CHAPTER 3: INTRODUCTION TO

MOLECULAR ORBITAL THEORY

Topic Outline
Homonuclear diatomic molecule: H2, He2, O2, F2, Ne2
Constructive and destructive combination of atomic

orbital
Energy level diagram and the shape of molecular orbital
Electron configuration for the diatomic molecule
Bond order

Lewis structure, Valence Bond Theory & Hybridization

Problems?????

No direct info on bond energies

Assuming all electron are localized (stay one place)

Not effective for unpaired electron

MO Theory
Molecular orbital (MO) theory describes bonding in terms

of molecular orbitals
A molecule is viewed on a quantum mechanical level as a

collection of nuclei surrounded by delocalized molecular

orbitals.
Molecular orbitals
Results from interaction of atomic orbitals of bonding

atoms
Associated with the entire molecule
According to MO theory, the overlap of 2 similar orbitals
leads to formation of 2 MOs one bonding MO and one
antibonding MO

Constructive combination
Adding the wave function together. This combination

forms a bonding MO
Bonding MO- has a region of high electron density
between the nuclei
For electron waves, the overlap increases the probability
that the electrons are between the nuclei

An analogy between

light waves and atomic

wave functions.
Amplitudes of wave
functions added

Destructive combination
Subtracting

wave function from each other. This

combination forms an antibonding MO
Antibonding MO- has a region of zero electron density (a
node) between the nuclei
Subtractive overlap to light cancelling
each other

Amplitudes of
wave functions
subtracted.

Energy level diagram, the shape of

molecular orbital, bond order and
electron configuration

Energy and shape of H2 in molecular orbitals

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.

Energy of H2 in molecular orbitals

Bonding MO ()
e- spread btw nuclei
e- being delocalized its
charge
e- repulsion reduce make
MO lower E

Antibonding MO (*)
Has node btw nuclei
e- density outside
internuclear region
e- do not shield nucleus,
increases of nucleus2
repulsion make
antibonding MO higher E

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 Hunds 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.

Filling the orbitals with electron

MOs filled in order increasing energy
MO Max capacity is 2 spin with opposite spin
Orbital of equal energy half filled, with spin parallel, b4

completely filled
Molecular Orbital Bond Order
Number of
Number of
1
electrons in
electrons in
bond order =
bonding
antibonding
2
MOs
MOs
BO > 0 molecular species is stable
BO = 0 no net stability, species does not exist

Higher bond order, the stronger the bond, shorter length

Energy Level Diagram- s orbitals

AO of H

MO of H2

AO of H

Shape of Orbitals- s orbitals

The

bonding & antibonding MO has

different shapes, due to the different
electron density region

Figure 11.15

The MO diagram for H2.

Filling molecular orbitals with electrons follows the

same concept as filling atomic orbitals.

Energy

s*1s

1s

1s

s1s

AO
of H

MO
of H2

AO
of H

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

Figure 11.16

MO diagram for He2+ and He2.

s*1s

1s

1s

Energy

Energy

s*1s

1s

1s

s1s

AO of
He

MO of
He2+

s1s

AO of
He+

He2+ bond order = 1/2

AO of
He

MO of
He2

AO of
He

He2 bond order = 0

SAMPLE PROBLEM 11.3 Predicting Stability of Species Using MO Diagrams

PROBLEM:
PLAN:

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

Determine their bond orders and electron configurations.

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

bonding and antibonding orbitals. Find the bond order.

SOLUTION:

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

H2- does exist

H2 does exist

1s

1s

1s
AO of H+

AO of H
s

MO of H2

bond order
= 1/2(2-1)
= 1/2

AO of H-

AO of H
)1

1s

configuration is (s1s

s
MO of H2-

configuration is
(s1s)2(s2s)1

Energy

Homonuclear Diatomic Molecules of the

Period 2 Elements

s*2s

s*2s

2s

2s

s2s

2s

2s

s2s

Figure 11.18

Be2

Li2
Li2 bond order = 1

Be2 bond order = 0

Energy Level Diagram- p orbitals

For p orbitals, the energy level diagram is slightly more

complex for 2 reasons:

The p orbitals can form 2 types of bond sigma & pi

bonds
End to end combination gives a pair of MO- 2p, *2p

side to side combination gives a pair of MO- 2p , *2p

The p orbitals can interact with the s orbitals the

interaction will affect the energy levels of the orbitals

 MOs formed from 2s orbitals

are lower in energy than MOs
formed from 2p orbitals

Energy

Bonding MOs are lower in

energy than antibonding MOs
atomic p orbitals can interact
more extensively end-to-end than
side-to-side. Thus 2p MO is
lower energy than 2p
Destabilizing effect of *2p MO is
greater than *2p

Energy order

adibatul@salam.uitm.edu.my
s2p <
p 2p < p2p < 2p

Shape of Orbitals- p orbitals

Figure 11.19

Contours and energies of s and p MOs through

combinations of 2p atomic orbitals.

adibatul@salam.uitm.edu.my

Figure 11.20

Relative MO energy levels for Period 2 homonuclear

diatomic molecules.

without 2s-2p
mixing

with 2s-2p
mixing

MO energy levels
for O2, F2, and Ne2

MO energy levels
for B2, C2, and N2

O, F and Ne
Atoms are small, so relatively strong repulsion occur as
the 2p electron pair up
These repulsion raise energy of the 2p orbitals high
enough above the energy of 2s orbitals to minimize
orbital mixing

B, C and N
Atoms are larger, when 2p AO are half-filled, repulsion are
relatively small
2p energy are much closer with 2s energy some mixing
occurs
This orbital mixing lowers the energy of the 2s and *2s MO
and raises the energy of 2p and *2p

Bonding in the p-block element

Higher bond order, the greater bond energy,

shorter bond length

Paramagnetic- unpaired electron -attracted to the

magnetic field
Diamagnetic- paired electron -unaffected by the

magnetic field

Figure 11.21

MO occupancy
and molecular
properties for B2
through Ne2

Sample Problem 11.4

N2+

N2

1/2(8 2) = 3

Using MO Theory to Explain Bond Properties

O2+

O2

s2p

s2p

p2p

p2p

s2p

p2p

p2p

s2p

s2s

s2s

s2s

s2s

1/2(7 2) = 2.5

1/2(8 4) = 2
1/2(8 3) = 2.5
O2 forms O2+, bond order increase,
+
N2 forms N2 , bond order decrease, bond
O2+ has a stronger, shorter bond than
+
N2 has a weaker, longer bond than N2orders
O2

Lewis diagram shows O2 is diamagnetic

No unpaired electrons

MOs shows 2 electron

unpaired
Paramagnetic /parallel

Experiments show O2 is paramagnetic

HOMO & LUMO

Carbon monoxide
In carbon monoxide, the
bonding orbitals reside more on
the oxygen atom, and the antibonding orbitals reside more on
the carbon atom.

Carbon monoxide
CO is a highly reactive
molecule with transition metals.
Reactivity typically arises from
the highest occupied molecular
orbital (HOMO), when
donating electrons.

Carbon monoxide
When acting as an
electron pair acceptor, the
lowest unoccupied molecular
orbital (LUMO), is
significant.

Carbon monoxide
When acting as an
electron pair donor, the
highest occupied molecular
orbital (HOMO), is
significant.

The highest
occupied molecular
orbital of CO is a
molecular orbital
which puts
significant electron
density on the
carbon atom.

The lowest
unoccupied
molecular orbital of
CO is the *
orbitals. The lobes
of the LUMO are
larger on the carbon
atom than on the
oxygen atom.