Chapter 11

Molecular Electronic Structure

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 PChem 11 - 2

11.1 The Born-Oppenheimer Approximation

The Born-Oppenheimer approximation decouples two sets of degrees of freedom that greatly
differ in their dynamics. The electronic energy is approximated as a parametric function of
nuclear coordinate R. An effective Hamiltonian is constructed with stationary nuclei.

 effective  T e  V ee  V Ne  V NN
H

 (r , R)   N ( R)  e (r; R)
  T N  H
H  effective

  (r , R )  E  (r , R)
H (T N  H
 effective ) ( R)  (r ; R)  E  ( R)  (r ; R)
N e N e

 effective  (r ; R)  E ( R ) (r ; R)
H e e e

[T N  Ee ( R )] N ( R)  e (r ; R)  E  N ( R)  e (r ; R)

[T N  Ee ( R)] N ( R )  E  N ( R)

The electronic degrees of freedom are separated from those of nuclei and described by a
parametric wavefunction of nuclear coordinates. The nuclei moves in a potential field due to
electrons..

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 PChem 11 - 3

11.2 The Hydrogen Molecule Ion

rA rB

the trial funcion

HA R HB
As two nuclei are identical, c1 = c2 = c = 1.0

overlap integral

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 PChem 11 - 4

Overlap Integrals

1.0

S
0.5

0.0
0 1 2 3 4
R / a0

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 PChem 11 - 5

H2+ Molecular Orbitals

J K

K J

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 PChem 11 - 6

H2+ Molecular Orbitals

J Coulomb integral

K Exchange Integral

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 PChem 11 - 7

Normalized H2+ Molecular Orbitals

the trial funcion

A ttwo nuclei
As id ti l c1 = c2 = c
l i are identical,

= c2 ( 1 ± S ± S + 1) = 2 c2 ( 1 ± S) = 1

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 PChem 11 - 8

H2+ Molecular Orbitals

bonding orbital

antibonding orbital

Ebinding = 170 kJ/mol

Re = 132 pm
Experiment
268 kJ/mol at 106 pm

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 PChem 11 - 9

H2+ Molecular Orbitals

nonbonding

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 PChem 11 - 10

H2+ Molecular Orbitals

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 PChem 11 - 11

H2+ Molecular Orbitals

AO MO AO

1s E-
nergy
En

E+

1s

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 PChem 11 - 12

H2+ Molecular Orbitals - Variational Approach

the variational trial funcion

the secular determinant

normalization

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 PChem 11 - 13

Linear Combination of Atomic Orbitals (LCAO)

The two atomic orbitals must have similar energy

and the same symmetry property with respect to
rotations about the internuclear axis.

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 PChem 11 - 14

LCAO – MO

u

s s

g

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 PChem 11 - 15

LCAO – MO

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 PChem 11 - 16

LCAO – MO

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 PChem 11 - 17

LCAO – MO Notation

i (*) AO Lz   

MO angular
Notation Property
momentum
0  Cyclindrically symmetric about the internuclear axis
1  One nodal plane that contain the internuclear axis
2 

Inversion
Notation Property
symmetry
gerade(even) g Symmetric about the internuclear inversion center
ungerade(odd) u Antisymmetric about the internuclear inversion center

bonding

antibonding *

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 PChem 11 - 18

11.4 Molecular Orbital Description of the Hydrogen Molecule

e1 r12
e2
r1A r1B r2A r2B

HA R HB

with the Born-Oppenheimer approximation

in atomic units

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 PChem 11 - 19

H2 Simple Molecular Orbital Treatments

the Slater determinant

u1s

nergy
En
1sA 1sB

g1s

LCAO-MO

Ebinding = 0.0990 Eh = 260 kJ/mol

Re = 1.61 a0 = 85 pm

Experimental values
Ebinding = 0.174 Eh = 457 kJ/mol
Re = 1.40
1 40 a0 = 74.1
74 1 pm

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 PChem 11 - 20

Extended Variational Treatment of H2 Molecle

The spatial part of the Slater determinant includes 50% HA+HB– + HA–HB+ and 50% H + H
1SA(1)1SA(2) + 1SA(1)1SB(2) + 1SB(1)1SA(2) + 1SB(1)1SB(2)

The problem can be reduced by introducing additional variational coefficients c1 and c2

  c1 ( R) covalent  c2 ( R) ionic Ebinding = 386 kJ/mol (was 260 kJ/mol)
 covalent  1s A (1)1s B (2)  1s A (2)1s B (1) Re = 74.9 pm (was 85 pm)
 ionic  1s A ((1)1s
) A ((2))  1s B ((1)1s
) B ((2)) Experimental values
Ebinding = 0.174 Eh = 457 kJ/mol
Re = 1.40 a0 = 74.139 pm

