General and Inorganic Chemistry PHCM101

Lecture 9
Covalent bonding: Molecular orbital theory

Dr. Nesrine El Gohary

 COMPETANCIES

1-1-1 Identify the different types of molecular orbitals.

1-1-2 Articulate knowledge in designing molecular

orbital diagrams for diatomic molecules.

2-2-1 Determine the bond order for diatomic molecules.

2-2-2 Determine the magnetic properties of diatomic

molecules.
2
 Molecular orbital theory

The theory describes covalent bonds in terms of

molecular orbitals.
Molecular orbitals result from interaction of the atomic
orbitals of the bonding atoms.
Molecular orbitals are orbitals that belong to the whole
molecule rather than to a single atom.
The electrons are found in the molecular orbitals.
 Molecular orbital theory
Atomic orbital Molecular orbital
Describes the volume of space
around the nucleus of an atom Describes the volume of space around
where an electron is likely to be a molecule where an electron is likely
found to be found

Atomic orbitals are associated with Molecular orbitals are associated with
only one atom. the whole molecule

Atomic orbitals have specific sizes, Molecular orbitals have specific sizes,
shapes and energies shapes and energies

An Atomic orbital carries a maximum A Molecular orbital carries a maximum

of two electrons with opposite spin of two electrons with opposite spin
 Molecular orbital theory
Molecular orbital theory helped in the explanation of some
properties of molecules that could not be explained by Lewis
structure and the Valence bond theory.
Example: Oxygen molecule O2

This is Lewis structure for O2

 According to this structure all the electrons are paired, so O2 is a
diamagnetic molecule.
 The reality is O2 is a paramagnetic molecule.
 This means that O2 should have unpaired electrons to be paramagnetic.
 The presence of unpaired electrons and its paramagnetism could be
explained by the molecular orbital theory.

https://www.youtube.com/watch?v=Lt4P6ctf06Q
 Molecular orbital theory
How are molecular orbitals formed?
Atomic orbitals of the bonding atoms combine together to form molecular orbitals.
In this theory, the wave nature of electrons explains the different types of molecular
orbitals obtained.
Remember! Electrons in orbitals have wave properties, they behave like waves.
It is known that waves can interact either constructively or destructively.

 If waves (atomic orbitals) interact constructively, the

resulting molecular orbital is lower in energy and
more stable than the two atomic orbitals. It is thus
called a bonding molecular orbital.
 If waves (atomic orbitals) interact destructively, the
resulting molecular orbital is higher in energy and is
less stable than the two atomic orbitals. It is thus
called an antibonding molecular orbital.

constructive interference; destructive interference

 Molecular orbital theory [H2 molecule]
 Each hydrogen atom has its 1s atomic orbital. As the hydrogen atoms approach each
other the two 1s atomic orbitals interact to form two molecular orbitals:
Bonding molecular orbital which is more Antibonding molecular orbital which is less
stable and of lower energy than the stable and of higher energy than the isolated
isolated 1s atomic orbitals. 1s atomic orbitals.
In the bonding molecular orbital, the In the antibonding molecular orbital, the
electron density in this molecular orbital is electron density in this molecular orbital is
concentrated in the region between the also concentrated along the internuclear axis
two nuclei along the internuclear axis, so it but it is on either side of the nuclei. Between
is called a sigma () bonding molecular the two nuclei we have a node
orbital. In this case it is called  1s. ( region where there is no probability of
finding electrons). This antibonding molecular
orbital is called * 1s.
 Molecular orbitals: s orbitals [H2 molecule]
 The bonding  1s molecular orbital is lower in energy than the antibonding * 1s,
consequently it is filled with electrons before the antibonding * 1s.
 Any molecular orbital can be filled with a maximum of 2 electrons and they have to
have opposite spin.
 Thus, the two electrons of the hydrogen molecule are present in the bonding  1s.
 This favors the bonding in hydrogen molecule since this molecular orbital is more
stable and of lower energy than the isolated 1s atomic orbital of each hydrogen atom.
 So with the presence of the two electrons in this more stable molecular orbital, it
favors bonding and the formation of the hydrogen molecule.
 Imagine if the two electrons were present
in the antibonding * 1s which is less
stable and of higher energy than the
isolated 1s atomic orbitals . This
condition will not favor bonding at all
(ANTIBONDING) and it will be more
stable for the hydrogen to remain as
separated atoms and not combine into a
molecule. Molecular orbital energy level diagram of H2 molecule

We conclude that presence of electrons in bonding molecular orbitals favors bonding,

while the presence of electrons in antibonding molecular orbitals is against bonding.
 Molecular orbitals: p orbitals
What are the molecular orbitals formed from interaction of p atomic orbitals??
Remember that there are three p atomic orbitals, that are oriented along, x, y and z axes
 Interaction of two p
orbitals, one from each
atom results in the
formation of two
molecular orbitals Bonding and antibonding molecular orbitals.

end-to-end overlap
Sigma () molecular orbitals

Side by side overlap

Pi (π) molecular orbitals
Electron density is
concentrated above and
below a line joining the
two nuclei.

