a|n sp|n |amce re|axanon
Sp|n-|amce re|axanon (|ong|tud|na|)
Spln-Lamce relaxauon ume (1
1
): 1hls relaLes Lhe characLerlsuc ||fenme of the e|ectron|c state
and ls determ|ned by the exchange of energy v|a therma| v|branons of the |amce.
SlmplesL lndlvldual resonance
llne referred Lo Sp|n packet.
Sp|n-|amce re|axanon rate (1]1
1
)
ulrecL process
8aman rocess Crbach rocess
D|rect process
1hls process ls llmlLed Lo elecLron-phonon lnLeracuon where Lhe phonon frequencles are
exacLly equal Lhe applled mlcrowave frquency.
Mechanlsm: Modulauon of llgand eld lnLeracLs wlLh Lhe vlbrauonal modes of Lhe lamce
kaman process
Pere, Lhe phonon of frequency "
1
ls scauered by Lhe paramagneuc cenLer and emerge
wlLh a dlerenL frequency "
2
, Lhe frequency dlerence belng equal Lo Lhe mlcrowave
frequency.
Crbach process
1hermal acuvauon from one elecLronlc sLaLes of L8 Lransluon and subsequenL emlsslon
or absorpuon of a phonon.
Sp|n-Sp|n re|axanon (1
2
)
Spln-Spln relaxauon ls concerned wlLh muLual spln lps caused by dlpolar and exchange
lnLeracuon beLween Lhe assembly of splns maklng up Lhe sample.
uue Lo spln-spln lnLeracuons, oen Lhe L8 llnes obLalned are broad, wlLhln LhaL ne
sLrucLural deLalls are burled. Lxample: Pyperne lnLeracuons (whlch wlll glve us Lhe aLoms
surrounded by Lhe meLal lons)
Cbservanon of magnenc resonance
Lpr resonance condluon can be achleved by Lwo ways
1. under consLanL magneuc eld, changlng Lhe frequency of mlcrowave lrradlauon lnLenslLy.
2. under consLanL lrradlauon of mlcrowave of parucular lnLenslLy, sweeplng Lhe
magneuc eld.
Se|ecnon ru|e for
obser v| ng t he
Lk resonance
!M
s
= 1

Advantage of record|ng Lk |n constant m|crowave frequency
Absorpnon
I|rst der|vanve of absorpnon
Lxamp|e 1:
Advantage of record|ng Lk |n constant m|crowave frequency
Lxamp|e 2:
lk spectto of ulbeozotblopbeoe toJlcol tecotJeJ lo
o) \-booJ (9.5 Cnz) b) w-8ooJ (95 Cnz)
Appears Lo be an lsoLroplc
SpecLrum. Powever due Lo spln-
orblL coupllng (very small), Lhe
resonance Lransluon occurs very
c l o s e l y , r e s u l L s l n l l n e
broadenl ng or l l ne wl dLh
lncreases.
uue Lo lncreased quanLa of
energy of mlcrowave, Lhe
dlsLance beLween Lhe peak
(resonance condl uon) al so
lncreases llnearly, resulLs ln hlgh
resoluuon anlsoLroplc specLra.
Instrumentanon of CW-Lk
1here are four lmporLanL componenLs ln CW-L8:
1. Mlcrowave resonaLor
2. Mlcrowave brldge
3. MagneL SysLem
4. ConLrol elecLronlcs
M|crowave kesonator
Mlcrowave resonaLor ls Lhe samp|e ce||. le 1hls ls where Lhe sample under lnvesugauon
needs Lo be place (samp|e ho|der)

ln addluon, oLher Lwo maln purpose of mlcrowave resonaLor ls
! 1o creaLe sumclenL mlcrowave magneuc eld aL Lhe sample posluon Lo drlve Lhe Lransluon
! 1o emclenLly converL Lhe sample response lnLo deLecLable mlcrowave slgnal

