CHEMICAL BONDING AND MOLECULAR STRUCTURE

The attractive force that binds the atoms together in a molecule is called a chemical bond. It is formed either by
the transfer of electrons or by the sharing of electrons.
Lewis symbols
In the formation of a chemical bond, only the outermost electrons participate and these electrons are called
valence electrons. The inner electrons are well protected and they are called core electrons.
G.N Lewis introduced simple notations to represent valence electrons in an atom. These notations are called Lewis
symbols or Lewis notations. Here the nucleus and the inner electrons are represented by the symbol of the element and
the valence electrons by dots or crosses.
E.g. for sodium [11Na -2,8,1], the Lewis symbol is Na and for chlorine [17Cl -2,8,7], the Lewis symbol is Cl
Lewis symbols are informative. It gives the valency of an atom, which is either equal to the number of dots or
crosses or equal to 8 – no. of dots or crosses.
Octet rule
This rule was proposed by Lewis and Kossel. According to this rule, atoms undergo chemical reaction in order to
attain octet of electrons in the valence shell. Or, atoms containing 8 electrons in their valence shell are stable. To attain
octet, they share electrons or exchange electrons.
Ionic or Electrovalent Bond
A bond formed by the transfer of electron between 2 atoms is called ionic or electrovalent bond. Or, it is the force
of attraction between two oppositely charged ions.
E.g. formation of NaCl
11Na + 17Cl Na+Cl-
2,8,1 2,8,7
In Na atom, there is only one electron in the valence shell and in Cl, there are 8 electrons in the valence shell. In
order to attain octet state, Na atom loses one electron and form Na+ ion and Cl atom gains one electron and form Cl- ion.
These two ions attract each other by electrostatic force called ionic bond.
Na Na+ +e-
2,8,1 2,8
-
Cl + e Cl-
2,8,7 2,8,8
Na+ + Cl- NaCl
Energy changes during the formation of an ionic bond
An ionic bond formation involves the following steps:
1) The formation of a positive ion (cation) from the electropositive atom. The amount of energy required for this
process is called ionisation enthalpy (∆iH).
M(g) + ∆iH M+(g) + e-
2) Formation of negative ion from the electronegative atom. The energy involved in this process is called electron
gain enthalpy (∆egH).
X(g) + e- X-(g) + ∆egH
3) The packing of the cation and anion to form an ionic compound. The energy change in this process is called lattice
enthalpy (∆latticeH)
M+ + X- MX(s) + ∆latticeH
So the factors favouring the ionic bond formation are:
i) Low ionisation enthalpy of the electropositive atom (metal atom)
ii) High negative electron gain enthalpy of the electronegative atom (non-metal atom)
iii) High lattice enthalpy of the ionic compound formed.
Lattice Enthalpy
It is the energy required to completely separate one mole of an ionic compound into corresponding gaseous ions.
Or, it is the energy liberated when one mole of an ionic compound is formed from gaseous ions.
The stability of an ionic compound is determined by its Lattice Enthalpy. Generally greater the Lattice Enthalpy,
stabler will be the compound.

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Covalent bond
A bond formed by the mutual sharing of electrons between two or more atoms is called covalent bond.
e.g. 1) The formation of Chlorine molecule (Cl2)
17Cl + 17Cl Cl2
2,8,7 2,8,7
Both the chlorine atoms have 7 electrons in their outermost shell. So here the exchange of electrons is not
possible. For the formation of Cl2 molecule, each Cl atom shares one pair of electron.
The bond thus formed is called a single covalent bond.

2) The formation of O2 molecule

8O + 8O O2
2,6 2,6
To attain octet, each oxygen atom shares 2 pairs of electrons. Thus a double covalent bond is formed.

or
3) The formation of N2 molecule
7N + 7N N2
(2,5) (2,5)
To attain the octet configuration, the nitrogen atoms share 3 pairs of electrons. Thus a triple bond is formed.