Note that: The two bonding π molecular Note that: The two antibonding π* molecular
orbitals are equal in energy (degenerate). orbitals are equal in energy (degenerate).
 Molecular orbital energy level diagram
Rules Governing Molecular Electron
Configuration and Stability:
1. The number of molecular orbitals formed is
always equal to the number of atomic orbitals
combined.
2. The more stable the bonding molecular orbital,
the less stable the corresponding antibonding
molecular orbital.
3. The filling of molecular orbitals proceeds from
low to high energies. In a stable molecule, the
number of electrons in bonding molecular orbitals
is always greater than that in antibonding molecular
orbitals.
4. Like an atomic orbital, each molecular orbital can
accommodate up to two electrons with opposite
spins in accordance with the Pauli exclusion
principle.
5. When electrons are added to molecular orbitals
of the same energy, we follow Hund’s rule; that is,
electrons enter singly with parallel spin before we
start pairing.
6. The number of electrons in the molecular orbitals
is equal to the sum of all the electrons on the
bonding atoms.
 Molecular orbital energy level diagram
Rules Governing Molecular Electron
Configuration and Stability:
1. The number of molecular orbitals formed is
always equal to the number of atomic orbitals
combined.
2. The more stable the bonding molecular orbital,
the less stable the corresponding antibonding
molecular orbital.
3. The filling of molecular orbitals proceeds from
low to high energies. In a stable molecule, the
number of electrons in bonding molecular orbitals
is always greater than that in antibonding molecular
orbitals.
4. Like an atomic orbital, each molecular orbital can
accommodate up to two electrons with opposite
spins in accordance with the Pauli exclusion
principle.
5. When electrons are added to molecular orbitals
of the same energy, we follow Hund’s rule; that is,
electrons enter singly with parallel spin before we
start pairing.
6. The number of electrons in the molecular orbitals
is equal to the sum of all the electrons on the
bonding atoms.
 Molecular orbital energy level diagram
Example Draw the molecular orbital energy level diagram for the oxygen molecule.
 Calculate the total electrons
present in the molecule.
 Oxygen atom has 8 electrons, so we
σ* 2px
have a total of 16 electrons.
 Draw the molecular orbitals п* 2pz
represented as boxes or lines , п* 2py
starting from the bottom which п 2pz п 2py
represents the molecular orbital of
lowest energy. σ 2px
 Arrange the rest of the molecular
orbitals moving upwards according to σ* 2s
increasing energy.
 If two orbitals have the same energy σ 2s
such as π 2pz and π 2py draw them
at the same level. σ* 1s
 Start putting electrons in the bottom
(orbital of lowest energy) and σ 1s
continue filling moving upwards.
 If all electrons are paired so diamagnetic O2 molecule has unpaired electrons so it is
molecule. PARAMAGNETIC.
 If there is unpaired electrons so paramagnetic
 Molecular orbital energy level diagram
Example Draw the molecular orbital energy level diagram for the oxygen molecule.
 Calculate the total electrons
present in the molecule.
 Oxygen atom has 8 electrons, so we
σ* 2px
have a total of 16 electrons.
 Draw the molecular orbitals п* 2pz
represented as boxes or lines , п* 2py
starting from the bottom which п 2pz п 2py
represents the molecular orbital of
lowest energy. σ 2px
 Arrange the rest of the molecular
orbitals moving upwards according to σ* 2s
increasing energy.
 If two orbitals have the same energy σ 2s
such as π 2pz and π 2py draw them
at the same level. σ* 1s
 Start putting electrons in the bottom
(orbital of lowest energy) and σ 1s
continue filling moving upwards.
 If all electrons are paired so diamagnetic O2 molecule has unpaired electrons so it is
molecule. PARAMAGNETIC.
 If there is unpaired electrons so paramagnetic
 Molecular orbital energy level diagram
Example Draw the molecular orbital energy level diagram for the oxygen molecule.
 Calculate the total electrons
present in the molecule.
 Oxygen atom has 8 electrons, so we
σ* 2px
have a total of 16 electrons.
 Draw the molecular orbitals п* 2pz
represented as boxes or lines , п* 2py
starting from the bottom which п 2pz п 2py
represents the molecular orbital of
lowest energy. σ 2px
 Arrange the rest of the molecular
orbitals moving upwards according to σ* 2s
increasing energy.
 If two orbitals have the same energy σ 2s
such as π 2pz and π 2py draw them
at the same level. σ* 1s
 Start putting electrons in the bottom
(orbital of lowest energy) and σ 1s
continue filling moving upwards.
 If all electrons are paired so diamagnetic O2 molecule has unpaired electrons so it is
molecule. PARAMAGNETIC.
 If there is unpaired electrons so paramagnetic
 Bond order in molecular orbital theory
It is the difference between the number of bonding electrons and the number of anti bonding
electrons divided by two.