8oLh of Lhese facLor depends on Lhe value of quallLy facLor
!
tes

= 8esonance frequency of Lhe resonaLor
!" = WldLh of Lhe resonance curve
L-8and = 1 CPz
S-8and = ~3 CPz
x-8and = 9.3 CPz
C-8and =~33 CPZ
W-8and = 93 CPZ
M|crowave kesonator
Mlcrowave energy ls sLored ln resonaLor leads Lo an enhancemenL ln mlcrowave
magneuc eld (8
1
) and elecLrlc eld (
1
) compare Lo lLs free space value
8
1
= c % (C%)
1/2
8
1
generaLed by mlcrowave power ls glven by
Where c = Converslon facLor of a resonaLor Lhe value oen depends
resonaLor slze (Smaller Lhe resonaLor, larger Lhe converslon facLor
Also more lmporLanLly Lhe peak Lo peak separauon ("5
pp
) ls
also depends on Lhe CuallLy facLor (C)

"5
pp
# $ % O
noLe:
"5
pp
# O
"5
pp
# !
tes
M|crowave kesonator
Accordlng Lo Lhe above equauon llsLed ln Lhe prevlous sllde, Lhe slgnal ampllLude wlll
lncreases wlLh lncreaslng sample volume, along wlLh C. Powever, oen C facLor ls
lowered upon lncreaslng Lhe sample volume, hence Lhe opumum sample needs Lo be
used for correspondlng lnsLrumenL depends on Lhe frequency
" 1he beneLs of resonaLor C facLor wlLh respecL Lo 8
1
(mlcrowave magneuc
eld) and Lhe sensluvlLy of Lhe lnsLrumenL (le, resoluuon of peak Lo peak
separauon)
" Mlcrowave frequency doesnL have large wlndow Lo sweep across, unllke
Lhe exLernal magneuc eld
" nence, Lk |s recorded w|th hxed m|crowave frequency w|th constant
|ntens|ty by sweep|ng the externa| magnenc he|d across.
M|crowave kesonator
Mlcrowave LlecLromagneuc radlauon Magneuc eld componenL (8
1
) and
LlecLrlc eld componenL (L
1
) (& Lo each oLher)
Magneuc eld componenL (8
1
) Magneuc resonance Lransluon
LlecLrlc eld componenL (L
1
) non-resonanL mlcrowave absorpuon
1hrough elecLrlc dlpole
momenL of Lhe sample
1hls causes decrease
ln C facLor and
undeslred sample
heaung.
Pence L8 resonaLor has been deslgned based on elecLrodynamlcs prlnclple
where Lhe sample felL Lhe 8
1
and mlnlmlzes Lhe L
1
aL Lhe sample posluon
Mlcrowave LlecLrlc and magneuc eld componenLs
II. M|crowave 8r|dge
Mlcrowave frequencles are Lradluonally classled ln Lerm of a bands.
L- 8and 1 CPz Malnly used for blologlcal sample and for llve anlmals sLudy (1o
reduce Lhe absorpuon of elecLrlc eld componenL)
S-8and (3 CPz), x-8and (9.3 CPz), C-8and (34 CPz), k-8and (24 CPz), W-8and (93 CPz)
usually Lhe hlgher frequency L8 lnsLrumenL ls used Lo geL deLalled lnslghLs abouL Lhe
sLrucLure. Lower frequency (L and S band) lnsLrumenLs are used for blologlcal appllcauon.
Cr|nca| coup||ng
When Lhe magneuc eld ls swepL Lhrough, resonance mlcrowave energy ls absorbed
by Lhe sample LhaL causes a change of Lhe resonaLor C facLor. lL ls Lhls change LhaL
resulLs ln Lhe reecuon of mlcrowaves from Lhe resonaLor LhaL ln Lurn ls reglsLered as
Lhe L8 slgnal.
1he compleLe absorpuon of CW mlcrowave power by Lhe resonaLor ls called Crlucal coupllng
or maLchlng.
8eference arm
1 o k e e p L h e
deLecLor ln Llnear
response
Large and smal l
slgnals wlll be glven
ln correcL ampllLude
rauo
Automanc Irequency Contro| (AIC)
1he change ln Lhe resonaLor C facLor, ls L8 dlsperslon slgnal

1he change ln Lhe maLchlng condluon of resonaLor (LhaL ls resonaLor reecLs Lhe
mlcrowave slgnal) ls L8 absorpuon

L8 absorpuon and L8 dlsperslon process appear ln parallel.

