Chapter 2 : Simple bonding theories of molecules

Atomic orbitals, Aufbau principle, multiple bonding (σ and π bond approach) and bond lengths, the
valence bond theory (VBT), Concept of hybridization, hybrid orbitals and molecular geometry, Bent’s
rule, Valence shell electron pair repulsion theory (VSEPR), shapes of the following simple molecules
and ions containing lone pairs and bond pairs of electrons: H2O, NH3, PCl5, SF6, SF4, ClF3, I3 - and
H3O +. Molecular orbital theory (MOT). Molecular orbital diagrams bond orders of homonuclear
and heteronuclear diatomic molecules and ions (N2, O2, C2, B2, F2, CO, NO, and their ions)

AUFBAU PRINCIPLE
Aufbau is a German word meaning 'building up'. This gives us a sequence in which various subshells
are filled up depending on the relative order of the energy of the subshells. The subshell with
minimum energy is filled up first and when this obtains maximum quota of electrons, then the next
suhshell of higher energy starts filling. The sequen~e in which. the various subshells are filled is the.
following: .:

The sequence in which various subshells are filled up can also be determined with the help of (n + l )
value for a given subshell. The subshell with lowest (n + I ) value is filled up first.
When two or more subshells have same (n + I) value, the.subshell with lowest value of 'n' is filled up
first.
Valence Bond Theory (VBT) and its limitations
This theory was put forward by Heitler and London in 1927 to covalent bond. They gave a theoretical
treatment molecule and the energy changes taking place therein. Later Slater in 1931 to account for
the directional characteristics of the covalent bond. The main points called the postulates of this
theory are given below:
(i) The atoms involved in the bond formation maintain their individuality after the bond is formed i.e.
in the molecule.
(ii) The bond is formed due to the overlapping of half filled atomic orbitals (or the interaction of
electron waves) belonging to the valence shell of the combining atoms as these approach each other.
Thus the spins of the two electrons get neutralized. The electrons in the orbitals of inner shells remain
undisturbed.
(iii) The filled orbitals (i.e. containing two electron) do not take part in the bond formation. However
by using energy, they are first unpaired by promoting to the orbitals of slightly higher energy and
then can take part in bonding. For example, N can form NCl3 only retaining a lone pair while P can
form both PCl3 and PCl5.
(iv) The electrons forming the bond undergo exchange between the atoms and thus stabilize the bond.
(v) The strength of the covalent bond depends on the extent to which the two atomic orbital overlap
in space.
Limitations of Valence Bond theory:
i) The formation of coordinate covalent bond (also known as dative bond) cannot be explained on the
basis of this theory because according to this theory a covalent bond is formed as a result of
overlapping of half filled orbitals of the combining atoms and the paired orbitals of the atoms do not
take part in normal covalent bond formation.
ii) The odd electron bond formation between the atoms cannot be explained by this theory because a
covalent bond is an electron pair bond means two electrons are required for a bond.
iii) This theory is unable to explain the paramagnetic behavior of oxygen molecule because
paramagnetism is a property caused by the presence of unpaired electrons and in an oxygen molecule,
according to VBT, two electron pair bonds are present between the oxygen atoms and hence it should
be diamagnetic.
iv) In some molecules, the properties like bond length and bond angles could not be explained by
assuming simple overlapping of atomic orbitals of the atoms.
Types of overlapping of atomic orbitals
Sigma (σ) Bond
A bond formed between two atoms by the overlap of singly occupied orbitals along their axes (end to
end overlap) is called sigma (σ) bond. In such a bond formation, maximum overlap is possible
between electron clouds and hence, it is a strong bond. Electron cloud of this bond is symmetrical
about the line joining the two nuclei of the two atoms. Sigma bond can, thus, be defined as: "Bond
orbital which is symmetrical about the line joining the two nuclei is known as sigma bond." It is
formed by head on or axial overlap. Sigma bonds are formed by three types of overlapping:
(i) s-s overlapping This type of overlapping occurs between the s- orbitals of the combining atoms
giving the s-s covalent bond. This type of overlapping always occurs in the direction of molecular or
internuclear axis.
(ii) s-p overlapping
The overlapping taking place between the s orbital of one atom and p-orbital of another atom is called
s-p overlapping. The resulting bond is the s-p covalent bond formed in the direction of p orbital
taking part in overlapping.
Formation of HF molecule: In the formation of HF molecule the 1s-orbital of hydrogen overlaps with
the p-orbital of fluorine containing unpaired electron.

(iii) p-p overlapping

The overlapping taking place between the p orbitals of two different atoms is called p-p overlapping.
Formation of fluorine molecule : This is illustrated by the formation of fluorine molecule. The
electronic configuration of fluorine atom is 1s2 2s22p5, i.e., one orbital is singly occupied. When p-
orbitals of two fluorine atoms approach each other with their heads directly towards one another, they
overlap and form a sigma bond.