A more flexible molecular orbital trial function can be used with the SCF-HF method

Kolos and Wolniewicz used 100-term wavefunctions to obtain

Ebinding = 457 kJ/mol and Re = 74.140 pm

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 PChem 11 - 21

Self-Consistent-Field LCAO-MO Approach

A more flexible molecular orbital trial function

The Hartree – Fock - Roothan method :

{ci} are determined by the self-consistent field (SCF) procedure
the best SCF – LCAO – MO wavefunction reaches the Hartree – Fock limit

Thee Slater
S e type
ype atomic
o c oorbital
b can
c be used :

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 PChem 11 - 22

The Convergence to the Hartree – Fock Limit for H2

Effective
Total Binding Bond
LCAO - MO nuclear
l
energy (Eh) energy (Eh) length (a0)
charge

1sA + 1sB 1.00 -1.0990 0.0990 1.61

1sA + 1sB 1.197 -1.1282 0.1282 1.38
Eq. 9.35 1.231 -1.1321 0.1321 1.40
Eq. 9.35 (1s)=1.378 -1.1335 0.1335 1.40
(2s)=1.176
((2p)=1.820
p)

Hartree-Fock -1.1336 0.1336 1.40

pe e ta
Experimental 0.1642
0 6 1.41

(9.35)

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 PChem 11 - 23

Excited States of H2

Potential energy curves for lower excited states of H2

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 PChem 11 - 24

11.5 Electron Configurations of Homonuclear Diatomic Molecules

Correlation diagram for homonuclear diatomic

molecules. The energy scale is schematic, but
the dashed lines show the correct sequence for
filling of orbitals for the molecules indicated
indicated.

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 PChem 11 - 25

LCAO – MO Energy Level Diagram

u2pz
u2pz
g2px g2py
g2px g2py
g2pz
2pp 2pp
2p u2px u2py 2p
u2px u2py
g2pz

u2s

2s 2s u2s

g2s
2s 2s
g2s
B2 O2

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 PChem 11 - 26

H2 / He2 Molecular Species

u1s

1sA 1sB

g1s
1

Number Ground state Bond Binding

Bond
S
Species
i off electron
l t l
length
th energy
order
electrons configuration (pm) (kJ/mol)

H 2+ 1 (g1s))1 ½ 106 268

H2 2 (g1s)2 1 74 457

He2+ 3 (g1s)2 (u1s)1 ½ 108 241

He2 4 (g1s)2 (u1s)2 0 6000 <<1

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 PChem 11 - 27

The 2nd Row Homonuclear Diatomic Ground States

Bond Bond
Bond
Ground state electron configuration order
length energy
(pm) (kJ/mol)

Li2 KK(g2s)2 1 267 105

B 2
Be KK( 2 )2(
( g2s) 2 )2
( u2s) 0 245 9

B2 KK(g2s)2(u2s)2(u2px)1(u2py)1 1 159 289

C2 KK(g2s)2(u2s)2(u2px)2(u2py)2 2 124 599

N2 KK(g2s)2(u2s)2(u2px)2(u2py)2(g2pz)2 3 110 942

O2 KK(g2s)2(u2s)2(g2pz)2(u2px)2(u2py)2(g2px)1(g2py)1 2 121 494

F2 KK( pz)2((u2p
( g2s))2((u2s))2((g2p px)2((u2p
py)2((g2p
px)2((g2p
py)2 1 141 154

Ne2 KK(g2s)2(u2s)2(g2pz)2(u2px)2(u2py)2(g2px)2(g2py)2(u2pz)2 0 310 <1

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 PChem 11 - 28

Oxygenic Species

O2+, O2, O2- and O22-

Bond Bond
Bond
Ground state electron configuration order
length energy
(pm) (kJ/mol)

O 2+ KK(g2s)2(u2s)2(g2pz)2(u2px)2(u2py)2(g2px)1 5/2 112 643

O2 KK(g2s)2(u2s)2(g2pz)2(u2px)2(u2py)2(g2px)1(g2py)1 2 121 494

O 2- KK(g2s)2(u2s)2(g2pz)2(u2px)2(u2py)2(g2px)2(g2py)1 3/2 135 395

O 22- KK(g2s)2(u2s)2(g2pz)2(u2px)2(u2py)2(g2px)2(g2py)2 1 149

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 PChem 11 - 29

Electron Density Contours of Li2

g2s

Total
u1s  K
nonbonding

g1s  K
nonbonding

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 PChem 11 - 30

SCF – LCAO – MO Electron Density Contours

Total electron
densityy map
p
O2 F2
MO B2 C2 N2
Li2
2 4
1g

3g 2 2

1u 2 4

2u 2

2g 2

1u 2
1g 2

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 PChem 11 - 31

The Photoelectron Spectrum of N2

N2 (g1s)2(u1s)2(g2s)2(u2s)2(u2px)2(u2py)2(g2pz)2

Ionization Energy (MJ/mol)