 Bond order indicates the approximate strength of a bond, the bigger the bond
order, the stronger is the bond.
If Bond order > zero Bond order =zero
the molecule is the molecule is unstable and
relatively stable and cannot exist.
exists.

 Bond order containing fractions are possible.

 Molecular orbital energy level diagram
Example Draw the molecular orbital energy level diagram for the oxygen molecule.
 Calculate the total electrons
present in the molecule.
 Oxygen atom has 8 electrons, so we
σ* 2px
have a total of 16 electrons.
 Draw the molecular orbitals п* 2pz
represented as boxes or lines , п* 2py
starting from the bottom which п 2pz п 2py
represents the molecular orbital of
lowest energy. σ 2px
 Arrange the rest of the molecular
orbitals moving upwards according to σ* 2s
increasing energy.
 If two orbitals have the same energy σ 2s
such as π 2pz and π 2py draw them
at the same level. σ* 1s
 Start putting electrons in the bottom
(orbital of lowest energy) and σ 1s
continue filling moving upwards.
 If all electrons are paired so diamagnetic O2 molecule has unpaired electrons so it is
molecule. PARAMAGNETIC.
 If there is unpaired electrons so paramagnetic
 Bond order
Compare the bond order of H2, H2+ and H2-
H2 H2+ H2-

 

1s 1s 1s 1s
AO of H
AO of H AO of
AO of H
 H-

MO of H2-
bond order
= 1/2(1-0)
= 1/2 bond
order =
1 H2+ does exist 1/2(2-1)
B.O = (2 − 0) = 1 = 1/2
2
H2- does exist
 Bond order
Compare the bond order of He2, He2+

He2+ He2

1 1
B.O = (2 − 1) = 1/2 B.O = (2 − 2) = 0
2 2
He2+ Exists He2 Cannot Exist
 Homonuclear Diatomic Molecules of
Second-Period Elements

They are diatomic molecules containing atoms of the

same elements.
E.g.Li2
Electronic configuration of Li
atoms:
1s2 2s1
Electron configuration of
molecular orbitals in Li2:
(1s)2 (*1s)2 (2s)2.
Bond Order = 1
Molecule is diamaganetic
 Homonuclear Diatomic Molecules of
Second-Period p-block elements
2px, 2py and 2pz atomic orbitals

2px and 2px M.O 2py ,2pz , *2py and * 2pz

(overlap of 2px orbitals) (overlap of 2py & 2pz orbitals)

 Normally, overlap of the two p orbitals is greater in a 

molecular orbital than in a  molecular orbital, so we
would expect the former to be lower in energy.

 However, the order 2p and 2p molecular orbitals is

flipped for light molecules such as B2, C2, N2.
 Homonuclear Diatomic Molecules of
Second-Period p-block elements

Light molecules with  half

filled p-orbitals; e.g B2, C2,
N2

Flipped
Order
General molecular orbital energy level
diagram for the second-period homonuclear
diatomic molecules Li2, Be2, B2, C2, and N2.
 Homonuclear Diatomic Molecules of
Second-Period p-block elements

Molecules with > half

filled p-orbitals; O2
and beyond

Order of molecular
orbitals is as expected;
 2py  2pz
i.e not flipped

 2px
 Practice Exercise
Use the molecular orbital model to predict the bond order
and magnetism of each of the following molecules:

HOMO = Highest
occupied molecular
orbital.

LUMO = Lowest
unoccupied
molecular orbital.
 Practice Exercise
For each of these species; O2, O2+ and O2- give:
The molecular electronic configuration & the bond order
Determine which has the strongest bond & predict the magnetism of
each.
No. of valence O2 = 12 O2+ = 11 O2- = 13
electrons: (6+6) (6+6-1) (6+6+1)
The simplified MO diagrams:

O2+ = Strongest
Bond

Bond Order ½ (8-4) = 2 ½ (8-3) = 2.5 ½(8-5) = 1.5

Magnetism Paramagnetic Paramagnetic Paramagnetic
 Heteronuclear Diatomic Molecules of Second-
Period Elements

E.g. CN-1 NO+1

No. of 10 10
valence (4+5+1) (5+6-1)
electrons=
Bond Order ½ (8-2) = 3 ½ (8-2) = 3
Magnetism Diamagnetic Diamagnetic

Molecular Orbital Diagram of CN-1 & NO+1

 References
• Chemistry, 6th ed., Zumdahl, Chapter 9.
• Lecture 9 by Dr. Noha Osman, GUC, WS 2016.
https://socratic.org/questions/5a64204ab72cff7b83554c78