Pi (п) Bond

п -bonds are formed by the sidewise or lateral overlapping of p-orbitals. The overlapping takes place
at the side of two lobes and hence, the extent of overlapping is relatively smaller. Thus, п bond is a
weaker bond in comparison to sigma bond. The molecular orbital is oriented above and below the
plane containing nuclear axis. A covalent bond formed between two atoms by side to side or lateral
(perpendicular to the molecular axis) overlapping of only p-atomic orbitals or sometimes p and d-
orbitals belonging to the valence shell of the atoms is called a π bond. If in a molecule, a particular
atom uses one of its p-orbitals for σ bond formation then rest of the two p-orbitals are used to form
the π bonds by lateral overlapping.
For σ and π bonds, the following points are important:
1. A σ bond is formed by axial overlapping of either pure or hybrid atomic orbitals of the two
combining atoms while a π bond results from the lateral overlapping of pure atomic orbitals.
2. A σ bond is stronger than a π bond due to greater extent of overlapping of orbitals along the
inter nuclear axis than in lateral overlapping.
3. A σ bonds determine the direction of the covalent bond and bond length, π bonds have no
effect on the direction of the bond. However, their presence shortens the bond length.
4. There is free rotation of the atoms about a σ bond because the electron cloud overlaps
symmetrically along the internuclear axis while this is not possible about a π bond because the
electron clouds overlap above and below the plane of the atoms.
5. A σ bond has its free existence between any two atoms in a molecule while π bond is formed
between the atoms only when σ bond already exists.

Hybridization
Mixing of orbitals in valance shell of an atom to produce equivalent no. of orbitals of similar
energy and shape is called as ‘hybridization’ and new orbitals are called as hybrid orbitals.

Salient features (or the Rules) of hybridization

1. The atomic orbitals belonging to the valence shell of the central atom/ion of a
molecule/ion with almost similar energies mix up together or hybridize to give the
hybrid orbitals. But the atomic orbitals of the central atom participating in the π bond
formation are excluded from the hybridization process.
6. The number of hybrid orbitals produced is equal to the number of atomic orbitals
undergoing hybridization. The hybrid orbitals like pure atomic orbitals can accommodate
a maximum of two electrons of opposite spins.
7. If required, electron(s) may be promoted from an orbital in ground state of the central atom
to the next empty higher energy orbital provided the value of n does not change as happens
in the central atom of BeCl2, BCl3, CH4, PCl5, SF6etc.
8. Most of the hybrid orbitals are equivalent in energy, shape and size but may not be identical.
They differ from one another in their orientation in space.
9. From the type of hybridization, the geometry and bond angles of a molecule can be
predicted.
10. In a few cases empty atomic orbitals or those with lone pairs of electrons (i.e. filled
atomic orbitals) are also involved in the hybridization process but in such cases normal
covalent bond is not formed rather this process leads to the formation of coordinate covalent
bond. Sometimes these filled hybrid orbitals do not form the bonds and the electron pair
remains as lone pair on central atom.
11. The hybrid orbitals are involved in the σ-bond formation only and π bond is not formed by
them at all.
Types of Hybridization

There are three types of hybridization in organic compounds.

1. sp³ hybridization
2. sp² hybridization
3. sp hybridization
1. sp³ hybridization

Mixing of one s- and three p-orbitals in valance shell of an atom and produce four sp³ hybrid
orbitals of similar energy and similar shape is called as sp³ hybridization. Molecule has
tetrahedral shape with bond angle 109º28՛ or 109.5º each.

Characteristics:

1. These sp3 hybrid orbitals are equivalent in energy and shape and are oriented along the four
corners of a regular tetrahedron. The bond angle between each pair of these orbitals is
109.50, called tetrahedral angle.
2. Each sp3 hybrid orbital has 25% s- character and 75% p- character, hence their shape
is closer to that of p- orbitals i.e. are pear shaped.
Examples are CH4, C2H6 etc.

In CH4, carbon has sp³ hybridization and it has four sp³ hybrid orbitals. Each orbital
overlap with s-orbital of four H-atoms to form CH4 molecule.

2. sp² hybridization:

Mixing of one s and two p-orbitals in valance shell of an atom hybridize together to give three
sp² orbitals of similar energy and shape, called as sp² hybridization. Molecule has trifocal
planar structure with bond angle 120º each.

Characteristics :
 1. The sp2 hybrid orbitals are equivalent in energy and shape and are oriented towards
the corners of an equilateral triangle, hence inclined at an angle of 1200with one
another, leading to trigonal planar geometry.

2. They all lie in one plane (i.e. planar).

3. They possess 33% s- character and 66% p- character and therefore are less sp- hybrid
orbitals.
Examples are C2H4, C3H6 etc.

