Molecular Orbital Theory

Dr Karimah Kassim
 The Central Themes of MO Theory

A molecule is viewed on a quantum mechanical level as a

collection of nuclei surrounded by delocalized molecular orbitals.

Atomic wave functions are summed to obtain molecular wave

functions.

If wave functions reinforce each other, a bonding MO is formed

(region of high electron density exists between the nuclei).

If wave functions cancel each other, an antibonding MO is formed

(a node of zero electron density occurs between the nuclei).
Figure 11.14
An analogy between light waves and atomic wave functions.

Amplitudes of wave
functions added

Amplitudes of
wave functions
subtracted.
Figure 11.14 Contours and energies of the bonding and antibonding
molecular orbitals (MOs) in H2.

The bonding MO is lower in energy and the antibonding MO is higher in

energy than the AOs that combined to form them.
Molecular Orbital (MO) Configurations

1. The number of molecular orbitals (MOs) formed is always

equal to the number of atomic orbitals combined.
2. The more stable the bonding MO, the less stable the
corresponding antibonding MO.
3. The filling of MOs proceeds from low to high energies.
4. Each MO can accommodate up to two electrons.
5. Use Hund’s rule when adding electrons to MOs of the
same energy.
6. The number of electrons in the MOs is equal to the sum of
all the electrons on the bonding atoms.
 Number of Number of
bond order =
1
2 ( electrons in
bonding
MOs
- electrons in
antibonding
MOs
)

bond
½ 1 ½ 0
order

•Small Value B.Order, indicate longer Bond Length.Thus, weaker bond strength .

* Big value B.Order, indicate shorter Bond Length. Thus, stronger bond strength
Figure 11.15 The MO diagram for H2.
Filling molecular orbitals with electrons follows the
same concept as filling atomic orbitals.

s*1s
Energy

1s 1s

H2 bond order
= 1/2(2-0) = 1
s1s

AO MO AO
of H of H2 of H
 Figure 11.16 MO diagram for He2+ and 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

SAMPLE PROBLEM 11.3 Predicting Stability of Species Using MO Diagrams

PROBLEM: Use MO diagrams to predict whether H2+ and H2- exist.

Determine their bond orders and electron configurations.

PLAN: Use H2 as a model and accommodate the number of electrons in

bonding and antibonding orbitals. Find the bond order.

SOLUTION:
bond order bond order
= 1/2(1-0) = 1/2(2-1)
= 1/2 = 1/2
H2- does exist

configuration is
configuration is (s1s)1 (s1s)2(s2s)1
 Figure 11.18 Bonding in s-block homonuclear diatomic molecules.

s*2s
Energy

s*2s

2s 2s 2s
2s

s2s s2s

Li2 Be2
Li2 bond order = 1 Be2 bond order = 0
Figure 11.19
Contours and energies of s and p MOs through
combinations of 2p atomic orbitals.
Figure 11.20 Relative MO energy levels for Period 2 homonuclear
diatomic molecules.
without 2s-2p with 2s-2p
mixing mixing

MO energy levels MO energy levels

for O2, F2, and Ne2 for B2, C2, and N2
 Figure 11.21

MO occupancy
and molecular
properties for B2
through Ne2
 Figure 11.23 The MO diagram for HF

s
Energy

1s

2px 2py 2p

s
AO MO of AO
of H HF of F
 Figure 11.24 s* s
The MO diagram for NO

* p

2p
Energy

s p
2p
possible Lewis
structures
 p
0 0
N O
s* s
-1 +1
2s N O
2s
AO of N AO of O
s s

MO of NO