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 PChem 11 - 32

Paramagenetism

Oxygen with unpaired electrons in

parallel spin

(g2px)1(g2py)1

is paramagnetic and attracted in the

magnetic field.

Nitrogen with all electrons paired (no

parallel spin)

(u2px)2(u2py)2(g2pz)2

iis diamagnetic
di ti andd repelled
ll d in
i the
h
magnetic field.

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 PChem 11 - 33

Heteronuclear LCAO – MO HF (2sF)2(b)2(2pxF)2(2pyF)2

Atomic orbitals of similar energy combine to give molecular orbitals.

H atom F atom
z antibonding
a
1s 2pz

1s
-0.500 Eh

z nonbonding
2px 2py 2p 1s
-0.684 Eh 2px or 2py

z bonding
b
1s 2pz
z nonbonding
2s 2s 2s
HF molecule
l l -1.477 Eh 1s

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 PChem 11 - 34

Heteronuclear LCAO – MO

N2 KK (2s)2 (2s)2(2px)2 (2py)2 (2pz)2 N  N 110 pm 942 kJ/mol

CN- KK (2s)2 (2s)2(2px)2 (2py)2 (2pz)2
CO KK (2s)2 (2s)2(2px)2 (2py)2 (2pz)2 C  O 113 pm 1071 kJ/mol

*2pz

*2px *2py
2p
2pz 2p

u2px u2py

*2s
2s

2s 2s

C atom CO O atom Ionization Energy (MJ/mol)

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 PChem 11 - 35

HF/6-31G* Results for Diatomic Molecules

Molecule Bond length / pm Experiment / pm

H2 73.0 74.2
LiH 163.6 159.6
HF 91.1 91.7
NaH 191 4
191.4 188 7
188.7
HCl 126.6 127.5
LiCl 207.2 202.1
CO 111.4 112.8
N2 107.8 107.9
ClF 161 3
161.3 162 8
162.8
Li2 281.2 267.3
Na2 313.0 307.8
NaCl 239.7 236.1
Cl2 199.0 198.8
F2 134.5 141.2

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 PChem 11 - 36

Molecular Term Symbols for Diatomic Molecules

the molecular state symbol

ML the
th orbital
bit l angular
l momentum
t quantum
t number
b
2S+1 +/-
g/u | ML | = 0 1 2 3 4 5 ...
      ...

2S + 1 the spin multiplicity

g / u the product of the inversion symmetry :
gerade / ungerade (homonuclei only)
+/- symmetry against the vertical mirror plane
symmetry + / antisymmetry - ( states only)

g 2, 4 and 4) are 1+g. Examine onlyy outer shells.

All filled shells ((e.g.,

The state of the hole is the state of the electron.

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 PChem 11 - 37

Molecular Term Symbols

B2 (1g)2(1u)2(2g)2(2u)2(1u)1(1u)1  (1u)1(1u)1 ml = ±1, ms = ±1/2

MS
1 0 -1
2 1+, 1+ 1+, 1- 1-, 1-
ML 0 1+, -1+ 1+, -1- ; -1+, 1- 1-, -1-
-2 -1+, -1+ -1+, -1- -1-, -1-

ML = 0, MS = -1, 0, 1 3S -
g  the ground state
ML = 2 and –2 ( |ML|=2 ), MS = 0 1D
g

ML = 0, MS = 0 1S -
ug • u=g

(+)(-) = (-)