AlC separaLes, more preclsely ellmlnaLes Lhe dlsperslon slgnal, only absorpuon slgnal ls
deLecLed.

noL only LhaL AlC ls llnked Lo osclllaLor frequency whlch ls locked Lo Lhe resonaLor
frequency.


III. Magnet system
MagneL
ower supply unlL
lleld sensor
lleld 8egulaLor
MagneL sysLem
Lower Lhan W-band (93 CPz), we can use elecLromagneLs

W-band and above, we have Lo use superconducung magneL
MagneL sysLem
supplles Lhe magneuc
eld
x-8and (9.3 CPz) = 0.3 1 or 3000 C
C-8and (33 CPz) = ~1.3 1 or 13 kC
PomogenelLy of magneuc eld aL Lhe sample posluon ls an anoLher lmporLanL
facLor Lo be keep ln mlnd
Magnet system
Measurlng and conLrol Lhe
sysLem Lo geL Lhe correcL
magneuc eld value
na|| sensor |s |nsta||ed |n between the
gap of e|ectromagnet:
! 1o glve us accuraLe value of Magneuc
eld posluon, llne wldLh, separauon
! MounLed o cenLer, Lo avold Lhe
eld modulauon applled Lo resonaLor
! needs callbrauon (sample posluon Lo
Pall sensor posluon, slnce lL ls
mounLed ocenLer)
! nM8 Causs meLer used Lo callbraLe
Lhe Pall sensor wlLh very hlgh
preclslon (10
-6
Lo 10
-7
)
A|ternanve|y samp|e ca||branon can be done by us|ng
standard samp|e:
2,2-ulphenyl-1-plcryl-hydrazyl (uP) = 2.0036
Cr
3+
= 1.979 (Cr
3+
ln MgC maLrlx)
Mn
2+
= 2.0011

Iundamenta|s
1. g values
- Spln-orblL coupllng
- Spln orblL coupllng arlslng from Lhe ground sLaLe
- Spln-orblL coupllng arlslng from mlxlng of ground sLaLe wlLh exclLed
sLaLes
2. llne sLrucLure
- Zero eld spllmng (uue Lo spln-orblL coupllng and spln-spln lnLeracuon)
3. Pyperne lnLeracuon
4. lsoLroplc and anlsoLroplc L8 SpecLra
Sp|n-orb|t coup||ng bas|c concepts
1o Lxplaln Lhe concepL we wlll conslder Lhe Lransluon meLal lons
ln gaseous lon all ve d-orblLals are degeneraLe and spllLs ln ocLahedral eld as below
!
o
1
2g
orblLal

e
g
orblLal

Sp|n-orb|t coup||ng bas|c concepts
e
-

orb|ta|

sp|n

tota|
Conslder an elecLron ln an orblLal, where elecLron splns by lLself (creaLes spln magneuc
momenL), whlch revolves around Lhe orblLal (hence orblLal angular momenLum).
lf LoLal spln angular momenLum (!) and LoLal orblLal
angular momenLum (") are lndependenL or noL
coupled wlLh each oLher Lhe resulLanL magneuc
momenL of Lhe sysLem ls glven by
[1]
Powever, ln reallLy boLh spln and orblLal angular
momenLum are coupled LogeLher, le. 5 and l are
no longer good quanLum numbers, Lhls requlres
dlerenL quanLum number I called LoLal
angular momenLum. 1he resulLanL magneuc
momenL ls glven by
1he LoLal angular momenLum quanLum
number Lakes Lhe absoluLe values
I = |l+5|..|l+5-1|.. |l-5|
q ls Landes q-facLor whlch has
denluve value for Lype of compounds
whlch depends on Lhe spln and orblLal
angular momenLum
ku|es for pred|cnng the ground state 1erm Symbo| (free gaseous |on)
1) lor any elecLronlc congurauon, sLaLes wlLh hlghesL 5 value ( 5 = n/2 where n =
number of unpalred elecLrons) ls lowesL ln energy
2)