In the formation of a covalent bond, each combining atoms contribute at least one electron to the shared pair. The
number of electrons contributed by an atom to the shared pair (bonded pair) during the formation of a covalent bond is
called covalency. In the formation of Cl2 molecule, the covalency of each Cl atoms is one, in O2 molecule, the covalency of
O atom is 2 and in N2, it is 3.
The double and triple bonds are together called multiple bonds. A covalent bond formed by the sharing of one pair
of electron is called a single bond. A double bond is formed when 2 pairs of electrons are shared between 2 atoms and a
triple bond is formed when 3 pairs of electrons are shared between two atoms.
Limitations of Octet rule
1) It could not explain the stability of compounds containing less than 8 electrons around the central atom. E.g. LiCl,
BeH2, BCl3 etc.
2) It could not explain the stability of molecules containing odd number of electrons like NO, NO2 etc.
3) It could not explain the stability of molecules containing more than 8 electrons around the central atom (i.e.
expanded octet). E.g. PF5, SF6, H2SO4, IF7 etc.
4) octet rule is based upon the chemical inertness of noble gases. But some noble gases like xenon and krypton form
compounds with F and O.
5) This theory does not account for the shape of molecules.
6) It does not explain the relative stability of the molecules.

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Bond Parameters
1) Bond Length: It is defined as the average equilibrium distance between the nuclei of two bonded atoms in a
molecule. It is measured by spectroscopic, X-ray diffraction and electron diffraction techniques. It is expressed in
pico-metre (pm) or in angstrom unit (A0).
2) Bond Angle: It is defined as the angle between the orbitals containing bonding electron pairs around the central
atom in a molecule. It can be experimentally determined by spectroscopic methods. It is expressed in degree.
3) Bond Enthalpy: It is defined as the amount of energy required to break one mole of a particular bond between 2
atoms in gaseous state. Its unit is kJ/mol.
For diatomic molecules, bond enthalpy is equal to bond dissociation enthalpy. Larger the bond
dissociation enthalpy, stronger will be the bond formed. For poly atomic molecules, the bond enthalpy is the
average of the bond dissociation enthalpies.
4) Bond order: It is defined as the number of bonds between 2 atoms in a molecule. For H2, bond order = 1, for O2,
bond order = 2 and for N2, bond order = 3. Isoelectronic molecules and ions have identical bond orders.
Generally with increase in bond order, bond enthalpy increases and bond length decreases.
Resonance Structures
In the case of some compounds, all the observed properties cannot be explained by a single structure. Here we
use more than one structures of the compound. These different structures are called resonance structures or canonical
structures or contributing structures. The phenomenon is known as resonance. Resonating structures are separated by
double headed arrows.
e.g. i) Ozone (O3)

The actual structure of ozone is not I or II. It is a resonance hybrid of the structures I and II which can be
represented as structure III.
ii) Carbon dioxide (CO2)

iii) Benzene (C6H6)

Characteristics of resonance
a) Resonance stabilizes the molecule. As the number of resonating structures increases, the stability also increases.
b) Resonance changes the bond length.
c) The difference in energy between the actual structure and the most stable canonical structure is called resonance
energy. Greater the resonance energy, stabler will be the molecule.
Polarity of bonds – Dipole moment
When a covalent bond is formed between 2 similar atoms, the shared pair of electrons is equally attracted by the two
atoms. So the electron pair is exactly between the two nuclei. The bond so formed is called a non-polar covalent bond.
But when the covalent bond is formed between 2 dissimilar atoms, the shared electron pairs are more attracted by
one of the atoms. So one atom gets a slight negative charge (δ-) and the other gets a slight positive charge (δ+). Such
molecules are called polar molecules. E.g. HCl, HF, H2O, HI etc.
The polarity of a molecule is expressed in terms of dipole moment (μ). It is defined as the product of the magnitude of
charge at one end (Q) and the distance between the charges (r).
Mathematically, μ = Q x r.
The unit of dipole moment is Coulomb metre (Cm). But it is usually expressed in the unit Debye (D). 1D = 3.336 x 10-30
Cm. Dipole moment is a vector quantity. i.e. it has both magnitude and direction. It is denoted by a small arrow with tail

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 on the positive centre and head pointing towards the negative centre.

e.g.: HF
In the case of poly atomic molecules, dipole moment depends on the individual bond dipoles and the spatial
arrangement of bonds. Here the dipole moment of the molecule is the vector sum of the bond dipoles of various bonds.
e.g. H2O

For BeF2, the net dipole moment is zero, since the two equal bond dipoles are in opposite directions and cancel
each other.

