Valence Shell Electron Pair Repulsion Theory

(VSEPR Theory)
BSc 1st Semester (Honours)

Presented by
Dr. Madhulika Dutta
Department of Chemistry
What is VSEPR Theory?
The Valence Shell Electron Pair Repulsion Theory is based on the fact
that there is a repulsion between the pairs of valence electrons in all
atoms, and the atoms will always tend to arrange themselves in such
a manner in which the repulsion among the electron pairs is
minimalized. This arrangement of the atom determines the geometry
of the resulting molecule.
Postulates of VSEPR Theory:
The postulates of the VSEPR theory are listed below:
 In polyatomic molecules (i.e. molecules made up of three or
more atoms), one of the constituent atoms is identified as
the central atom to which all other atoms belonging to the
molecule are linked.
The total number of valence shell electron pairs decides the shape of the
molecule.
The electron pairs have a tendency to orient themselves in a way that
minimizes the electron-electron repulsion between them and maximizes the
distance between them.
The valence shell can be thought of as a sphere wherein the electron pairs
are localized on the surface in such a way that the distance between them is
maximized.
 When the central atom of the molecule be surrounded by bond pairs of
electrons, then, then the regular shaped molecule can be expected.
When the central atom be surrounded by both lone pairs and bond pairs of
electrons, the molecule would tend to have a distorted shape.
The strength of the repulsion is strongest in two lone pairs and weakest
in two bond pairs.

If electron pairs around the central atom are closer to each other, they
will repel each other. This results in an increase in the energy of the
molecules.
If the electron pairs lie far from each other, the repulsions between
them will be less and eventually, the energy of the molecule will be
low.
The different geometries that molecules can assume in accordance with the VSEPR
theory can be seen in the illustration provided below:
Limitations of VSEPR Theory:
Some significant limitations of the VSEPR theory include:
 This theory fails to explain isoelectronic species (i.e. elements
having the same number of electrons). The species may vary in
shapes despite having the same number of electrons.
 The VSEPR theory does not shed any light on the compounds
of transition metals. The structure of several such compounds
cannot be correctly described by this theory. This is because the
VSEPR theory does not take into account the associated sizes of
the substituent groups and the lone pairs that are inactive.
 Another limitation of VSEPR theory is that it predicts that halides
of group 2 elements will have a linear structure, whereas their
actual structure is a bent one.
For example:
There are only two places in the valence shell of the central atom in BeF 2 where electrons
can be found. Repulsion between these pairs of electrons can be minimized by arranging
them so that they point in opposite directions. Thus, the VSEPR theory predicts that
BeF2 should be a linear molecule, with a 180o angle between the two Be-F bonds.

Repulsion between the five pairs of valence electrons on the phosphorus atom in PF 5 can be
minimized by distributing these electrons toward the corners of a trigonal bipyramid.
Three of the positions in a trigonal bipyramid are labeled equatorial because they lie along
the equator of the molecule. The other two are axial because they lie along an axis
perpendicular to the equatorial plane. The angle between the three equatorial positions is
120o, while the angle between an axial and an equatorial position is 90o.
Sigma and Pi bond approach:
Sigma and pi bonds are types of covalent bonds that differ in the overlapping
of atomic orbitals. Covalent bonds are formed by the overlapping of atomic
orbitals. Sigma bonds are a result of the head-to-head overlapping of atomic
orbitals whereas pi bonds are formed by the lateral overlap of two atomic
orbitals.

Various bond parameters such as bond length, bond angle, and bond enthalpy depend on
the way the overlapping of atomic orbital takes place. This overlap occurs in two major
ways, giving rise to two primary types of covalent bonds, i.e. sigma and pi bonds.
The Sigma (σ) Bond:
This type of covalent bond is formed by head-on positive (same phase)
overlap of atomic orbitals along the internuclear axis. Sigma bonds are the
strongest covalent bonds, owing to the direct overlapping of the
participating orbitals. The electrons participating in a σ bond are commonly
referred to as σ electrons.
Generally, all single bonds are sigma bonds. They can be formed via the
following combinations of atomic orbitals:
S-S Overlapping:
In this kind of overlapping, one ‘s’ orbital from each participating atom
undergoes head-on overlapping along the internuclear axis. An s
orbital must be half-filled before it overlaps with another.
The overlapping of two s orbitals resulting in a
sigma bond is illustrated above. This type of
overlap occurs in H2 molecules, where each
S-P Overlapping:
Here, one half filed s orbital overlaps with one half-filled p orbital along the internuclear
axis, forming a covalent bond. This condition is illustrated below:

This type of overlapping can be observed in ammonia. An NH3 molecule features 3

sigma bonds, formed by the overlap of the 2px, 2py, and 2pz orbitals belonging to the
nitrogen atom and the 1s orbitals of the three hydrogen atoms.
P-P overlapping:
In this condition, one half-filled p orbital from each participating atom undergoes
head-on overlapping along the internuclear axis. This type of overlapping is illustrated
below: A Cl2 molecule features a p-p overlap of the
3pz orbitals of two chlorine atoms. It is important to
note that the head-to-head overlapping of two p
orbitals gives a sigma bond whereas the lateral
overlap of these orbitals leads to the formation of
pi bonds.
The Pi (π) Bond:
Pi bonds are formed by the sidewise positive (same phase) overlap of atomic orbitals
along a direction perpendicular to the internuclear axis. During the formation of π
bonds, the axes of the atomic orbitals are parallel to each other whereas the
overlapping is perpendicular to the internuclear axis.
This type of covalent bonding is illustrated below:

Pi Bonds are generally weaker than sigma bonds, owing to the significantly lower degree
of overlapping. Generally, double bonds consist of one sigma and one pi bond, whereas
a typical triple bond is made up of two π bonds and one σ bond. It is important to note
that a combination of sigma and pi bonds is always stronger than a single sigma bond.
 Difference Between Sigma and Pi Bonds:

Sigma Bond Pi Bond

1.The overlapping orbitals can 1.The overlapping orbitals must
be pure or hybrid be unhybridized
2.These bonds are strong and 2.These bonds are relatively
have high bond energies. weak.

3.Can exist independently 3.Must exist along with a sigma

bond.
4.Has an impact on the shape 4.Has no role in determining
of molecules the shape of molecules
 Calculation of percent ionic character in a covalent bond from dipole moment:
The asymmetrical charge distribution in a polar substance such as HCl
produces a dipole moment where Qr ​in meters (m). is abbreviated by
the Greek letter mu (µ).
The dipole moment is defined as the product of the partial charge Q on
the bonded atoms and the distance r between the partial charges:
μ=Qr
where Q is measured in coulombs (C) and r in meters. The unit for dipole
moments is the debye (D):
1D=3.3356×10-30 C.m

We can measure the partial charges on the atoms in a molecule such as HCl. If
the bonding in HCl were purely ionic, an electron would be transferred from H to
Cl, so there would be a full +1 charge on the H atom and a full −1 charge on
the Cl atom. The dipole moment of HCl is 1.109 D, as determined by measuring
the extent of its alignment in an electric field, and the reported gas-phase H–Cl
distance is 127.5 pm. Hence the charge on each atom is
Q=μr=1.109D(3.3356×10−30C⋅m/1D)/(1/127.8pm)(1pm/10-12m)=2.901×10−20C
By dividing this calculated value by the charge on a single electron (1.6022 ×
10−19 C), we find that the electron distribution in HCl is asymmetric and that
effectively it appears that there is a net negative charge on the Cl of about
−0.18, effectively corresponding to about 0.18 e−. This certainly does not
mean that there is a fraction of an electron on the Cl atom, but that the
distribution of electron probability favors the Cl atom side of the molecule by
about this amount.

