General Chemistry

Molecular Orbital Theory

Dr. S. K. Tan
Topics to be Covered in this Lecture

Concepts of Molecular Orbitals

Correlation Energy Diagram
Prediction of Reactivity of Molecules
 Bonding Theories

We have already been introduced to one of the main bonding theories -

The Valence Bond Theory (VB)

* Pairs of electrons repel each other, therefore orient themselves in a

way that minimizes these repulsions.

* Covalent bonds are formed by overlapping of atomic orbitals.

* The electrons that form a bond between two atoms are localized
between the atoms.
 Bonding Theories

There is however another contender to the throne for bonding theory

- and this is called The Molecular Orbital Theory (MO)

* Atomic orbitals are combined into new orbitals, called molecular

orbitals (MOs).
* MOs need not be localized between two atoms.
* The number of MOs formed is equal to the sum of atomic orbitals in
all the atoms comprising the molecule.
* When atomic orbitals combine to form bonding MOs, the resulting
MO is lower in energy.
* Antibonding MOs are less stable than the AOs.
 Molecular Orbital Theory

Here, if we have two nuclei that are close to each other, when we
include the electrons into consideration, the electrons will move into
molecular orbitals.
This is analogous to the electrons occupying atomic orbitals in the case
of the atoms.
For the atomic orbitals, there are s, p, d, f,... orbitals.
In the case of molecular orbitals, there are σ, π, δ, ...; where the
orbitals are determined by quantum numbers.
 Molecular Orbital Theory (2)

To obtain the molecular orbital, the Schrödinger equation must be

solved, and here lies the problem.
The equation cannot be solved exactly and therefore certain
approximations must be made.
One of them involves the Born-Oppenheimer Approximation,
Approximation
which assumes that nuclei moves much more slowly than electrons
(also known as the Clamped-Nuclei Approximation).
This separates the situation into two problems - an electronic and a
nuclear motion problem.
 Molecular Orbital Theory (3)

The electronic problem solves for the wave function of the electrons
while the nuclear motion solves for the motion of the nuclei.
Another approximation that is made is that the molecular orbitals may
be approximated by taking the Linear Combination of Atomic
Orbitals (LCAO).
The rationale is that most of the time the electrons are close to nuclei
and will most probably be ‘controlled’ by one of the two nuclei.
Hence, the molecular orbital will most probably be a combination of
the atomic orbitals.
 Molecular Orbital Theory (4)

So, if we have two atomic orbitals, Ψ and Ψ , we can combine them

A B
to obtain two molecular orbitals.

Ψ = Ψ + Ψ ; and Ψ = Ψ - Ψ , where Ψ is a bonding molecular

b A B a A B b
orbital and is an Ψ anti-bonding molecular orbital.
a

The electron distribution is then calculated by taking the square of

that function.
2 2 2
Hence, Ψ =Ψ + 2Ψ Ψ + Ψ , while the corresponding electron
b A A B B
2 2
distribution for the anti-bonding molecular orbital is Ψ = Ψ - 2Ψ
a A A
2
Ψ + Ψ .
B B
 Molecular Orbital Theory (5)

The two orbitals Ψ and Ψ differ from

b a
each other. ΨA and ΨB
In the bonding molecular orbital, the
wave functions for the component atoms
reinforce each other in the region
between the nuclei.
Ψb2 is the electron distribution in the Ψb = ΨA + ΨB
hydrogen molecule, also known as the
probability function.

Ψb 2
 Molecular Orbital Theory (6)

Note that in the bonding situation, the

ΨA and ΨB
electrons are in between two nuclei.
In the anti-bonding orbital, the wave
functions cancel, forming a node between
the nuclei.
Ψa = ΨA - ΨB
In this situation, the electrons are not in
between the two nuclei.

Ψa 2
 Correlation Energy Diagrams (1)

The diagram in the opposite panel shows

Energy
the energy correlation diagram of the
1s
σ*
molecular orbitals and the atomic
orbitals.
1s ↑ ↑ 1s
A B
The atomic orbitals are both on the
right and the left of the diagram. 1s
σ

The energy levels in the centre are those
of the corresponding bonding (1s ) and
σ
anti-bonding (1s ) molecular orbitals.
σ*
Notice that the bonding
orbitals have a lower energy
level compared to the
atomic orbitals - one of the
reasons for bonding is to
achieve lower energy levels
 Correlation Energy Diagrams (2)

