Important theories and concepts in Chemical bonding

HYBRIDISATION 3) In order to reduce the repulsion, the

Hybridisation is defined as the mixing of the electron pairs stay at maximum distance.
atomic orbitals belonging to the same atom 4) Presence of lone pairs of electron causes
but having slightly different energies so that a distortion in the expected geometry of the
redistribution of energy takes place between molecule.
them resulting in the formation of new orbitals 5) The repulsion between two lone pairs of
of equal energies and identical shapes. The new electrons is different from those between two
orbitals thus formed are known as hybrid bond pairs or between a lone pair and bond
orbitals. pair. The repulsion decreases in the order lone
Some Important Points about Hybridisation pair - lone pair > lone pair - bond pair > bond
(i) Only those orbitals which have approximately pair - bond pair.
equal energies and belong to the same atom 6) As the angle between the electron pairs
or ion can undergo hybridisation. increases, the repulsion decreases.
(ii) Number of hybrid orbitals produced is equal
Comparison of sigma and pi bonds
to the number of atomic orbitals mixed.
(iii) It is not necessary that all the half-filled
orbitals must participate in hybridisation.
Similarly, it is not necessary that only half-fi lled
orbitals should participate in hybridisation.
Even completely filled orbitals with slightly
different energies can also participate.
(iv) Hybridisation never takes place in isolated
atoms but it occurs only at the time of bond
formation.
(v) Type of hybridisation indicates the geometry
of molecules.One can tell the shape of a
molecule by knowing the kind of hybridisation
involved.
(vi) The bigger lobe of the hybrid orbital always
has +ve sign while the smaller lobe on the
opposite side has a -ve sign.

The Valence Shell Electron Pair
Repulsion [VSEPR] Theory
This theory was proposed by Sidgwick and
Powell and later modified by Nyholm and
Gillespie. The important postulates of this
theory are:
1) The shape of the molecule depends on the
number of valence shell electron pairs (VSEPRs)
around the central atom.
2) The valence shell electron pairs repel each
other.
Postulates of Valence Bond Theory
The important postulates of the valence
bond theory are listed below.
• Covalent bonds are formed when
two valence orbitals (half filled)
belonging to two different atoms
overlap on each other. The electron
density in the area between the two
bonding atoms increases as a result
of this overlapping, thereby
increasing the stability of the
resulting molecule.
• The presence of many unpaired
electrons
trons in the valence shell of an
atom enables it to form multiple
bonds with other atoms. The paired
electrons present in the valence shell
do not take participate in the
formation of chemical bonds as per
the valence bond theory.
• Covalent chemical bonds aare
directional and are also parallel to
the region corresponding to the
atomic orbitals that are overlapping.
• Sigma bonds and pi bonds differ in
the pattern that the atomic orbitals
overlap in, i.e. pi bonds are formed
from sidewise overlapping whereas
the overlapping along the axis
containing the nuclei of the two
atoms leads to the formation of
sigma bonds.
The formation of sigma and pi bo
bonds is
illustrated below.
It can be noted that sigma bonds involve the
head-to-head
head overlapping of atomic orbitals
whereas pi bonds involve parallel
overlapping.
Applications and Limitations of VBT
The maximum overlap condition which is
described by the valence bond theory can
explain the formation of covalent bonds in
several molecules. This is one of its most
important applications.
ions. For example, the
difference in the length and strength of the
chemical bonds in H2 and F2 molecules can
be explained by the difference in the
overlapping orbitals in these molecules.
The covalent bond in an HF molecule is
formed from the overlap of the 1s orbital of
the hydrogen atom and a 2p orbital
belonging to the fluorine atom, which is
explained by the valence bond theory.
Limitations of Valence Bond Theory
The shortcomings of the valence bond
theory include:
• Failure to explain the tetravalency
exhibited by carbon
• No insight offered on the energies of
the electrons.
• The theory assumes that electrons
are localized in specific areas.

Molecular Orbital Theory
This theory was developed by F.Hund and R.S
Mulliken. The important postulates of this
theory are:
1) In molecules, the electrons are present in
some special type of orbitals called molecular
orbitals (M.Os).
2) The atomic orbitals (A.Os) of comparable
energy and proper symmetry combine to form
molecular orbitals.
3) Atomic orbitals are monocentric, while
molecular orbitals are polycentric. i.e. electrons
present in atomic orbitals are attracted by only
one nucleus. While the electrons present in
molecular orbitals are attracted by more than
one nuclei.
4) The number of molecular orbitals formed =
the number of atomic orbitals combined. i.e. if
2 atomic orbitals combined, 2 molecular
orbitals are formed. One is called bonding
molecular orbital (BMO) and the other is called
Anti-bonding molecular orbitals (ABMO)
5) The BMO has lower energy and greater
stability than the corresponding ABMO.
6) The molecular orbitals give the electron
probability distribution around a group of
nuclei.
7) The molecular orbitals are filled according to
3 rules – Aufbau principle, Pauli’s exclusion
principle and Hund’s rule.
Formation of molecular orbitals – Linear
Combination of Atomic Orbitals (LCAO)
method
Molecular orbitals are formed by the
combination of atomic orbitals by an
approximate method known as Linear
Combination of Atomic Orbitals (LCAO).
According to this theory, the combinations of
atomic orbitals take place by addition and
subtraction of wave functions of atomic
orbitals. The M.O formed by the addition of
A.Os is called the bonding molecular orbital
(BMO) and by the subtraction of A.Os is called
the anti-bonding molecular orbitals (ABMO).
The electron density in a BMO is located
between the nuclei of the bonded atoms. So the
repulsion between the nuclei is very low.
Therefore a BMO always possess lower energy
than the combining A.Os. While in the case of
an ABMO, most of the electron density is
located away from the space between the
nuclei. There is a nodal plane between the
nuclei and hence the repulsion between the
nuclei is high. So an ABMO possess higher
energy than the combining A.Os. ABMO is
denoted by using an asteric (*) mark.
Conditions for the combination of atomic
orbitals
The combination of A.Os to form M.Os takes
place only if the following conditions are
satisfied:
1. The combining A.Os must have the same or
nearly the same energy.
2. The combining A.Os must have the same
symmetry about the molecular axis.
3. The combining A.Os must overlap to the
maximum extent.
Types of molecular orbitals
M.Os of diatomic molecules are designated as σ
(sigma), π (Pi), δ (delta) etc. the sigma M.Os are
symmetrical about the bond axis, while the pi
M.Os are not symmetrical.
Linear combination of two 1s atomic orbitals
produces two M.Os – a BMO σ1s and an ABMO
σ*1s.
Similarly linear combination of two 2s atomic
orbitals produces two M.Os – σ2s and σ*2s.
If z-axis is taken as the inter nuclear axis, linear
combination of two 2pz orbitals produces two
sigma M.Os σ2pz and σ*2pz. While the
combination of 2px and 2py orbitals produce
M.Os which is not symmetrical about the bond
axis. So two 2px orbitals produces 2 sigma M.Os
– π2px and π*2px and two 2py orbitals produce
2 M.Os – π2py and π*2py.