General Chemistry (CHEM F111)

Lecture 37:15.11.2018
 RECAP
Worked out examples on spectral data
Quantum Theories of Chemical Bonding
•Valence bond theory
•Molecular orbital theory
(Both theories use wave functions to describe molecules)

Total wave function (H2 molecule)

PE curves of H2
Polyatomic molecule: Valence bond treatment

VB Theory - Drawbacks
Hybrid Orbitals: hybridization, number; shape
Molecular Orbital Theory
hybrid orbitals – sp, sp2, or sp3
formation of s bond
 s bond

remaining p orbitals form sp or sp2

 Planar molecule (each carbon
p bond hinders rotation
is trigonal planar) with p
about the carbon-to-
cloud above and below the
carbon bond
plane

formation of p bond
 Molecular Orbital Theory
• Orbital, ie., one electron wavefunction based description.
• Simplest one electron molecular species H2+
• Ĥe = Ťe – e2/4πε0ra - e2/4πε0rb + e2/4πε0R

• Can treat exactly within Born Oppenheimer approximation, but

more useful to develop approximate description

• Write ψ = caφa + cbφb where φa and φb are the 1s orbitals centered

on nuclei a and b respectively, vary ca and cb
• ψ is a molecular orbital formed by a linear combination of atomic
orbitals (LCAO MO)
• From symmetry, expect combination ψ1 = N1(φa + φb)
• Obtain a second linear combination ψ2 = N2(φa – φb)
Molecular Orbital wave function (H2+ molecule)

Constructive interference (accumulation of

electron density between the nuclei ):
Ψ(σ) or Ψ+ = (1/√2 ) [φ(1s ) + φ(1s ) ]
a b

Destructive interference (depletion of

electron density between the nuclei ):
Ψ(σ*) or Ψ- = (1/√2 ) [φ(1s ) - φ(1s ) ]
a b

Overall wavefunction= superposition of atomic orbitals

 Bonding Molecular Orbital

Bonding: Energy shows a

minimum as a function of the
inter-nuclear separation

Origin of bonding character:

• Bonding because bound state
• The bonding orbital results in increased electron density
between the two nuclei, and is of lower energy than the two
separate atomic orbitals.
 Antibonding Molecular Orbital

Antibonding: Energy decreases

monotonically as a function of the
inter-nuclear separation with no
minimum

Origin of antibonding character:

• Antibonding since repulsive state with no minimum in energy
• Note the node between nuclei.
• Decreased electron density between nuclei due to destructive
interference and is of greater energy than the two separate
atomic orbitals.
 Ground State of H2+ - Simple MO Picture

• Electronic configuration (1σ)1

• Predicts an equilibrium bond length of 130 pm and bond

dissociation energy of 171 kJ/mole

• Experimental values are 106 pm and 250 kJ/mole

• Reasonable agreement given crude nature of description

 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
•Transformation under inversion – symmetric (g), antisymmetric
(u). (molecules with center of symmetry)
 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 between
the contributions to the integral are small, as 1s orbitals centered on the
when the two nuclei are far apart. two nuclei of H2 as a
function of separation R

• Clearly, the integral depends on the distance.

• 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
Overlap Integral
S = ∫ΦaΦbdτ

Does not contribute to bonding

 Comparison of VB and MO pictures of H2
• VB picture of H2 as two hydrogen atoms perturbing
each other, MO based on H2+ picture with inter-electronic
repulsion as a perturbation correction.
• 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 corrected also by varying the amount of ionic
character using the variation theorem, by mixing other
configurations (1σ)2 + (1σ*)2.
 Ionic-Covalent Resonance

What about HF?

ψc(1,2) = {a(1)b(2) + b(1)a(2)} {  }
with a and b being the 2s of H and the 2pz of F, say. But HF is
polar. So expect
ψi(1,2) = b(1)b(2) {  } also to be highly
reasonable
Write ψ = ψc + λψi (trial wave function), and vary the
parameter λ to minimize the energy, an example of the
Variation theorem. (No approximate wavefunction can yield
an energy that is lower than the exact energy of the ground
state)
 Nature of polar bond

•Polar bond – electron pairs are shared unequally-

partial charges on atoms.

•A polar bond consists of two electrons in atomic

orbitals of the form ψ = cAψA + cB ψB

•Relative contributions determined by cA2 and cB2.

•Coefficients determined by variation theorem:

cA2 = cB2 Purely covalent compound

cA2 = 0, cB2=1, purely ionic species
 VB wave function for polar molecules

Example: HCl (purely covalent):

H-Cl (1,2) =  H 1s (1)  Cl 2pz(2) +  H 1s (2)  Cl 2pz(1)

Unrealistic – unequal sharing is not described!
HCl (purely ionic):

H+-Cl- (1,2) =  Cl 2pz(1)  Cl 2pz(2)

Unrealistic – fully ionic species
 VB wave function for polar molecules

 = covalent + ionic
•Keep on varying the  until reaching lowest
possible energy (Variation theorem)
For ex., lowest energy is reached when  =
0.1, hence, 2 =0.01
 = covalent + 0.1ionic
The probability of finding the molecule in its
ionic form is 1 in 100
 Resonance

• Kekule Structures of benzene

• Resonance Stabilization
• Molecule not to be thought of as flickering between
contributing structures
• Mathematical device for closer approximation to
the true wavefunction

 = Kekule1 +  Kekule2
Write the valence bond function of LiH considering it to be
(i)Purely covalent (ii) Purely ionic (iii) 60% covalent and 40%
ionic. Neglect the hybridization in Li atom and assume that only
the Li 2s-orbital and the H1s-orbital are involved.

Solution:
(i) cov = C1H(1)Li(2) + C2H(2)Li(1)

(ii) ion =CH(1)H(2)

(iii) C3cov + C4ion

C32 = 0.60 similarly C42 = 0.40  C3 = 0.77 and C4 = 0.63

 = 0.77cov + 0.63ion
MO : Molecular Hydrogen
Transformation under inversion

Sigma (s): The interaction occurs along the

internuclear axis
Pi (p): 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

s s

1s 1s 1s 1s

AO of H AO of H AO of H-
AO of H
s s
MO of H2+ MO of H2-
configuration is
configuration is (s1s)1 (s1s)2( s1s)1
 Helium: He2+ vs He2

s*1s s*1s
Energy

Energy
1s 1s 1s 1s

s1s s1s
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
1sg and 1su from the 2s orbitals
2sg and 2su from the 2pz orbitals
 π Molecular Orbitals

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

pair of p* orbitals
Inversion Symmetry of π Orbitals
 Bonding in 2s & 2p orbitals

s*2s s*2s

2s 2s
Energy

s2s s2s Be2

Li2

s*1s s*1s

1s 1s

Li2 B.O. = 1 s1s Be2 B.O. = 0

s1s
 Relative Energy Levels for 2s & 2p
WITH big 2s-2p WITHOUT big
repulsion 2s-2p repulsion

MO energy levels MO energy levels

for B2, C2, and N2 for O2, F2, and Ne2
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

s and s of mixed s and p character.

Molecular Energy level diagram: O2

1s22s2 2p2x 2p1y 2p1z 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
The diradical nature of triplet oxygen causing it to be paramagnetic
Orbital energy variation
Molecular Orbitals using Atomic d Orbitals
 Heteronuclear Diatomic molecules
Example: HF


More
Energy
 +
Less
electronegative

electronegative -

Atomic Orbital with lower energy (belonging to

more electronegative atom) makes larger
contribution to lowest energy MO
General wavefunction for HF:
ψ = cH1sH + cF2pzF; variation theorem can be used
to find two sets of coefficients.