In H , each atom provides 1 electron to Energy

2
1s
the molecular orbital. σ*

This results in the two electrons pairing

up in the 1s bonding orbital (Hund’s 1s ↑ ↑ 1s
A B
σ
rule, Pauli Exclusion principle).
↑↓ 1s
σ
This results in a stable bonding between
H-H atoms, and this is exemplified
experimentally.
 Correlation Energy Diagrams (3)

+
How about H2 ?
Energy
In this case, the dihydrogen cation has
1sσ*
only one electron and therefore has only
one electron in the bonding molecular
↑
orbital of 1sσ. 1sA 1sB
∆E
Although only one electron exists, this ↑ 1sσ
provides an energy stabilisation of ∆E
compared to the atomic orbitals.
In the case of H2, it has a total energy
stabilisation of 2∆E.
 Correlation Energy Diagrams (4)

-
How about H2 ?
Energy
For the dihydrogen anion, there are three
electrons to distribute to the molecular
↑ 1sσ*
∆E’
orbitals, and the third electron populates
the 1sσ* orbital.
↑↓ ↑
1sA 1sB
∆E
This is an anti-bonding orbital and will ↑↓ 1sσ
result in the electron gaining
destabilisation energy of ∆E’.
Assuming ∆E = ∆E’, the bond energy for
-
H2 is then 2∆E – ∆E’ = ∆E (similar to
+
that of H2 ).
 Energy Correlation Diagrams (5)

How about He2?

Energy
In He2, we have a total of four electrons to ↑↓ 1sσ*
populate into the molecular orbitals.
The third and fourth electron goes into the
↑↓ ↑↓
1sA 1sB
1sσ* orbital, and since it is an anti-bonding
orbital, the net stabilisation obtained from ↑↓ 1sσ
the bonding orbital is lost as it is
cancelled by the anti-bonding orbitals.
As a result, He2 is predicted to be
unstable.
 Considerations for Molecular Orbital formation

In order to determine which atomic orbitals interact to form molecular

orbitals, we have to consider the factors that impact on the interaction
between atomic orbitals.

They are:

* The energy difference between the interacting orbitals must be small,

* The overlap between the orbitals must be large.

This means that the 2s orbitals will only interact with other 2s orbitals
and not with the 1s or 2p orbitals.
 Molecules with Electrons in the 2s Orbitals (1)

When we include the 2s atomic orbitals

2sσ*
into the formation of molecular orbitals, we
combine them in the same fashion as we
2sA 2sB
did for the 1s atomic orbitals.
The 2s results from 2s + 2s , while 2s 2sσ
σ A B σ*
results from 2s - 2s . 1sσ*
A B
The molecular orbital diagram appears as
in the panel. 1sA 1sB

1sσ
 Molecules with Electrons in the 2s Orbitals (2)

In the case of Li , there are a total of 3

2
electrons for an atomic configuration of
2 1
2sσ*
1s 2s .
These will combine as shown in the panel ↑ ↑
2sA 2sB
- only a single bond results.
Note that the 1s orbitals do not form ↑↓ 2sσ
bonds (as we expect) from the MO theory ↑↓ 1sσ*
as it is cancelled out by the anti-bonding
orbitals. ↑↓ ↑↓ 1s
1sA
B
The electronic configuration of Li is then
2
2 2 2
(1s ) (1s ) (2s ) .
σ σ* σ
↑↓ 1sσ
 Molecules with Electrons in the 2s Orbitals (3)

For Be , there are four electrons for each

2
Be atom thus giving an electronic ↑↓ 2sσ*
2 2
configuration of 1s 2s .
The MO for Be is as shown in the
↑↓ ↑↓ 2s
2
2sA
B
opposite panel.
↑↓ 2sσ
The electrons populating the 2s molecular
orbitals gives use an electronic ↑↓ 1sσ*
2 2 2 2
configuration of (1s ) (1s ) (2s ) (2s ) .
σ σ* σ σ*
1sA
↑↓ ↑↓ 1s
Be is not expected to be stable, and thus
2 B
will not exist.
↑↓ 1sσ
 Molecules with Electrons in the 2p Orbitals (1)
There are three 2p orbitals, each of these orbitals are in the x, y and z
directions of the Cartesian coordinates.
Elements such as B, C, N, O, F, ... have electronic configurations that
utilise the p-orbitals.
Here, if the p-orbital is lying along the internuclear axis, then it can
undergo symmetric combination to give a bonding orbital.
Alternatively, it can undergo anti-symmetric combination to give an
anti-bonding orbital.

