VALENCE SHELL ELECTRON PAIR REPULSION

(VSEPR) THEORY
Definition: The Valence-Shell-Electrons-Pair-Repulsion Theory
(VSEPR), proposes that the stereochemistry of an atom in a
molecule is determined primarily by the repulsive interactions
among all the electron pairs in its valence shell.
Postulates of VSEPR Theory : The main postulates of this
theory are :
(1) The shape of the molecule is determined by repulsion
between all of the electron pairs present in the valence shell.
 VALENCE SHELL ELECTRON PAIR REPULSION
(VSEPR) THEORY
(2) A lone pair of electrons takes up more space round the
central atom than a bond pair, since the lone pair is attracted
to one nucleus whilist the bond pair is shared by two nuclei. It
follows that repulsion between two lone pairs is greater than
the repulsion between a lone pair and a bond pair, which in
turn is greater than the repulsion between two bond pairs.
The repulsive interactions decrease in the order :
LP-LP > LP-BP > BP-BP
(3) The magnitude of repulsion between bonding pairs of
electrons. depends on the electronegativity difference
between the central atom and the other atoms.
VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR)
THEORY
(4) Double bonds cause more repulsion than single bonds, and
triple bonds cause more repulsion than a double bond.
Repulsive forces decrease sharply with increasing bond angle
between the electron pairs.
Example: BF3 Molecule
In BF3 the central B atom has the configuration : 1s2, 2s2, 2px1.
During the bond formation one 2s-electron is promoted to
vacant 2py orbital. Thus, excited B (configuration: 1s2, 2s1,
2Px1, 2py1, 2pz0) has three unpaired eIectrons for bond
formation with three fluorine atoms. The three bonds
between B and F atoms should be slightly different strengths,
because in one, 2s; while in other, two 2p-orbital electrons
are involved. But in fact, all the three bonds is BF3 are of
equal strength with bond angle of 120°.
 VALENCE BOND THEORY
Introduction: Atoms with unpaired electrons tend to combine
with other atoms which also have unpaired electrons. In this
way the unpaired electrons are paired up, and the atoms
involved all attain a stable electronic arrangement. This in
usually a full shell of electrons (i.e., a noble gas configuration).
Two electrons shared between two atoms constitute a bond.
The number of bonds formed by an atom is usually the same
as the number of unpaired electrons in the ground state, i.e.,
the lowest energy state. However, in some cases the atom
may form more bonds than this. This occurs by excitation of
the atom (i.e., providing it with energy) when electrons which
were paired in the ground state are unpaired and promoted
into suitable empty orbitals. This increases the number of
unpaired electrons, and hence the number of bonds which
can be formed.
 VALENCE BOND THEORY
Postulates of Valance Bond Theory :
(i) A molecule is considered to be made up of atoms.
(ii) Electrons in atoms occupy atomic orbitals.
(iii) Orbitals may or may not be hybridized.
(iv) The atomic orbitals (or the hybrid orbitals) are thought to
remain even when the atom is chemically bonded in a
molecule.
Example: 1. In HF, H has a singly occupied s-orbital that overlaps
with a singly filled 2p orbital on F.
2. In NH3, there are three singly occupied p-orbitals on N which
overlap with S-orbitals from three H atoms.
 VALENCE BOND THEORY
Limitations of valence Bond Theory :
This theory does not explain :
(i) The directional nature of covalent bond.
(ii) The formation of co-ordinate bond in which shared pair of
electrons is contributed by only one of the combining
atoms.
(iii) The paramagnetic nature of O2 molecule.
(iv) The structures of odd electron molecules or ions where no
pairing of electrons takes place.
 MOLECULAR ORBITAL THEORY
Introduction: The molecular orbital theory given by Hund and
Mullikens considers that the valency electrons are associated
with all the concerned nuclii, i.e., with the molecule as a
whoIe. Thus, in other words, the atomic orbitals combine
together to form molecular orbitals in which the identity of
both the atomic orbitals is lost.
Postulates of Molecular Orbital Theory :
(a) During the formation of bond, the two half-filled
atomic·orbitals with opposite spins combine to form two
molecular orbitals (M.O.). One of which is bonding M.O. and
other antibonding M.O. The energy of combining atomic
orbitals, however, should be of similar magnitude.
 MOLECULAR ORBITAL THEORY
(b) A bonding M.O. has lower energy than the atomic orbitals
from which it is formed; while antibonding M.O. has higher
energy than the atomic orbitals from which it is formed.
(c) Two s or p-orbitals can overlap end-to-end to form one sigma
bonding molecular orbital (σ) and one sigma antibonding
molecular orbital (σ *).
(d) Two p-orbitals can overlap sideways to form one pi (π)-
bonding molecular orbital and pi (π *) anti bonding orbital.
(e) The energies of σ -bonding orbitals are lower than those of π
-bonding orbitals.
(f) The orbitals of lower energy are filled first. Each orbital may
hold up two electrons, provided that they have opposite
spins.
 MOLECULAR ORBITAL THEORY
(g) When several orbitals have the same energy, (i.e., they are
degenerate), electrons will be arranged so as to give the
maximum number of unpaired spins (Hund‘s rule).
(h) The order of energy of molecular orbitals has been
determined mainly from spectroscopic data. In simple
homonuclear diatomic molecules, the order is :
 MOLECULAR ORBITAL THEORY
The energies of the σ2p and π2p M.Os. are very close together.
The order of M.Os shown above is correct for oxygen and
heavier elements, but for the lighter elements boron, carbon
and nitrogen the π2py and π2pz are probably lower than σ2px.
For these atoms the order is :
 MOLECULAR ORBITAL THEORY

(g) Molecules or ions having one or more unpaired electrons in

the M.O. are paramagnitic in nature; while those with paired
electron in the M.O., are diamagnitic in nature.
Bond order : Bond order of a molecule is :
 MOLECULAR ORBITAL THEORY

Significance of Bond order

(a) A -ve or zero value of bond order indicates that the
molecule is unstable and does not exist. A +ve value of
bond order indicates that the molecule exists and is stable.
Greater the value of bond order, greater is stablity of the
molecule.
(b) A bond order of + 1, +2, +3 indicates that the molecule is
formed by joining of two atoms by single, double or triple
bond respectively.