In BF3, the net dipole moment is zero. Here the resultant of any 2 bond dipoles is equal and opposite to the third.

Both ammonia (NH3) and nitrogen fluoride (NF3) are pyramidal in shape. Even though F is more electro negative
than H, the net dipole moment of NF3 is smaller than that of NH3. This is because in the case of NH3, the orbital dipole due
to lone pair is in the same direction as the resultant dipole moment of the three N – H bonds. But in NF3, the orbital dipole
is in the opposite direction to the resultant dipole moment of the three N-F bonds. So the dipole moments get partially
cancelled.

NH3 (μ = 1.47D) NF3 (μ = 0.23D)

Covalent character in ionic bonds – Fajans Rules

The partial covalent character of ionic bonds was explained by Fajans in terms of the following rules:
1) The smaller the size of the cation and the larger the size of the anion, the greater the covalent character of an
ionic bond.
2) The greater the charge on the cation, the greater the covalent character of the ionic bond.
3) For cations of the same size and charge, the ion with electronic configuration (n-1)dnns0 is more polarising than
the ion with a noble gas configuration (ns2 np6).
The shapes of molecules
Covalent bonds are directional in nature. i.e. they are directed to some specified positions in space. So covalent
compounds have definite shapes.
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.
3) In order to reduce the repulsion, the electron pairs stay at maximum distance.
4) Presence of lone pairs of electron causes distortion in the expected geometry of the molecule.

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 5) The repulsion between two lone pairs of electrons is different from those between two bond pairs or between a
lone pair and bond pair. The repulsion decreases in the order lone pair - lone pair > lone pair - bond pair > bond
pair - bond pair.
6) As the angle between the electron pairs increases, the repulsion decreases.
Prediction of geometry of molecules using VSEPR theory
I) Molecules containing only bond pairs of electrons
1) AB2 type (where A is the central atom and B is the no. of bond pairs)
Here there are 2 VSEPs. In order to reduce the repulsion, these electron pairs are arranged at an angle
of 180 . Thus the shape of the molecule is linear with bond angle 1800.
0

e.g. BeCl2, HgCl2 etc.

2) AB3 type
Here there are 3 VSEPs. In order to reduce the repulsion, these electron pairs are arranged at an angle
of 1200. Thus the shape of the molecule is planar triangular (trigonal planar) with bond angle 1200.
e.g. BF3, BCl3 etc.

3) AB4 type
Here there are 4 VSEPs. These are arranged at the four corners of a tetrahedron and hence the shape of
the molecule is tetrahedral with bond angle 109028l. e.g.: CH4, NH4+ etc.

4) AB5 type
Here there are 5 VSEPs. To reduce the repulsion, they are arranged at the five corners of a trigonal
bipyramid with bond angles 1200 and 900. E.g. PCl5

5) AB6 type
Here there are 6 VSEPs. To reduce the repulsion, they are arranged at the six corners of an octahedron
with bond angles 900. E.g.: SF6

II) Molecules containing both bond pairs and lone pairs

The presence of lone pairs of electron causes distortion in the shape of the molecules.

Type of Total no. No. of No. of Shape e.g.

molecule of VSEPs b.ps l.ps
Bent SO2, O3
AB2E 3 2 1

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 Trigonal Pyramid NH3
AB3E 4 3 1

Bent H2O
AB2E2 4 2 2

See-saw SF4
AB4E 5 4 1

T-Shape ClF3
AB3E2 5 3 2

Square Pyramid BrF5

AB5E 6 5 1

Square Planar XeF4

AB4E2 6 4 2

Explanation of shapes of ammonia and water molecules by VSEPR theory

1. NH3
In ammonia, the central atom N has 5 valence electrons (7N – 2,5). Among these electrons, three are used for the
formation of bonds with hydrogen atoms and the remaining 2 electrons stay as lone pairs. So there are 4 VSEPs. Hence
the expected shape of the molecule is tetrahedral. But due to the presence of lone pairs, the shape is distorted to trigonal
bipyramidal and the bond angle changes from 109028l to 1070.