SLaLes wlLh hlghesL l wlll be ln lowesL energy
J) I wlLh |" - !| value wlll be ln lowesL energy lf Lhe orblLal ls less Lhan half lled
and I wlLh |" + !| value wlll be ln lowesL energy lf Lhe orblLal ls greaLer Lhan half
lled.
Ceneral noLauon for Lerm Symbol:
Where S ls spln mulupllclLy (S = 2s+1) [s = o/2]
L ls Lhe 1L8M corresponds Lo Lhe hlghesL l value
I ls LoLal angular momenLum (I = |l+s|..|l+s-1|..|l-s|)
Lxample:
d
1
conhguranon:
'
+2 +1 0 -1 -2
S = 2(1/2)+1 = 2
l = 1% (-2) = 2
I = "$! = 2-1/2 = J/2
! va|ue 1LkM
0 S
1
2 D
3 I
4 G
S n
6 I
Work out for d
2
to d
10
conhguranon?
Ground state 1erm Symbo| for gaseous |on
m
l
Configuration Example 2 1 0 -1 -2 L S Ground Term
d
1
Ti
3+
d
2
V
3+
d
3
Cr
3+
d
4
Mn
3+
d
5
Mn
2+
d
6
Fe
2+
d
7
Co
2+
d
8
Ni
2+
d
9
Cu
2+
2
2
D 1/2
3
3 F 1
4
3 F 3/2
2
5
D 2
0
6
S 5/2
2
5
D 2
3
4
F 3/2
3
3
F 1
2
2
D 1/2
M
L
=(m
l
Genera| compar|son of 1erm Symbo| for gaseous |on d
1
-d
9
m
l
Configuration Example 2 1 0 -1 -2 M
L
S Ground Term
d
1
Ti
3+
2
2
D
d
2
V
3+
3
3
F
d
3
Cr
3+
3
4
F
d
4
Cr
2+
2
5
D
d
5
Mn
2+
0
6
S
d
6
Fe
2+
2
5
D
d
7
Co
2+
3
4
F
d
8
Ni
2+
3
3
F
d
9
Cu
2+
2
2
D
1/2
1
3/2
2
5/2
2
3/2
1
1/2
m
l
Configuration Example 2 1 0 -1 -2 M
L
S Ground Term
d
1
Ti
3+
2
2
D
d
2
V
3+
3
3
F
d
3
Cr
3+
3
4
F
d
4
Cr
2+
2
5
D
d
5
Mn
2+
0
6
S
d
6
Fe
2+
2
5
D
d
7
Co
2+
3
4
F
d
8
Ni
2+
3
3
F
d
9
Cu
2+
2
2
D
1/2
1
3/2
2
5/2
2
3/2
1
1/2
m
l
Configuration Example 2 1 0 -1 -2 M
L
S Ground Term
d
1
Ti
3+
2
2
D
d
2
V
3+
3
3
F
d
3
Cr
3+
3
4
F
d
4
Cr
2+
2
5
D
d
5
Mn
2+
0
6
S
d
6
Fe
2+
2
5
D
d
7
Co
2+
3
4
F
d
8
Ni
2+
3
3
F
d
9
Cu
2+
2
2
D
1/2
1
3/2
2
5/2
2
3/2
1
1/2
m
l
Configuration Example 2 1 0 -1 -2 M
L
S Ground Term
d
1
Ti
3+
2
2
D
d
2
V
3+
3
3
F
d
3
Cr
3+
3
4
F
d
4
Cr
2+
2
5
D
d
5
Mn
2+
0
6
S
d
6
Fe
2+
2
5
D
d
7
Co
2+
3
4
F
d
8
Ni
2+
3
3
F
d
9
Cu
2+
2
2
D
1/2
1
3/2
2
5/2
2
3/2
1
1/2
2
3
4
5
6
5
4
3
2
Lnerg|es of " |eve|s |n V(III) |on

I =2
I =3
I =4
-2
-1
0
+1
+2
3
l
Lnergles of I sLaLes can be calculaLed by
" = 3
! = 1
% = |"&!| ..|"&!$'|((|"$!|
% * +,-,.
-4)
-)
3)
!L
}, }+1
= )(}+1)
!L
S,2
= S )