In C2H4, each carbon has sp² hybridization. One sp² hybrid orbital of each carbon overlap
together while other two sp² hybrid orbitals overlap of two H-atoms on each carbon. Each
carbon also has one unpaired p-orbital which overlap sideways together to form bond.

3. sp Hybridization:

Mixing of one s and one p-orbital in valance shell of an atom hybridize together to give two sp
hybrid orbitals of similar energy and shape called as sp-hybridization. Molecule has linear
shape with bond angle 180º.

Characteristics:
1. These hybrid orbitals are equivalent in energy, shape (oval shaped) and are oriented in the
opposite directions at an angle of 1800 from each other, leading to linear geometry.
2. Each hybrid orbital has one large lobe and one small lobe. The larger lobe takes part in
overlapping process.
3. These hybrid orbitals possess 50% character of s-orbital (spherical) and 50% that of p- orbital
(pear shaped) and hence are oval shaped.
Examples are C2H4, C3H4 etc.

In C2H2, each carbon has sp hybridization. One sp hybrid orbital of each carbon overlap together
and other sp hybrid orbital of each carbon overlap with H-atoms. Each carbon atom also has two
unpaired p-orbitals which undergo sideways overlap together to form two -bonds.
 4. Sp3d hybridization:
When one s, three p and one d (generally dz2) atomic orbitals of the valence shell of the
central atom of a given molecule/ion mix up together and give rise to the formation of a set
of five hybrid orbitals, the process is known as sp3d hybridization and the new orbitals
formed are called sp3d hybrid orbitals. The process of this type of hybridization has been
shown here:

Characteristics:
1. The sp3d hybrid orbitals are equivalent in energy and shape and are oriented towards
the five corners of a regular trigonal bipyramid i.e. their spatial arrangement is
trigonal bipyramidal.
2. They do not lie in one plane. Three of the five hybrid orbitals called the basal or
equatorial hybrid orbitals are oriented towards the corners of an equilateral triangle
forming a triangular plane while the remaining two called axial hybrid orbitals lie
above and below the plane on the axis passing through the centre of plane. The
angle between each adjacent pair of basal hybrid orbitals is 1200, that between two
axial hybrid orbitals is 1800 and that between the axial and basal hybrid orbitals is
900.
Examples: AX5 molecule (A = P, As, Sb and X = F, Cl, Br). Let us discuss the
hybridization and bonding in PCl5 molecule.
yz
5.Sp3d2 hybridization:
On mixing one s-orbital, three p-orbitals and two d (generally dx2-y2 and dz2) orbitals of the
valence shell of central atom of the given molecule/ion, a set of six hybrid orbitals is formed.
This process is known as sp3d2 hybridization and the new orbitals formed are called sp3d2

hybrid orbitals. The formation of these orbitals is shown below:

Formation of six sp3d2 hybrid orbitals from the mixing of one s, three p and two d-
atomic orbitals

Characteristics:

1. All the six hybrid orbitals formed are equivalent in energy and shape and are o riented
along
the six corners of a regular octahedron i.e. their arrangement in space is octahedral.
2. All the orbitals do not lie in a plane. Four hybrid orbitals of the six called basal or
equatorial hybrid orbitals are lying in square plane while the remaining two called
axial hybrid orbitals lie above and below the plane on the axis passing through the
centre of the square base. The angles between any adjacent pairs of hybrid orbitals
(basal or axial) is 900.
3. Examples: AF6 type molecule (A=S, Se, Te). Let us see the process of bond formation in
SF6 molecule.

Formation of six σ-covalent bonds by the overlapping of sp3d2 hybrid orbitals of S

central atom with p-orbitals of six F atoms

1. Sp3d3 hybridization:
When one s, three p and three d (generally dxy, dyz, dzx) orbitals of the valence
 shell of the central atom in a given molecule/ion mix up together, a set of seven
new orbitals is formed. This process of mixing is called sp3d3 hybridization and the
new orbitals formed are known as sp3d3hybrid orbitals. Their formation occurs as
follows:

Formation of seven sp3d3 hybrid orbitals from the mixing of one s, three p and three
d-orbitals of the central atom

Characteristics:

1. All the seven hybrid orbitals are equivalent in energy and shape and are oriented
towards the seven corners of a regular pentagonal bipyramidal i.e. their spatial
arrangement is pentagonal bipyramidal.
2. All of them do not lie in one plane. Five of them lie in the pentagonal plane and are
called basal or equatorial hybrid orbitals while remaining two called axial hybrid
orbitals lie above and below the plane on the axis passing through the centre of the
pentagonal plane.
3. The angle between any adjacent pair of basal hybrid orbitals is of 720 and that
between an axial and a basal hybrid orbital is equal to 900.
Example: IF7 (an interhalogen compound)
The whole act of hybridization and bond formation in this molecule can be shows
as given below:
Formation of seven covalent bonds from the overlapping of sp3d3 hybrid orbitals of central
I-atom and p-orbitals of seven F-atom
 VALENCE SHELL ELECTRON PAIR REPULSION (VSEPR) THEORY
The valance bond theory also called the atomic orbital theory can explain the geometrical
shape of many molecules/ions of both transition and non-transition elements by employing
the concept of hybridization. But many molecules/ions remain unexplained in terms of their
geometry by this method. To overcome this shortcoming, a modification of VBT was
developed by Gillespie and Nyholm which can predict the shapes of many species which are
left uncovered by the concept of simple hybridization. According to this theory “The shape
or the geometry of a polyatomic molecule/ion of non-transition (mostly non-metallic)
element depends upon the number and nature of the electron pairs contained in the valence
shell of the central atom.” Thus the electrons already present in the valence shell plus the
additional electrons acquired by the central atom as a result of bonding with other atoms are
called its valence shell electrons. These electrons may be present as bonding or non-bonding
electron pairs in the central atom which arrange themselves in such a way that there is a
minimum repulsion between them and the molecule has minimum energy and maximum
stability. Since there can be only one orientation of orbitals corresponding to minimum
energy, hence the molecule attains a definite shape/geometry.
Thus lone pairs experience more freedom than the bonded pairs and hence exert
more repulsion on any adjacent electron pair than a bond pair does on the same
adjacent electron pair. The repulsion among the electron pairs follows the
sequence as:
l.p.-l.p. repulsion>l.p.-b.p. repulsion>b.p.-b.p. repulsion

maximum intermediate minimum

Because of this fact, if the central atom in a molecule/ion contains both lone pairs (l.ps.)
and bonded pairs (b.ps.), there occurs a contraction in the bond angle (which is formed
between two adjacent b.ps.). More the number of l.ps. on the central atom, greater is the
contraction caused in the bond angle. This statement is supported by the bond angles
observed in CH4, NH3 and H2O:
molecules CH4 NH3 H2O
Type of hybridization involved sp3 sp3 sp3
No. of l.ps. on the central atom 0 1 2
Bond angle 109.50 107.30 104.50

A. Shape of NH3 Molecule ( sp3 hybridization)

In NH3 molecule, the central atom N has following ground state valence shell
configuration: Ng : 2s2px1py1pz1 → sp3 hybridization

All these atomic orbitals participate in hybridization and give four equivalent sp3
hybrid orbitals. One of them contains an electron pair (lone pair) and three half
filled hybrid orbitals then overlap with 1s orbitals of three H-atoms to form σ-
covalent bonds (N-H bond).

Formation of hybrid orbitals and their overlapping with 1s orbitals of 3H atoms to give NH3
molecule

From the figure, it is evident that one lone pair of electrons is present in NH3
molecule which exerts more repulsion on bonded pairs than that operating between
the bonding pairs of electrons. The net result is that the NH3 molecule attains
trigonal pyramidal shape with the bond angle of 107.30, a deviation of about 20
from the tetrahedral angle of 109.50.
B. Shape of H2O Molecule (sp3 hybridization)
The ground state valence shell configuration of the central atom O of H 2O
molecule is: O: 2s2 px2py1pz1 → sp3 hybridization
All these atomic orbitals undergo hybridization and give rise to four equivalent sp3
hybrid orbitals. Two of these hybrid orbitals are half filled and remaining two
 contain lone pairs of electrons. The unpaired hybrid orbitals than overlap with 1s
orbitals of two H-atoms to form σ covalent bonds (O-H bonds).

Formation of hybrid orbitals and their overlapping with 1s orbitals of two

H-atoms to give H2O molecule

There are two lone pairs of electrons present in H2O molecule which exert strong
repulsion on each other and move away towards the bonded pairs of electrons. This
brings the bonded pairs closer to each other thereby causing contraction in the bond
angle. H2O molecule thus attains a V-shaped geometry with the bond angle of
104.50, a deviation of a bond 50 from the tetrahedral angle of 109.50
C. Shape of H3O+ Ion (sp3 hybridization)
Hydronium ion (H3O+) is formed by the combination of H2O molecule and H+
ion in which H2O molecule donates one of its lone pairs of electrons to H+
ion and it accepts that lone pair of electrons in its vacant 1s orbital.
Actually, filled sp3 hybrid orbital of O-atom in H2O molecule overlaps with
empty s-orbital of H+ ion as follows thereby forming a coordinate covalent
bond:

Fig. Overlapping of filled sp3 hybrid orbital of O-atom in H2O and empty 1s orbital of H+ ion
to form H3O+ ion

