Chemical bonding and Molecular structure Module1 (5 of 12)-MKM

[Molecular Orbitals of diatomic molecules and plots of the multicentre orbitals. Equations for atomic and
molecular orbitals. Energy level diagram of diatomics. Pi molecular orbitals of butadiene and benzene and
aromaticity]
“Scientists are constantly discovering new compounds, orderly arranging the facts about them,
trying to explain with existing knowledge, organising to modify the earlier views or evolve
theories for explaining the newly observed facts”.
The attractive force which holds various constituents (atoms, ions, etc.) together in different
chemical species is called a chemical bond.

Since the formation of chemical compounds takes place as a result of combination of atom of
various elements in different ways, it raises many questions.

Why do atoms combine?

Why are only certain combinations possible?

Why do molecules possess definite shapes? Etc-

To answer such questions different theories and concept have been put forward from time to
time.
• Kossel-Lewis Theory
• VSEPR Theory
• Valence Bond Theory (VBT)
• Molecular Orbital Theory(MOT)
Kossel- Lewis (1916) approach to chemical bonding.
• Octet rule
• Covalent bond
• Formal charge
Limitation of octet rule: -
• Incomplete octet of the central atom
Cl-Li-Cl , H:Be:H , Cl:B:Cl

• Odd electron molecule

• The expanded octet

PF5, SF6, H2SO4

Ionic or electrovalent bond: -

• Lattice enthalpy

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Bond parameter: -
• Bond length
• Bond angle
• Bond enthalpy
• Bond order
• Resonance structure
• Polarity of bond, dipole moment
VSEPR theory
• Valence bond theory
• Orbital overlap concept
Directional properties of bonds: -
• Overlapping of atomic orbitals.
Types of overlapping and nature of covalent bond: -
1. Sigma bond (σ)
• s-s overlapping
• s-p overlapping
• p-p overlapping
2. Pi bond (π)
Molecular orbital theory:
Molecular orbital theory (MOT) was developed by R.S Mulliken in 1932.
The salient features of this theory are:

• The electrons in a molecule are present in the various molecular orbitals as the electrons
of atoms are present in the various atomic orbitals.
• The atomic orbitals of comparable energies and proper symmetry combine to form
molecular orbitals.
• While an electron in an atomic orbitals is influenced by two or more nuclei depending
upon the number of atoms in the molecule. Thus an atomic orbital is mono centric while
a molecular orbital is polycentric.
• The number of molecular orbital formed is equal to the number of combining atomic
orbitals. When two atomic orbitals combine, two molecular orbitals are formed. One is
known as Bonding Molecular Orbital, while other is called Antibonding Molecular
Orbital.
• The Bonding Molecular Orbital has lower energy and hence greater stability than the
corresponding Antibonding Molecular Orbital. .
• Just as the electron probability distribution around a nucleus in an atom is given by an
atomic orbital, the electron probability distribution around a group of nuclei in a molecule
is given by molecular orbital.
• The molecular orbitals like atomic orbitals are filled in accordance with the Aufbau
principle obeying the Pauli’s exclusion principle and Hund’s rule.

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 Differentiate between atomic and molecular orbital: -

Atomic orbitals Molecular orbitals

1. Their electron cloud extends Their electron cloud extends around all the
around the nucleus of a single
nuclei of bounded atoms in the molecule, i.e., a
atom, i.e., atomic orbital ismolecular orbital is polycentric. They are
monocentric. obtained by combining atomic orbitals of
comparable energy.
2. They are less stable They are more stable.
3. They have simple shapes. They have complex shape.
4. They are represented by s, p, They are represented by σ, σ*, π, π* etc. They
d, f, etc may be bonding or antibonding.
Difference between bonding and antibonding orbitals:

Bonding Molecular orbitals Anti-Bonding Molecular orbitals

1. They are formed by the additive They are formed by the subtractive effect of
effect of atomic orbitals. atomic orbitals.
Φb=ψ1+ ψ2 Φa=ψ1- ψ2

2. The electrons present in the The electrons present in the antibonding

bonding orbitals result in an orbitals (if any) result in an repulsion
attraction between the two atoms between the two atoms
3. The electron density increases in The electron density decreases in the region
the region between the nuclei of between the nuclei of atoms and it increases
bonded atoms. in the region away from the internuclear
region. This is responsible for the
instability of the bond.
4. They are formed when the lobes They are formed when the lobes of the
of the combining orbitals have the combining orbitals have the opposite sign.
same sign.
5. These orbitals are represented by These orbitals are represented by σ* and
σ and π. π*.
Difference between σ and π molecular orbitals:

σ - molecular orbitals π - molecular orbitals

1. It is formed by the overlap of It is formed by the sideway overlap of
atomic orbitals along the atomic orbitals.
internuclear axis.
2. Due to head on overlap, the Due to side way overlap, the overlapping is
overlapping is maximum. minimum.
3. It consists of one electron cloud.It consists of two electron clouds, one lying
above and the other lying below a plane
passing through the nuclei.
4. Its electron cloud is symmetrical Its electron cloud is unsymmetrical about

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 about the internuclear axis. the internuclear axis.

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