2.901×10-20C/1.6022×10-19C=0.1811e−

To form a neutral compound, the charge on the H atom must be equal but
opposite. Thus the measured dipole moment of HCl indicates that the H–Cl
bond has approximately 18% ionic character (0.1811 × 100), or 82%
covalent character.
Example:
In the gas phase, NaCl has a dipole moment of 9.001 D and an Na–Cl distance
of 236.1 pm. Calculate the percent ionic character in NaCl.
Solution:
The charge on each atom is given by
Q=μr=9.001D(3.3356× 10-30 C.m /1D)(1/236.1pm)(1pm/ 10-12m)=1.272×
10-19 C
Thus NaCl behaves as if it had charges of 1.272 × 10−19 C on each atom
separated by 236.1 pm.
The percent ionic character is given by the ratio of the actual charge to
the charge of a single electron (the charge expected for the complete
transfer of one electron):
%ionic character=(1.272× 10−19 C /1.6022× 10−19 C )(100)=79.39%≃79%
Do yourself:
In the gas phase, silver chloride (AgCl) has a dipole moment of 6.08 D and an Ag–Cl distance
of 228.1 pm. What is the percent ionic character in silver chloride?
Metallic bond:
 It is the force that holds atoms together in a metallic substance. Such a solid
consists of closely packed atoms.
 In most cases, the outermost electron shell of each of the metal atoms
overlaps with a large number of neighbouring atoms. As a consequence, the
valence electrons continually move from one atom to another and are not
associated with any specific pair of atoms.
 The valence electrons in metals, unlike those in covalently bonded
substances, are nonlocalized, capable of wandering relatively freely
throughout the entire crystal. 
 The atoms that the electrons leave behind become positive ions, and the
interaction between such ions and valence electrons gives rise to
the cohesive or binding force that holds the metallic crystal together.
Valence Bond Theory:
Main postulates of Valence bond theory:

1) Valence orbitals of atom overlap each other to form a bond. 

2) A pair electrons is present in overlapping orbitals.
3) Electron density is maximum around bonded atoms.
4) Degree of overlapping determines strength of the bond.

Limitations of valence bond theory are:

1. It fails to explain the tetravalency of carbon.
2. This theory does not discuss the electrons' energies.
3. The assumptions are about the electrons being localized to specific
locations.
 BAND THEORY:
Molecular orbital theory extended to solids is referred as Band Theory.
 The characteristic physical properties as well as the high co-ordination number
(either 8 or 1) suggest that the bonding in metals is quite different from those in
other substances.
 There is ionic contribution and it is also not possible to have 2c-2e covalent
bonding between all the adjacent pairs of atoms since there are neither sufficient
electrons nor sufficient orbitals.
 The configurational study of elements reveals that the presence of empty AOs in
the valence shell is a prerequisite for metallic properties.
 The elements which lack in empty AOs in their valence shell are all non-metals. For
example, carbon in excited state and N, O, F, Ne, etc. lack in empty AOs and are
therefore non metals.
Band Theory of Metals Example:
Let us take the example of sodium:
 Sodium has an atomic configuration of 1s2, 2s2, 2p6, 3s1.
 It has one unpaired electron in the 3s orbital.
 The 3s valence atomic orbital of sodium overlaps with another such orbital of
the same energy to form molecular orbitals.
 The atomic orbitals continue to combine in some fashion forming a band.
 The energy spread of this band is calculated as the difference in energy
between the most strongly bound “bonding orbital” and the highest energy “anti
bonding orbital”.
 When the gap between the valence band and the conduction band (next higher
unoccupied band) is quite high, electrons fail to jump from valence band to the
conduction band. Such compounds show very less or no conductivity.
 When the gap between the valence band and conduction band is small, some
electrons may jump from valence band to conduction band and thus show
some conductivity. Such substances are known as semiconductors. For
example silicon, germanium.
 In case of metal, there is no separation between the bands. This helps the
incited electrons to easily move from one orbital to another and hence metals
are good conductors of electricity.
 In the case of semiconductors, there is a small gap between the valence
band and the conduction band.
 Only a small fraction of electrons (having sufficient energy) jumps when
incited.
  The conductivity of such substances can be increased by increasing the
temperature or doping.
 In insulators, the difference between the valence band and conduction band
is very high. Hence, no conductivity is shown by such substances.

Thus, according to the Band Theory, the conduction band is the band of
electron orbitals that electrons can jump up into from the valence band when
excited. When the electrons are in these orbitals, they have enough energy to
move freely in the material. This movement of electrons creates an electric
current.
Semi conductors (Metalloids):
The solids which are basically insulators at absolute zero but which can
conduct electricity to certain extent by migration of electrons at room
temperature are called as the semi-conductors. The conductivity of a
semiconductor lies between those of metallic good conductor and non metallic
insulator. Commercially, the best known semi –conductors are silicon and
germanium
Insulator: An insulator has a large gap between the
valence band and the conduction band. The valence
band is full as no electrons can move up to the conduction
band. As a result, the conduction band is empty.
Examples : plastics, paper, rubber, glass and dry air. 

All of the electrons in insulators are tied up in

interatomic bonds. To remove these electrons from their
bonds it takes a large amount of energy, several electron
volts, eV. This is manifested as the band gap.