!L
4,S
= 4 )
Lnergy dlerence beLween Lhe ! sLaLes ls calculaLed by
ln magneuc eld
M|crostates

MlcrosLaLes: ln 1erms of Molecular Lnergy Levels",
ln conLrasL, a mlctostote for a sysLem ls all abouL ume and Lhe energy of Lhe molecules ln
LhaL sysLem. "ln a sysLem lLs energy ls consLanLly belng redlsLrlbuLed among lLs parucles. ln
llqulds and gases, Lhe parucles Lhemselves are consLanLly redlsLrlbuung ln locauon as well
as changlng ln Lhe quanLa (Lhe lndlvldual amounL of energy LhaL each molecule has) due Lo
Lhelr lncessanLly collldlng, bounclng o each oLher wlLh (usually) a dlerenL amounL of
energy for each molecule aer Lhe colllslon.. Lach spec|hc way, each arrangement of the
energy of each mo|ecu|e |n the who|e system at one |nstant |s ca||ed a #$%&'()*)+."
hup://enLropyslLe.oxy.edu/mlcrosLaLe/lndex.hLml
I =2
I =3
I =4
3
l
-4)
-)
3)
1o calculaLe number of mlcrosLaLe avallable for a parucular
ground sLaLe Lerm symbol ls glven by
(spln mulupllclLy (2! + 1) % CrblLal mulupllclLy(2" +1))
lor v(lll) lon, d
2
congurauon, hence n= 10 and r = 2
1oLal number of mlcrosLaLes avallable for d
2
lon ls = 10!/2!8! = 43
M|crostates |n V(III) |on

lor
3
l = 3%7 = 21 sLaLes
(because ! = 1 and " = 3)
21
-2
-1
0
+1
+2
3
ln magneuc eld
7
9
! spllL malnLaln Lhe cenLer of gravlLy le Lhe energy of Lhe hlgher energy sLaLe (I=4) ls
compensaLed by Lhe sum of energles of lower energy sLaLe (! = 2 and 3)
9*3-7*1-3*4 = 0
lor a d
2
lon maxlmum " value LhaL we can obLaln ls = 4 and oLher posslble " values are 3,2,1,0
'*
+2 +1 0 -1 -2
" = 4; ! = u
1
u
Niciostates: Spin multiplicity (2! +1) % 0ibital multiplicity (2" +1)
1% 9 = 9
' '
+2 +1 0 -1 -2
" = S; ! = 1
S
F
Niciostates: Spin multiplicity (2! +1) % 0ibital multiplicity (2" +1)
S% 7 = 21
" = 4
" = 3
M|crostates for d
2
|on

' '
+2 +1 0 -1 -2
" = 2; ! = 1
S
B
Niciostates: Spin multiplicity
(2! +1) % 0ibital multiplicity
(2" +1)
S% S = 1S
" = 2
'*
+2 +1 0 -1 -2
" = 2; ! = u
1
B
Niciostates: Spin multiplicity
(2! +1) % 0ibital multiplicity
(2" +1)
1% S = S
" = 2
' '
+2 +1 0 -1 -2
" = 1; ! = 1
S
P
Niciostates: Spin multiplicity
(2! +1) % 0ibital multiplicity
(2" +1)
S% S = 1S
" = 1
'*
+2 +1 0 -1 -2
" = u; ! = u
1
S
Niciostates: Spin multiplicity
(2! +1) % 0ibital multiplicity
(2" +1)
1% S = S
" = 0
M|crostates for d
2
|on

ke|anonsh|p between 1erm symbo|s and 1anabe-Sugano d|agram
1
u
S
F
S
B
1
B
S
P
1
S
When CrblLal conLrlbuuon arlses ?
,- '&/+& )0*) *- +1+%)&'- %*- 0*2+ '&3$)*1 *-451*& #'#+-)5#6 $) #5() 3+
7'(($31+ )' )&*-(8'&# )0+ '&3$)*1 )0*) $) '%%57$+( $-)' *- +9*%)1: +;5$2*1+-) *-/
/+4+-+&*)+ '&3$)*1 3: &')*<'-=

