MOLECULAR ORBITAL THEORY (MOT)

This theory was given by Hund and Mulliken in 1932.

FEATURES OF MOLECULAR ORBITAL THEORY –

1. The atomic orbitals overlap to form new orbitals called molecular orbitals (M.O.). As a
result the atomic orbitals lose their individual identity.
2. A molecular orbital gives the electron probability distribution around a group of nuclei
just as an atomic orbital gives the electron probability distribution around the single
nucleus.
3. Only those atomic orbitals can combine to form molecular orbitals which have
comparable energies and proper orientation. For example 1s can combine with 1s not with
2s.
4. The number of molecular orbitals formed is equal to the number of combining atomic
orbitals.
5. When two atomic orbitals combine, they form two new orbitals called ‘bonding molecular
orbital’ and ‘antibonding molecular orbital’.
6. The bonding molecular orbital has lower energy and hence greater stability than the
corresponding antibonding molecular orbital.
7. The bonding molecular orbitals are represented by σ, π, δ etc. Whereas the corresponding
antibonding molecular orbitals are represented by σ*, π*, δ* etc.
8. The shapes of the molecular orbitals formed depend upon the type of the combining
atomic orbitals.
9. The filing of molecular orbitals takes place according to the same rules as those of the
atomic orbitals. These are as follows :-
(a) Aufbau principle – The molecular orbitals are filled in order of their increasing energies.
(b) Pauli exclusion principle – A molecular orbital can have maximum two electrons and
these must have opposite spin.
(c) Hund’s rule of maximum multiplicity – Pairing of the electrons in the degenerate
molecular orbitals does not take place until each of them has got one electron each.
 ATOMIC ORBITALS
1. Their electron cloud extends around the
nucleus of a single atom that is, atomic
orbital is monocentric.
2. They are less stable.
3. They have simple shapes.
4. They are represented by s, p, d, f, etc.
MOLECULAR ORBITALS
Their electron cloud extends around all the
nuclei of bonded atoms in the molecule that
is, a molecular orbital is polycentric.
They are more stable.
They have complex shapes.
They ae represented by σ, π, δ etc.

Main Characteristics of Bonding Molecular Orbitals –

1. The probability of finding the electron in the intermolecular region of the bonding
molecular orbital is greater than that of the combining atomic orbitals.
2. The electrons present in the bonding molecular orbital result in an attraction between the
two atoms.
3. As a result of attraction, the bonding molecular orbital has lower energy and hence
greater stability than that of the combining atomic orbitals.
4. They are formed by the additive effect of the atomic orbitals that is, crests fall over the
crests and troughs over the troughs so that the amplitude of the new wave is given by
φ = ψA + ψB .
5. They are represented by σ, π, δ.

Main Characteristics of the Antibonding Molecular Orbitals –

1. The probability of finding the electron in the intermolecular region decreases in the
antibonding molecular orbital.
2. The electrons present in the antibonding molecular orbital (if any) result in the repulsion
between the two atoms.
3. Because of the repulsive force, the antibonding molecular orbital has higher energy lower
stability, that is, it does not favor the formation of bond (that is why the name
‘antibonding’).
4. They are formed by the subtractive effect of the atomic orbitals, that is, crests fall over
the troughs so that the amplitude of the new wave is given by φ’ = ψA – ψB .
5. They are represented by σ*, π*, δ*.
Conditions for the Combination of Atomic Orbitals to form Molecular Orbitals –
1. The combining atomic orbitals should have comparable energies. For example, for
homonuclear diatomic molecules of the type A2, 1s atomic orbital of one atom can combine
with 1s atomic orbital of another atom.
2. The combining atomic orbitals must have proper orientation (same symmetry) so that
they are able to overlap to a considerable extent. For example, taking z-axis as the
internuclear axis, 2pz orbital of one atom can combine with 2pz of another atom but 2pz
orbital of one atom cannot combine with 2px or 2py of another atom.
3. The extent of overlapping should be large. Greater the overlap, the greater will be the
electron density between the nuclei.
Difference between σ - and π - molecular orbital-

σ - MOLECULAR ORBITAL π- MOLECULAR ORBITAL

1. It is formed by the overlap of atomic
orbitals along the internuclear axis.
2. Due to head on overlap, the overlapping
is maximum.
3. It consists of one electron cloud.
4. Its electron cloud is symmetrical about
the internuclear axis.
It is formed by the sideway overlapping of
the atomic orbitals.
Due to sideway overlap, overlapping is less.
It consists of two electron clouds, one lying
above the other lying below a plane passing
through the nuclei.
Its electron cloud is not symmetrical about
the internuclear axis.