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 38

Molecular Term Symbols

The ground state electron configurations and term symbols

Term
Molecule Electron configuration
g
symbol
H 2+ (1g)1 2 +
g

H2 (1g)2 1 +
g

He2+ (1g)2(1u)1 2 +
u

Li2 (1g)2(1u)2(2g)2 1 +
g

B2 (1g)2(1u)2(2g)2(2u)2(1u)1(1u)1 3 -
g

C2 (1g)2(1u)2(2g)2(2u)2(1u)2(1u)2 1 +
g

N 2+ (1g)2(1u)2(2g)2(2u)2(1u)2(1u)2(3g)1 2 +
g

N2 (1g)2(1u)2(2g)2(2u)2(1u)2(1u)2(3g)2 1 +
g

O 2+ (1g)2(1u)2(2g)2(2u)2(3g)2(1u)2(1u)2(1g)1 2
g

O2 (1g)2(1u)2(2g)2(2u)2(3g)2(1u)2(1u)2(1g)1(1g)1 3 -
g

F2 (1g)2(1u)2(2g)2(2u)2(3g)2(1u)2(1u)2(1g)2(1g)2 1 +
g

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 PChem 11 - 39

11.6 Electronic Structure of Polyatomic Molecules

Valence Bond Method

Heitler and London described chemical bonds with overlap of valence electrons

Orbital Hybridization
Linear combinations of atomic orbitals on the same atom Hybrid orbitals

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 PChem 11 - 40

Orbital Hybridization

BeH2 H-Be-H = 180° linear

Be-H
B H = c1 Be(2s)
B (2 ) + c2 Be(2p)
B (2 ) + c3 H(1s)
H(1 ) = c Be(2sp)
B (2 ) + c3 H(1s)
H(1 )

2
2s
sp- H Be H
2pz
sp+

H Be H

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 PChem 11 - 41

sp Hybrid Orbitals

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 PChem 11 - 42

Bonding in BeH2

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 PChem 11 - 43

sp2 Hybrid Orbitals

2pz

2s

2px

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 PChem 11 - 44

sp3 Hybrid Orbitals

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 PChem 11 - 45

d2sp3 Hybrid Orbitals

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 PChem 11 - 46

sp3.98 Hybridization of H2O

- 0.71 0.71
 HOH = 104.5° in the yz-plane y

1 = c11 2s + c12 2py + c13 2pz

2 = c21 2s + c22 2py + c23 2pz
33’ = c33’11 2s + c33’22 2ppy + c33’33 2ppz
0.55

c12 = - c22, c33’22 = 0,, c122 + c222 + c33’222 = 1.0

z
c12 = 0.7071, c22 = -0.7071 c11 = 0.4474
c12 = 0.7071
tan  = tan 52.25 = 1.2915 = c12 / c13 , c13 = 0.5475 c13 = 0.5475
c21 = 0.4474
c112 + c122 + c132 = 1.0, c11 = 0.4474 c22 = -0.7071
c23 = 0.5475
c21 = c11 = 0.4474, c23 = c13 = 0.5475
c31 = 0.7743
c21 c3’1 + c23 c3’3 = 0, c3’2 = -c21 c3’1 / c23 = -0.8172 c3’1 c32 = -0.6328
c3’12 + c3’22 = 1.0, c3’1 = 0.7743, c3’2 = -0.6328 c33 = 0.0

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 47

sp3.98 Hybridization of H2O

1 = 0.45 2s + 0.71 2py + 0.55 2pz

2 = 0.45 2s - 0.71 2py + 0.55 2pz
3’ = 0.77 2s - 0.63 2py

3 = d3 3’ + d34 2px = 0.77

0 77 d3 2s - 0.63
0 63 d3 2py + d34 2px
4 = d4 3’ + d44 2px = 0.77 d4 2s - 0.63 d4 2py + d44 2px
(0.45)2 + (0.45)2 + (0.77 d3 )2 + (0.77 d4 )2 = 1.0, d3 = d4 = 0.7110
(0.77 d3 )2 + (0.63 d3 )2 + d342 = 1.0, d34 = 0.717
(0.77 d3 )(0.77 d4 ) + (0.63 d3 )(0.63 d4 ) + d34 d44 = 0 , d44 = -0.717

1 = 0.45 2s + 0.71 2py + 0.55 2pz O-H bond : s(sp3.98 - 1s)

2 = 0.45 2s - 0.71 2py + 0.55 2pz p / s = ( 0.712 + 0.552 ) / 0.452 = 3.98

3 = 0.54
0 54 2s
2 - 0.44
0 44 2p
2 z + 0.72
0 72 2p
2 x
4 = 0.54 2s - 0.44 2pz - 0.55 2px