This ion has trigonal pyramidal shape like that of NH3 molecule with one lone pair of electrons
on O-atom.
 D. Shape of SF4 molecule (sp3d hybridization)

In this molecule the central S-atom is in its first excitation state in which one of its px
electrons is promoted to the next empty dz2 orbital. The electronic configuration in
the ground and first excited state has been shown below:
Sg: 3sy 2pzx2p 1p 1 S1ex : 3s2ypx1p 1pz1 (dz2)1 sp3d

All these atomic orbitals of Sex central atom get hybridized to give five sp3d hybrid
orbitals directed toward the corners of a trigonal bipyramidal, one of these hybrid
orbitals contains an electron pair (b.p.) and the next four orbitals have unpaired
electrons which overlap with the p-orbitals of four F-atom to form SF4 molecule.

Fig. Formation of five hybrid orbitals of Sex atom and their overlapping with p-orbitals
of four F-atom to give SF4 molecule

This molecule attains a see-saw shape because of the presence of one lone pair of
electron (sometimes also called distorted tetrahedral) and lone pair lies at one of the
basal positions (the molecule has 1 lone pair and 4 bonded pairs)
E. Shape of ClF3 molecule (sp3d hybridization)
Cl is the central atom in this molecule with valence shell electronic configuration in
ground and first excited state as given below wherein one electron from a filled p-
orbital say py is promoted to a vacant d-orbital (viz. dz2) of the same shell:

Clg: 3sy 2pzx2p 2p 1

Cl Ex : 3s2p 2p 1pz1 3(dz2)1 sp3d
All the orbitals of the valence shell of Cl Ex atom are mixed up together to produce five
l ex
3
sp d hybrid orbitals. Two of the hybrid orbitals have lone pairs of electrons and three

Fig. Formation of five hybrid orbitals of Cl Ex atom and their overlapping with
p- orbitals of three F-atoms to give ClF3 molecule

have unpaired electrons which then overlap with unpaired p-orbitals of three F-
atoms to form σ covalent bonds. The lone pairs are said to occupy the equilateral
positions and the molecule attains T-shaped structure with the bond angle of 87.60
instead of 900 due to the distortion caused by lone pairs The T-shaped
structure has been confirmed by the experimental evidences. The whole act of
hybridization, overlapping and bond formation can be shown as below (molecule has 2
lone pairs and 3 bonded pairs).

The mode of hybridization shape and bonding in BrF3 and ICl3 molecules can also b explained as in
the ClF3.
F. Shape of ICl-2 ion (sp3d2 hybridization)
In ICl-2 ion, the central atom I (iodine) has the ground state electronic configuration in
its valence shell as shown below:
Ig: 5s2px2py2pz1 (dz2)0
All these atomic orbitals including a vacant dz2 orbital participate in hybridization to
produce five sp3d hybrid orbitals of which three orbitals contain lone pairs, one hybrid
orbital is half filled which overlaps with half filled p-orbitals of Cl-atom to give normal
σ bond and one overlaps with the filled orbital of Cl- ion to give hybrid orbital remains
vacant and coordinate covalent σ-bond (dative bond). The lone pairs occupy the
equatorial positions and the bonded pairs are situated in axial positions. The ion has 3
lone pairs and 2 bonded pairs as shown below and has almost linear shape:

Fig. Formation of five sp3d hybrid orbitals of central atom, I and overlapping of one
of these hybrid orbitals with p-orbital of Cl atom and that of filled p-orbital of Cl-ion
with vacant hybrid orbital of I atom

G. Shape of NO3- ion (sp2 hybridization)

The central N-atom in this ion is sp2 hybridized leaving a pure pz orbital behind. These
sp2 hybridized orbitals then overlap with the orbitals of one O atom and one O-ion to
form two normal σ-bonds and one dative σ- bond as follows:

Fig. Formation of two normal σ-bonds, one dative σ bond and one π bond central atom and
oxygen atoms/ion
 H. Shape of SO42- ion (sp3 hybridization)

S atom has 6 electron its valence shell and in this ion all the valence electrons of S are
present in unpaired state i.e. S2ex state. Out of six, four orbitals are hybridized as
follows:
Sg : 3s2px2py1pz1 S2ex : 3s1px1py1pz1 (dx2-y2)1(dz2)1 sp3

The SO42- ion can be shown as follows:

It has tetrahedral shape like CH4 molecule but has two single and two double bonds (σ-
and π-bonds). On the similar grounds the type of hybridization and shape of XeF2,
XeF4, XeOF4 and XeF6 molecules can be discussed. It is to be kept in mind that F-atom
is monovalent, O-atom is bivalent (forms one σ-and one π-bond with central atom) and
central atom requires only that number of hybrid orbitals which can form σ-bonds with
approaching atoms and these hybrid orbitals are generally unpaired or half filled. Hence
in the above molecules partial hybridization may take place.
XeF : sp3d 3 lone pairs + 2 bonded pairs and linear in
shape XeF4: sp3d2 2 lone pairs + 4 bonded pairs and
square planar
XeOF4 : sp3d2 1 lone pair + 5 bonded pairs +1 π-bond and is square
pyramidal
XeF6 : sp3d3 1 lone pair + 6 bonded pairs and pentagonal pyramidal
 Fig Shapes of XeF2, XeF4, XeOF4 and XeF6 molecules
MOLECULAR ORBITAL THEORY (MOT)

To explain the formation of the covalent bond in molecules/ions and their behavior
like relative bond strength, magnetic property etc., a new approach was
developed By Hund & Mulliken in 1932. This theory treats the covalent bonds in
terms of Molecular Orbitals (MOs) which are associated with the entire molecule
and result from the linear combination of atomic orbitals (LCAOs) of constituent
atoms of the molecule/ion. Thus the molecules are supposed to have their own
orbitals of varying energy in the same way as the isolated atoms have. The difference
between an atomic orbital and a MO is that an electron in an atomic orbital is
influenced by one nucleus only i.e. an atomic orbital is monocentric while an
electron in a M.O. is under the influence of all the nuclei contained in the
molecule/ion i.e. a M.O. is polycentric.

The atomic orbitals combining linearly to form the MOs must be of the
similar energy and same symmetry and may be of the two similar atoms of a
homonuclear diatomic molecule/ion (e.g. H2, H2+, N2, O2, O22- etc.) or may be of two
different atoms of a heterodiatomic molecule/ion (e.g. CO, NO, CN-, NO+ etc.).
The main characteristics of MOT are as follows:
(i) The atomic orbitals (AOs) combining linearly together to form the molecular
orbitals (MOs) lose their identity and the number of atomic orbitals is equal to
the number of molecular orbitals formed.
(ii) MOs are the energy states of the molecules/ions in which the electrons are
filled just like in AOs of the atoms.
(iii) The linear combination of the AOs may occur in two different ways, i.e. the
ad
 ditive combination gives bonding molecular orbitals (BMOs) and the
subtractive combination gives antibonding molecular orbitals (ABMOs).
(iv) The bonding MO has lower energy and hence greater stability than the
antibonding MO obtained from two AOs.
(v) The bonding MOs are denoted by σ,π,δ,Ψetc. symbols while the
antibonding MOs by
σ*,π*,δ*,Ψ* etc. symbols.
(vi) The shapes of MOs formed depend on the type of combining AOs and mode of
combination and their filling takes place according to the rules which are
applicable for AOs, viz. Aufbau principle, Pauli’s exclusion principle and
Hund’s rule of maximum multiplicity. Formation of MOs LCAO
approximation
Suppose ΨA and ΨB represent the wave function of the electrons in the A.Os.
of the atoms A and B respectively. Then linear combination of these A.Os.
may be done in two ways:
i) Ψb = ΨA+ΨB (++ combination) ……… (4.10)
This additive combination
A of AOs gives bonding molecular orbital for which the wave
function is denoted by Ψb. This is also called constructive interaction. Further, from
the above equation, we have (Ψb)2 = (ΨA+ΨB)2 = Ψ 2+ΨB2+2ΨAΨB -……….
(4.11)
Or (ΨAb)2>ΨB 2+Ψ 2 by a factor
A B 2Ψ Ψ where squares of respective Ψs give the

probability of locating the electrons in the different orbitals. From this we

infer that electrons prefer to reside in the BMO rather than the AOs and
placing electrons in BMO yields a stable covalent bond. In this MO the
electron density is greater between the nuclei of bonding atoms.
ii) Ψ* (or Ψa) = ΨA-ΨB ( +- (plus minus combination) ….. (4.12)
This subtractive combination of AOs gives the antibonding molecular orbital,
the wave function for which is represented by Ψ* ( psi star). This is also
called destructive interaction.
From this equation, we have
(Ψ*)2 = (ΨA-ΨB)2 = ΨA2+ΨB2 - 2ΨAΨB … (4.13)
Or (Ψ*A)2< Ψ
B +Ψ
2 2
by a factor
A B. 2Ψ Ψ From this relation it can be concluded
that electrons prefer to occupy the AOs rather than the ABMO and placing
electrons in this MO opposes the bond formation. The electron density in
this MO, decreases to zero between the nuclei.
 s-orbitals: combination of s-orbitals gives only σ MOs (both bonding and antibonding
g)

s and p-orbitals: This combination also gives only σ-M.Os. This is possible only along molecular axis i.e.
orientation of p-orbital is along molecular axis.

p-orbitals: The linear combination of p-orbitals may give σ as well as π MOs (b and *
both).
 It is to be noted that the interaction of AOs occurs to form the MOs only if the
symmetry consideration are taken care of, e.g. s-px combination is allowed but
s-py and s-The pz combination is disallowed if px lies along the molecular axis.
Similarly, px-py, px-pz and py-pz combinations are disallowed. py-py and pz-pz
combination will produce π M.Os. If X-axis is the molecular axis. The πbpy and πbpz as
well as πpy* and πpz* MOs have the same energy, i.e. these are degenerate orbitals.

