LEC15_20.02.24

General Chemistry (CHEM F111)
Lecture-15
20/02/2024
Recap
VB Theory
Bonding in N2 and H2O molecules
-Modifications of VB theory- Promotion of
electrons and hybridization
-Resonance
- Molecular Orbital Theory
Today’s Topic
LCAO-MO theory
-Bonding and Anti-bonding MOs
-Overlap integral and Symmetry
-Comparison between VB and MO theory
-Symmetries of MOs in Homonuclear Diatomic
-MOs of Period 2 Homonuclear Diatomic Molecules
-MOs of Heteronuclear Diatomic Molecules
H2+ - Simple MO Treatment
Electronic energy of
H2+ corresponding to
electron occupying
the bonding (+), and
antibonding (-)
molecular orbitals,
respectively. While
the first is bound, the
second is an
unbound or repulsive
state
H2+ Simple LCAO MOs : Energy levels
MO’s characterized by
• Energy - Bonding / Antibonding (*) character based on whether
the energy shows a minimum as a function of inter-nuclear
distance or not
• Number of nodal planes - 0 (), 1 () etc. [excluding nodal plane
in antibonding]
Simple MO Picture of H2
• Use the molecular orbitals obtained for H2+, fill in accordance
with Aufbau principle
• Place both electrons in bonding MO ψ1, ie., (1σ)2
• ψ = ψ1(1)ψ1(2) 2-1/2[()() − ()()
• Also in fair agreement with experiment (Bound state – eq. bond
length 0.81 A, and dissociation energy 260 kJ/mole)
Overlap Integral
• An important consideration in bonding is the

Overlap Integral, S = ∫ΦaΦbdτ over all space
• If the two functions are both large as in the
inter-nuclear region at typical bond distances,
then the integral is large
• If one, or both of the functions are small, then Overlap integral
the contributions to the integral are small, as between 1s orbitals
when the two nuclei are far apart. centered on the two
nuclei of H2 as a
function of separation
• Clearly, the integral depends on the distance. R
• For the case of the two 1s orbitals, one can show that the
integral S = e-R/a0 {1 + R/a0 + R2/3a02}
• The exponential factor makes sure that the integral goes to zero
as the distance becomes very large.
Symmetry and Overlap
Does not contribute to bonding

Overlap Integral and Symmetry
Same symmetry, S = ∫ΦaΦbdτ

but S is small.
Low contribution While building MO, we
to form bond. need to do linear
combination of atomic
Same symmetry
and large S. orbitals of the same
Atomic orbitals symmetry w.r.t the
contribute internuclear axis.
significantly to
form bond.
Orbitals of different symmetries,

S = 0. No bond formation.
Comparison of VB and MO pictures of H2
•Localized electron pair bond in VB, electrons fill

delocalized orbitals in MO picture.
• Simple VB and MO spatial wavefunctions:
• ψVB = 1sa(1)1sb(2) + 1sb(1)1sa(2) = ψcov
• ψMO = (1sa + 1sb)(1) (1sa + 1sb)(2) =
1sa(1)1sb(2)+1sb(1)1sa(2)+1sa(1)1sa(2)+1sb(1)1sb(2)
= ψcov + ψion
Comparison of VB and MO pictures of H2
While simple VB totally ignores ionic structures,

simple MO gives equal weights to covalent and
ionic structures.
VB corrected by adding ionic structures – an
example of resonance. Ψ = ψcov + ψion. Ionic
contribution proportional to 2. Parameter 
determined by the Variation theorem – Energy of
trial wavefunction is never less than the true
energy.
MO : Molecular Hydrogen
Symmetries of MOs in Homonuclear Diatomic
Molecule: Transformation under Inversion
Sigma (): The interaction occurs along the

internuclear axis
g = gerade (even) symmetry

u = ungerade (odd) symmetry
Symmetries of MOs in Homonuclear Diatomic
Molecule: Transformation under Inversion
Pi (): The interaction occurs in two regions, one
directly above and the other directly below the
internuclear axis
MO bonding anti-bonding
σ g u
π u g
General Rule to fill-up the MOs
1. Number of MOs = Number of AOs.

2. Bonding (lower energy) and antibonding
(higher energy) MOs formed from AOs.
3. e- fill the lowest energy MO first (aufbau
process)
4. Maximum 2 e- per orbital (Pauli Exclusion
Principle)
5. Degenerate orbitals fill singly before they pair
up (Hund’s Rule).
Calculation of Bond order
•Strength of a bond is estimated from the Bond order
No. e- in bonding MOs - No. e- in antibonding MOs

Bond Order =
2
•Unpaired electrons gives rise to Magnetic Moments:

Paramagnetic
Predicting Stability: H2+ & H2-
bond order = bond order =

1/2(1-0) = 1/2 1/2(2-1) = 1/2
H2+ does exist H2- does exist
u u
1s 1s 1s 1s
AO of H AO of H AO of H-
AO of H
g g
MO of H2+ MO of H2-
configuration is : g1 configuration is : g2u1