1he elecLron ls Lhen eecuvely roLaung abouL Lhe axls used for Lhe orblLal roLauon.
(Lhe clrculauon of an elecLron around Lhe nucleus ls llke Lhe clrculauon of a currenL
Lhrough Lhe Lurns of a solenold)
Crb|ta| contr|bunon to the magnenc moment
e.q. Lhe d
xz
orblLal ls Lransformed lnLo Lhe d
yz
orblLal by a roLauon of 90 abouL Lhe z-axls -
durlng Lhls roLauon Lhe elecLron ls orblung Lhe nucleus
1he degeneraLe L
2g
orblLals (d
xy
, d
xz
, d
yz
) can be lnLerconverLed by 90 roLauons
Sp|n-Crb|t coup||ng |n trans|non meta| octahedra| comp|exes
!
o
1
2g
orblLal

e
g
orblLal

C4
C4
1hus, an elecLron ln a L
2g
orblLal can
conLrlbuLe Lo orblLal angular
momenLum
Is sp|n-orb|t coup||ng w||| be there |n e
g
orb|ta| |n Ch?
1he unpalred elecLron ln e
g
orblLal cannot conLrlbuLe Lo spln-orblL coupllng
1he e
g
orblLals cannoL be lnLerconverLed by roLauon due Lo Lhelr naLure of shape
of orblLal
dxy / dx
2
-y
2
orblLal mouon abouL z axls
dxz / dyz orblLal mouon abouL z axls
dxz / dxy orblLal mouon abouL x axls
dyz / dxy orblLal mouon abouL y axls
Is t
2g
to e
g
|nter-convers|on poss|b|e by rotanon?
es. Inter convers|on |s poss|b|e.
Powever, ln ocLahedral eld or any
llgand eld, L
2g
and e
g
orblLal
separaLed by !
0
(ln Ch eld), hence
Lhe mlxlng of d
xy
and d
x
2
-y
2
wlll depend
on Lhe energy gap beLween Lhese Lwo
level.
d
1
1hlnk of posslble L
2g
elecLron arrangemenLs

d
xz
d
yz
d
xy
d
xz
d
yz
d
xy
d
xz
d
yz
d
xy
osslble L
2g
arrangemenLs = 3
CrblLal conLrlbuuon =
d
1
e.q. 1l(lll)
d
2
osslble L
2g
arrangemenLs = 3
CrblLal conLrlbuuon = yes
d
xz
d
yz
d
xy
d
xz
d
yz
d
xy
d
xz
d
yz
d
xy
d
2
e.q. v(lll)
LS
Crb|ta| contr|bunon to the magnenc moment: n|gh sp|n octahedra| d
n
|ons
8ut, e|ectrons |n t
2g
orb|ta|s w||| not a|ways contr|bute to orb|ta|
angu|ar momentum
e.q. conslder ocLahedral Cr(lll) d
3
, L
2g
3

an elecLron ln Lhe d
xz
orblLal cannoL by roLauon be placed ln e.q.
Lhe d
yz
orblLal because Lhls orblLal already conLalns an elecLron
wlLh Lhe same spln as Lhe lncomlng elecLron

d
xz
d
yz
d
xy
d
xz
d
yz
d
xy
1herefore, Lhere ls only one posslble L
2g
arrangemenL,
and orblLal angular momenLum NC
Crb|ta| contr|bunon to the magnenc moment: n|gh sp|n octahedra| d
n
|ons
d
4
hlgh spln L
2g
half-lled
1hlnk of posslble L
2g
elecLron arrangemenLs

osslble L
2g
arrangemenLs = 1
CrblLal conLrlbuuon =
d
4
e.q. Cr(ll)
d
xz
d
yz
d
xy
d
3
hlgh spln L
2g
half-lled
osslble L
2g
arrangemenLs = 1
CrblLal conLrlbuuon =
d
3
e.q. Mn(ll),
le(lll)
d
xz
d
yz
d
xy
NC
NC
Crb|ta| contr|bunon to the magnenc moment: n|gh sp|n octahedra| d
n
|ons
d
6
hlgh spln