Energy level diagrams of the molecules/ions

The MOs of the molecules/ions if arranged in the increasing order of their energy, we
get the so called energy level diagrams for them in which the MOs are taken as energy
levels. The electron are filled in these energy levels (MOs) from the lowest energy MO
to higher energy MOs according to Aufbau principle. The degenerate MOs are
filled according to Hund’s rule, i.e. first singly and then in pairs. This
condition is applicable to both homonuclear and heteronuclear diatomic
molecules/ions.

At the same time if these MOs are written is a sequence using their symbols along with
the number of electrons contained in them, then we get the molecular electronic
configuration in the same way as the electronic configuration of atoms. This sequence
according to increasing energy is:

This sequence has been found to hold for O2, F2 etc. but for hypothetical B2,
C2, N2 etc. σb2px is of slightly higher energy than πb2py/z MOs due to certain
well established reasons and hence the sequence becomes (taking x axis as
the molecular axis).
 Bond order: The bond order is the number of bonds in the molecular species
and is given as: Bond Order = (Na – Nb)/2, Na= number of antibonding
electrons, Nb=number of bonding electrons

Homonuclear diatomic molecules/ions:

i) H2 molecule ( i.e. 1+1=2 valence shell electrons) It is simplest case with 1s1
configuration in each H-atom. Molecular electronic configuration:
(σ 1 ) < 1s(σ* )0. Also denoted as KK in the higher molecules.
b 2
s
Bond Order = (2–0)/2=1
.: There is single bond between H-atoms in H2 molecule (H-H).

Fig Energy level diagram of H2

ii) N2 molecule (5+5=10 valence shell electrons)

Each N-atom has 2s22p3 electronic configuration in the valence shell. Thus
Molecular electronic configuration of N2 is:
 Fig Energy level diagram of N2
Bond order= 8-2=6/2=3. Hence there is a triple bond between N atoms in
N2 molecule. KK are non bonding orbitals.
iii) O2 molecule (6 + 6 = 12 valence shell electrons)
Each O-atom has 2s22p4 valence shell electronic configuration. 1s2 electrons
of both O atoms belonging to KK MOs. are non-bonding.

Electronic configuration of O2 molecule is:

Because of the presence of two unpaired electrons in ABMOs, O2 molecule is

paramagnetic in nature.
Bond order = (8-4)/2 = 2, There is a double bond between O-atoms in O2 molecule (O=O)
Similarly we can write down the electronic configuration and draw the energy level
diagrams for O2+, O2- (super oxide
2 ion), O 2-
(peroxide ion) and F2 molecule.O2+
(oxygenyl ion) has one electron less than O2 molecule. O2- ion will have one electron
more than O2 molecule. Both are paramagnetic. O22- ion and F2 molecule will have
 two electrons more than O2 which go to π2py* and π2pz* MOs thereby making them
diamagnetic.
Heteronuclear diatomic molecules/ions:
i) CO molecule ( 4+6=10 valence shell electron).
This molecule is isoelectronic with N2 molecule and has similar molecular electronic
configuration and energy level diagram to that of N2 molecule. There is only a difference in
electronic distribution in A.Os. as given below:
C : 2s22p2 ; O : 2s2 2p4
Electronic configuration of CO molecule is (the M.O. energy level sequence is like that of N2

Fig Energy level diagram of CO

Bond order =8-2/2=3 (triple bond)
ii) NO molecule (5+6=11 valence shell electron)
N: 2s22p3 and O: 2s22p4
The electronic configuration of NO molecule is (the M.O. energy level sequence is like
that of O2) but electron distribution is slightly different. It is paramagnetic due to the
presence of one unpaired electron. The bond between N and O is 2½ times as strong as a
normal covalent bond.
 Similarly, we can write down the electronic configuration and draw energy level
diagram for NO+ (one electron less than NO) ion which is diamagnetic and
has only paired electrons upto πbzpx M.Os. and πzp*y M.O. is vacant.