Helium: He2+ vs He2
u u
Energy
Energy
1s 1s 1s 1s
g g
AO of MO of AO of AO of MO of AO of
He He+ He+ He He2 He
He2+ bond order = 1/2 He2 bond order = 0

Bond Length vs. Bond Order
Period 2 Homonuclear Diatomic Molecules
Electrons in the K shell do not participate in

bonding
1g and 1u from the 2s orbitals
 Molecular Orbitals
2g and 2u from the 2pz orbitals
π Molecular Orbitals
The 2px and 2py orbitals lead to a pair of  and a

pair of * orbitals
Bonding in 2s & 2p orbitals
*2s *2s
2s 2s
Energy
Li2 2s 2s Be2
*1s *1s
1s 1s
Be2 B.O. = 0
1s
Li2 B.O. = 1 1s
Relative Energy Levels for 2s & 2p
WITHOUT big WITH big 2s-

2s-2p repulsion 2p repulsion
MO energy levels MO energy levels

for O2, F2, and Ne2 for Li2, Be2, B2, C2,
and N2
Relative Energy Levels for N2 & O2
N2 O2
Molecular Energy level diagram: N2
BO = ½(n-n*) = 3
Note that π is lower than σ
s and p are close in energy, s-p

Interactions are high
1σg2 1σu*2 1πu4 2σg2
‘ and  are of mixed s and p character’

Molecular Energy level diagram: O2
1s22s2 2p2x 2p1y 2p1z

1σg2 1σu*2 2σg2 1πu4 1πg*2
BO = ½(n-n*) = 2
Note that σ is lower than π
O2 is paramagnetic
Orbital energy variation
Molecular Orbitals using Atomic d Orbitals
Heteronuclear Diatomic Molecules
Heteronuclear diatomics
• Polar bonds, electron pair shared unequally,
and resultant partial charges on atoms.
• Electronegativity – power of an atom to attract

electrons to itself when it is part of a compound
• Pauling: │χA – χB│= 0.102 [ΔE/(kJ mol-1)]1/2
where
ΔE = E(A-B) – 0.5[E(A-A) + E(B-B)]
• Mulliken: χ = 0.5 (IE + EA)
BITSPilani, Pilani Campus

Heteronuclear diatomics
• In MO, ψ = cAψA + cBψB, relative contributions

determined by cA2 and cB2
• Coefficients determined by variation theorem.
•For purely covalent compound: cA2 = cB2

•For purely ionic compound (e.g. Cs+F-): cA2 = 0,
cB2=1.
•For Bonding MO: if χA > χB, then cA2 > cB2 .
•For Anti-bonding MO: if χA > χB, then cA2 < cB2 .

General wavefunction for HF:
ψ = cH1sH + cF2pzF; variation theorem can be used
to find two sets of coefficients.
Molecular orbitals of HF
Atomic Orbital with lower energy (belonging to more

electronegative atom) makes larger contribution to lowest
energy MO.
The bonding orbital has principally 2pzF character, and the
antibonding orbital, H1s. The bond will be polar with a partial
negative charge on F.
CO molecule
LUMO
10 valence electrons
HOMO
MO energy level diagram of CO
Lowest energy orbitals are of
‘O’ character being more
electronegative.
HOMO: 3 has significant C 2s
and 2p character. The two
electrons that occupy it are
regarded as a lone pair on C.
LUMO: 2 has predominantly C
2p character.
1σ2 2σ2 1πu4 3σ2
Lone pair on C and a pair of
empty  orbitals also largely on
C: CO acts as a ligand

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General Chemistry (CHEM F111)

• An important consideration in bonding is the

Does not contribute to bonding

Same symmetry, S = ∫ΦaΦbdτ

Orbitals of different symmetries,

•Localized electron pair bond in VB, electrons fill

While simple VB totally ignores ionic structures,

Sigma (): The interaction occurs along the

g = gerade (even) symmetry

1. Number of MOs = Number of AOs.

•Strength of a bond is estimated from the Bond order

No. e- in bonding MOs - No. e- in antibonding MOs

•Unpaired electrons gives rise to Magnetic Moments:

bond order = bond order =

H2+ does exist H2- does exist

configuration is : g1 configuration is : g2u1

He2+ bond order = 1/2 He2 bond order = 0

Electrons in the K shell do not participate in

The 2px and 2py orbitals lead to a pair of  and a

Li2 2s 2s Be2

WITHOUT big WITH big 2s-

MO energy levels MO energy levels

Note that π is lower than σ

s and p are close in energy, s-p

1σg2 1σu*2 1πu4 2σg2

‘ and  are of mixed s and p character’

1s22s2 2p2x 2p1y 2p1z

Note that σ is lower than π

• Electronegativity – power of an atom to attract

• Mulliken: χ = 0.5 (IE + EA)

BITSPilani, Pilani Campus

• In MO, ψ = cAψA + cBψB, relative contributions

•For purely covalent compound: cA2 = cB2

BITSPilani, Pilani Campus

Atomic Orbital with lower energy (belonging to more

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