Symmetric

Anti-symmetric
 Molecules with Electrons in the 2p Orbitals (2)

The σ molecular orbital has bulk of the electron density between the
2p
nuclei, thus contributes towards the bonding.
The σ* molecular orbital has the electron density mainly outwith the
2p
internuclear area, thus does not contribute towards the bonding.
 Molecules with Electrons in the 2p Orbitals (3)

The remaining p-orbitals (px and py) do not overlap, but they lie
perpendicular to the internuclear axis.
They can undergo either plus or minus combination to give 2pπ orbitals
and are called doubly degenerate as the orbitals formed are equal in
energy and size but differ in direction.
 MO Theory in Bonding of O2 (1)
O has eight electrons; O has 16 electrons.
2
It has the following electronic configuration
2 2 2 2 2 4 2
(1s ) (1s ) (2s ) (2s ) (2p ) (2p ) (2p )
σ σ* σ σ* σ π π*
There are 4 nett bonding electrons.

2p
σ*
↑ ↑ 2p
π*
↑↓ ↑ ↑ ↑↓ ↑ ↑
2p 2p
↑↓ ↑↓ 2p
π
↑↓ 2p
σ
↑↓ 2s
σ*
2s ↑↓ ↑↓ 2s
↑↓ 2s
σ
↑↓ 1s
σ*
1s ↑↓ ↑↓ 1s
↑↓ 1s
σ
 MO Theory in Bonding of O2 (2)
4 (2p ) + 2 (2p ) - 2 (2p )
π σ π*
Hence there are 4/2 = 2 bonds present (O=O). There are also 2 anti-bonding
unpaired electrons.
This explains the paramagnetic behavior of dioxygen.
2p
σ*
↑ ↑ 2p
π*
↑↓ ↑ ↑ ↑↓ ↑ ↑
2p 2p
↑↓ ↑↓ 2p
π
↑↓ 2p
σ
↑↓ 2s
σ*
2s ↑↓ ↑↓ 2s
↑↓ 2s
σ
↑↓ 1s
σ*
1s ↑↓ ↑↓ 1s
↑↓ 1s
σ
 MO Theory in Bonding of F2 (1)
F has 9 electrons while F has 18 electrons.
2
It has the following electronic configuration
2 2 2 2 2 4 4
(1s ) (1s ) (2s ) (2s ) (2p ) (2p ) (2p )
σ σ* σ σ* σ π π*
There are 2 nett bonding electrons and a single bond (F-F).
There are four anti-bonding electrons, thus F is highly reactive species.
2
2p
σ*
↑↓ ↑↓ 2p
π*

↑↓ ↑↓ ↑ ↑↓ ↑↓ ↑
2p ↑↓ 2p
↑↓ 2p
↑↓ 2p
σ
π

↑↓ 2s
σ*
2s ↑↓ ↑↓ 2s
↑↓ 2s
σ
↑↓ 1s
σ*
1s ↑↓ ↑↓ 1s
↑↓ 1s
σ
 MO Theory in Bonding of N2
N has a different energy level compared to those of O and F .
2 2 2
N has the following electronic structure
2
2 2 2 2 4 2
(1s ) (1s ) (2s ) (2s ) (2p ) (2p )
σ σ* σ σ* π σ
There are 6 nett bonding electrons, giving 3 bonds.
N is therefore very stable and unreactive as there are no anti-bonding
2
electrons. 2p
σ*
2pπ*

↑ ↑ ↑ ↑ ↑ ↑
2p 2p 2p
↑↓ ↑↓ π

2p
↑↓
σ
↑↓ 2s
σ*

2s ↑↓ ↑↓ 2s
↑↓ 2sσ
↑↓ 1s
σ*

1s ↑↓ ↑↓ 1s
↑↓ 1s
σ
 MO Theory in Bonding of Ne2
Ne has 10 electrons and Ne2 has 20 electrons.
It has the following electronic structure
2 2 2 2 2 4 4 2
(1s ) (1s ) (2s ) (2s ) (2p ) (2p ) (2p ) (2p )
σ σ* σ σ* σ π π* σ*
This means that there are no nett bonding electrons and Ne2 will not exist.

↑↓ 2pσ*
↑↓ ↑↓ 2pπ*
↑↓ ↑↓ ↑↓ ↑↓ ↑↓ ↑↓
2p ↑↓ ↑↓ 2pπ 2p
↑↓ 2pσ
↑↓ 2sσ*
2s ↑↓ ↑↓ 2s
↑↓ 2sσ
↑↓ 1sσ*
1s ↑↓ ↑↓ 1s
↑↓ 1sσ
Topics Covered in this Lecture

Concepts of Molecular Orbitals

Correlation Energy Diagram
Prediction of Reactivity of Molecules