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 48

Molecular Shapes

A 2s, 2px, 2py, 2pz

AH2  = c1 1sHa + c2 1sHb + c3 2sA + c4 2pxA + c5 2pyA + c6 2pzA
H 1s

LINEAR 2u
2u

3g
3g
2p 1u, 1u
y y

2s
z z 1u, 1u

1s x x

1u
1u

2g
2g
Be BeH2 H

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 PChem 11 - 49

Bending the H – A – H Angle

y y

z z

x x
2b2

2u
4a1
3g

1u 1b1

1b2
3a1
2a1
1u
2g
180° Bond angle 90°

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 50

AH2 MO Diagrams

LINEAR BENT

2b2
2u
4a1
3g

2p 1u, 1u
1b1 1s

2p
2s
3a1

1s
1b2

1u
2s
2g
2a1

Be BeH2 H O H2O H

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 51

Photoelectron Spectroscopy

2b2 H2O

4a1

1b1 1s
1b1
2p
3a1
3a1

1b2 1b2

2s

2a1 1.2 1.4 1.6 1.8 2.0

O H2O H Ionization Energy ( MJ / mol )

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 52

Photoelectron Spectroscopy

2t2

3a1 CH4

1t2

2p

1s

2a1

2s
1t2

1.3 1.5 1.8 2.1 2.4

2a1 Ionization Energy ( MJ / mol )
C CH4 H

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 53

Photoelectron Spectroscopy

C2H4
2b3g
2b2u
4b1u
4ag

3b1u
1b3u
1b2g

2p
1b3u 1b3g
3ag
1s 3ag
1b3g 1b2u
1b2u
2b1u
2ag
2b1u
2s

2ag 1.0 1.4 1.8 2.2 2.6

C C2H4 H gy ( MJ / mol )
Ionization Energy

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 54

Bonding in Ethane

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 55

Bonding in Ethene

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 56

Bonding in Methanal

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 57

Bonding in Ethyne

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 58

Bonding in N2

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 59

11.7 Hückel Molecular Orbital Theory

The  Electron Approximation
 electrons in the fixed effective electrostatic potential of the  frame work

C 2H 4

1930 Erich Hückel, Hückel Molecular Orbital Theory

Ĥ the effective Hamiltonian
H11 = H22 =  the Coulomb integral
H12 = H21 = i(i±1) the resonance integral / the exchange integral
Sij = ij the overlap integral of p-AO
AO’ss

 = E2p  = ~ -75 kJ/mol

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 60

Hückel Molecular Orbital Theory

E =  ± 

E
E = - 
c 1 = -c 2 =



E = + 
c1 = c2 =

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 61

Delocalization : Butadiene

Hii = 
Hij = i(j±1)
Sij = ij

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 62

Delocalization : Butadiene

 - 1.168
1 168

 - 0.168


 + 0.168

 + 1.168

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 63

Delocalization : Butadiene

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 64

Delocalization : Butadiene

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 65

Aromaticity : Benzene

x = ±1, ±1 and ±2

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 66

Aromaticity : Benzene

E
 - 2

-

+

 + 2

Edeloc = E(benzene) – 3 E(ethene) = 6 + 8 – 3(+) = 2 < 0

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 67

Aromaticity : Benzene

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 68

Aromaticity : Benzene

E6 =  - 2

E4 = E5 =  - 

E2 = E3 =  + 

E1 =  + 2

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 69

11.9 Intermolecular Forces

1
Short-range repulsive interactions  in Lennard-Jones potential
R12

Long-range attractive interactions

2
2  A B  1
p p interaction
Permanent dipole-dipole V ( R)   
dd
3kT  4 0  R 6

 B A2   A B2
Dipole-induced
p dipole
p interaction V ( R) 
ind
(  0 ) 2 R 6
(4

3  EA EB   A B 1
London force ((dispersion
p force)) V ( R)   
 EA  EB  (4
(  0 ) 2 R 6
disp
2

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 70

The Lennard-Jones Potential

  12   6  Lennard-Jones Potential Parameters

V ( R )  4      
 R   R    / k (K)  (pm)
Ar 120 341
 Rmin 12  Rmin  
6
V ( R )      2   Xe 221 410
  R   R  
H2 37 293
N2 95.1 370
O2 118 358
Cl2 256 440
CO2 197 430
CH4 148 382
C6H6 243 860

The energy of interaction of two nitrogen molecules

as a function of distance according to the Lennard-
Jones potential.

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 71

11.10 Band Theory of Solids

Formation of a band of very closely spaced energy levels as atooms overlap

s levels in a one-dimensional solid.

한양대학교 HANYANG UNIVERSITY

 PChem 11 - 72

Band Theory of Solids

Formation of a band of an s band and a p band in a one-dimensional solid. The lowest level in the s band is
fully bonding and the highest level in the s band is fully antibonding. This also applies to the p band. There is
a gap between the s band and the p band in the solid that is smaller than the difference in the energies of the s
l l andd the
level th p level
l l iin
ii the
th isolated
i l t d atoms.
t

한양대학교 HANYANG UNIVERSITY