Fig. Energy level diagram of NO

Multiple Choice Questions

Q.1.The enolic form of acetone contains:
(a) 9 sigma bonds, I pi bond and 2 lone pairs of electrons
(b) 8 sigma bonds, 2 pi bonds and 2 lone pairs of electrons
( c) 10 sigma bonds, I pi bond and I lone pair of electrons
(d) 9 sigma bonds, 2 pi bonds and I lone pair of electrons
Q.2. The number of sigma and pi bonds in but-l-ene-3-yne are:
(a) 5 sigma and 5 pi (b) 7 sigma and 3 pi (c) 8 sigma and 2 pi (d) 6 sigma and 4 pi
Q.3. How many sigma and pi bonds are there in tetracyano ethylene molecule?
(a) 9σ and 9п (b) 9σ and 7п (c) 5σ and 9п(d) 5σ and 7п
Q.4. In benzene molecule, there are 3 pi bonds and:
(a) 3 sigma bonds (b) 6 sigma bonds (c) 10 sigma bonds (d) 12 sigma bonds
Q.5. The compound buta-I,2-diene has:
(a) only sp-hybridized carbon atom (b) only sp2-hybridized carbon atom (c) both sp-and sp2-
hybridized carbon atoms (d) sp, sp2-and sp3-hybridized carbon atoms
Q.6. In the compound HC≡C-C(CH3)=CH2, the hybridization of C2 and C3 carbons are
respectively:
(a) Sp3 and sp2 (b) sp2 and sp3 (c) sp3 and sp (d) sp2 and sp
Q.7. The CI-C-CI angle in 1,1,2,2-tetrachloroethene and tetrachloromethane will be about:
(a) 90֠ and 109.5֠ (b) 109.5֠ and 900 (c) 109.50 and 1200
Q.8. The shape of acetylene molecule is:
(a) linear (b) planar ( c) pyramidal (d) tetrahedral
Q.9. The compound in which carbon uses only its sp3-hybrid orbitals for bond formation is:
(a) HCOOH (b) (CH3)3COH (c) NH2CONH2 (d) (CH3)3C –CHO
Q.10. All carbon atoms are sp2-hybridised in :
(a) HC≡C-C≡CH (b) H2C . C=CH2 (c) 2-butene (d) 1,3-butadine (e) cyclohexane

Short Answer type Question

Q.1. State three main points of valence bond theory.
Q.2. With the help of a diagram indicate various forces of attraction and repulsion in a molecule
of hydrogen.
Q.3. Write the resonating structures of N2O and CO32-.
Q.4. Explain with the help of a diagram formation of σ and п bonds.
Q.5. Define hybridization. Name different kinds of hybridization and the shapes of molecules
obtained from such hybridization.
Q.6. Name two factors that determine the shapes of molecules. Briefly discuss them.
Q.7. Which type of hybridization is involved in the formation of a molecule of XeF4 What is the
shape of this molecule
Q.8. Bond energy of N2 molecule is higher than that of O2. Explain.
Q.9. Draw MO energy level diagram of HF.

Long Answer type Question

Q.1.What is the valence bond theory of bonding How does valence bond theory account for
bonding in a hydrogen molecule
Q.2. Write the various resonating structures of carbon monoxide molecule.
Q.3. What do you understand by the term resonance and resonance energy
Q.4. What are the essential conditions for writing resonating structure Draw all the resonating
structure of nitrous oxide.
Q.5.Explain silent feature of valence bond theory.
Q.6. What do you understand by resonance and regulation energy Discuss the resonance
structure of carbonate ion.
Q.7. Write the resonance structure of CO and cause of it low dipole moment.
Q.8. i. Give two examples of three electron Bond
ii. N2O is linear structure explain with the help of resonating structure
iii. Why CO2 is linear Explain with the help of resonating structure.
Q.9. Use valence bond theory in bonding in N2 and CO2
Q.10. What is hybridization Define following types of hybridization
i. sp3 ii. sp3d iii. sp3d2
Q.11. On the basis of hybridization explain the shapes of the following molecules and ions
NH3, BF3 , IF7 , NO3-
Q.12. Discuss the geometry of PF3 on the basis of VSEPR theory. compare its bond angle with
PCl3 and PBr3.
Q.13. i. Why is the use of hybrid orbitals preferred than atomic orbitals. Explain with answer.
ii. Give the hybridization of central atom and expected as well as actual geometry of following
molecule and ions
NH3, BF3 , IF7 , NO3- , CO32-
Q.14. Using VSEPR theory predict the shapes of the following molecules

PF5, NH3, SF4

Q.15. What is hybridization What are the important characteristics of hybridization
Q.16. Give the region of following
i. all the bond length in SF6 are equal but these are not equal in IF5 molecule.
 ii. BeF2 molecule is linear while SF2 is angular although both are triatomic molecule
Q.17. i. The geometry of H2O and H2S are same but their bond angles are different
ii. BF3 is Trigonal planar while NH3 is pyramidal
Q.18. What is hybridization Discuss the shapes of the following molecules on the basis of
hybridization
PF5, NH3, SF4
Q.19. i. What is LCAO a molecular orbital approach
ii. What do you understand by bonding and antibonding molecular orbitals