1hlnk of posslble L
2g
elecLron arrangemenLs

osslble L
2g
arrangemenLs = 3
CrblLal conLrlbuuon =
d
6
e.q. le(ll)
d
xz
d
yz
d
xy
d
xz
d
yz
d
xy
d
xz
d
yz
d
xy
d
7
hlgh spln
osslble L
2g
arrangemenLs = 3
CrblLal conLrlbuuon =
d
7
e.q. Co(ll)
LS
LS
Crb|ta| contr|bunon to the magnenc moment: n|gh sp|n octahedra| d
n
|ons
nl(ll) d
8
L
2g
lled
1hlnk of posslble L
2g
elecLron arrangemenLs

osslble L
2g
arrangemenLs = 1
CrblLal conLrlbuuon =
d
8
e.q. nl(ll)
Cu(ll) d
9
L
2g
lled
osslble L
2g
arrangemenLs = 1
CrblLal conLrlbuuon =
d
9
e.q. Cu(ll)
NC
NC
Crb|ta| contr|bunon to the magnenc moment: n|gh sp|n octahedra| d
n
|ons
nl(ll) d
8 L
2g
lled
Lhlnk of posslble L
2g
elecLron arrangemenLs

osslble L
2g
arrangemenLs = 1
CrblLal conLrlbuuon = NC (due to ground state)
L
2g
noL comp.
lled
d
8
hlgh spln LS
osslble L
2g
arrangemenLs = 3
CrblLal conLrlbuuon =
Lxc|ted state
LS

exp
>
s
for CcL. nl
2+

Crb|ta| contr|bunon to the magnenc moment: Contr|bunon due to
exc|ted state
1herefore for C
h
N|(II) the magnenc moments are |arger |f the GS-LS gap |s sma||.
8U1 ICk 1etrahedra| N|(II) s|tuanon |s ennre|y d|erent ..
osslble L
2g
arrangemenLs = 3
CrblLal conLrlbuuon =
LS
M
exp
C
h
N|(II) |s sma||er than M
exp
1
d
N|(II)
Lxp. nlCl
4
2-
, nl(PMA)
4
2+
(PMA=hexameLhyl phosphoramlde)
have magneuc momenL larger Lhan 4 8M.
(larger Lhe dlsLoruon smaller Lhe magneuc momenL )

uSLluL ln ulSC8lMlnA1lnC C
h
vs 1
d
sLrucLures.
d
8
PS 1eLrahedral
now to d|snngu|sh N| 1d and Ch comp|exes?
now does th|s sp|n-orb|t coup||ng aect the g-va|ue?
! lor free or lsolaLed elecLron, Lhe /-value ls deLermlned as 2.0023

! resence of orblLal angular momenLum can lnLeracL wlLh spln angular momenLum
consLrucuvely or lL may oppose each oLher. ln such cases, Lhe observed magneuc
momenL elLher hlgher Lhan or lower Lhan (respecuvely) compare Lo free elecLron.
Pence Lhere wlll be change ln g-value of complex.
! Magneuc eld ln llnear relauonshlp wlLh magneuc momenL, le larger Lhe momenL,
spllmng of momenL ln magneuc eld wlll be hlgher.
! lrom g-value we can deduce Lhe elecLronlc envlronmenL of an aLom or lon.
Magneuc eld (C)
llrsL derlvauve Absorpuon
Measure 8 (resonance eld") for
glven applled .

What contro|s g-va|ue?
) = osluve for less Lhan half lled orblLals
) = negauve for more Lhan half lled orblLal
Pence, Lhe /-value ls hlgher Lhan Lhe free elecLron q-value (/
0
) for more Lhan half lled
elecLronlc congurauon and Lhe same wlll be less Lhe free elecLron g-value (/
0
) for less Lhan
half lled d-orblLal.
Where
a denoLes cova|ency, usually a
2
wlll be 1 (lf an unpalred elecLron
delocallzed, Lhe spln-orblL coupllng wlll be reduced.
) = Spln orblL coupllng consLanL
!L = Lnergy gap beLween Lhe orblLals
(8lgger !L + less mlxlng + smaller shl of g from g
e
. noLe !L
corresponds Lo an e|ectron|c dd trans|non!)
n = depends on Lhe ldenuLy of orblLals whlch are belng mlxed
red|cnon of n va|ue from Mag|c entagon