2. H2O
In water, the central atom O has 6 valence electrons (8O – 2,6). Two of them are used for the formation of bonds
with hydrogen atoms and the remaining 4 electrons stay as lone pairs. So there are 4 VSEPs. Hence the expected shape of
the molecule is tetrahedral. But due to the presence of 2 lone pairs, the shape is distorted bent or angular or inverted v
shape and the bond angle changes from 109028l to 104.50.

Orbital overlap concept

Orbital overlapping is the process of partial interpenetration of atomic orbitals. The important characteristics of
orbital overlapping are:
1. A covalent bond is formed by the overlapping of half filled atomic orbitals present in the valence shell of atoms.

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 2. The overlapping orbitals should contain electron with opposite spin.
3. As a result of overlapping, the electrons get paired and a stable covalent bond is formed.
4. The strength of a covalent bond depends on the extent of overlapping. The greater the extent of overlapping, the
stronger will be the covalent bond formed.
Types of overlapping
There are two types of orbital overlapping.
1. Axial overlapping:
If the overlapping of atomic orbitals take place along inter nuclear axis, it is called axial overlapping or end
to end overlapping. A bond formed by axial overlapping is called sigma (σ) bond. The electrons present in sigma
bond are called sigma electrons. All single bonds are sigma bonds. A sigma bond can be formed by the following
ways:
i) s-s overlapping: Here the overlapping of two half filled s-orbitals take place along the inter nuclear axis.

ii) s-p overlapping: It occurs with the overlapping of one half filled s-orbital and one half filled p-orbital.

iii) p-p overlapping: Here two half filled p- orbitals of two atoms overlap.

2. Lateral overlapping:
Here the overlapping take place perpendicular to the inter nuclear axis. The bond formed as a result of
lateral overlapping is called pi (π) bond. The electrons in pi bond are called π electrons.

A π bond is always present along with σ bonds. A double bond contains one σ bond and one π bond. A triple bond
contains one sigma bond and two pi bonds.
A sigma bond is stronger than a pi bond. This is because the extent of overlapping is greater in a sigma bond.
Hybridisation
It is the process of inter mixing atomic orbitals having slightly different energies to form new orbitals having
equivalent energy and identical shape. The new orbitals formed are called hybrid orbitals.
Characteristics of hybridisation
1. The number of hybrid orbitals formed is equal to the number of atomic orbitals undergo hybridization.
2. The hybrid orbitals are always equivalent in energy and in identical shape.
3. The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals.
4. The hybrid orbitals are directed to some fixed positions in space. So the type of hybridization gives the shape of
the molecule.
Important conditions of hybridisation
a) The orbitals present in the valence shell of the atom are hybridized.
b) The orbitals undergoing hybridization should have almost equal energy.
c) Promotion of electrons is not an essential condition before hybridisation.
d) Completely filled orbitals of valence shell can also take part in hybridisation.
Types of hybridisation
1. sp3 hybridisation: It is the process of inter mixing of one s-orbital and three p-orbitals to form four new orbitals
having equivalent energy and shape. The 4 new orbitals formed are called sp3 hybrid orbitals. They are directed to the four

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corners of a regular tetrahedron with bond angle 109028l. Each sp3 hybrid orbitals has 25% s-character
s and 75% p-
character.
e.g. i) . Formation of methane (CH4)
In CH4, the central
ral atom C has the electronic configuration
2 2 2
6C – 1s 2s 2p

C (ground state) –
In order to explain the tetra valency of C, it is suggested that one of the electrons of 2s orbital is promoted to 2p
orbital.

C (excited state) –
Now, one s-orbital and three p--orbitals undergo sp3 hybridisation. These sp3 hybrid orbitals are directed to the
four corners of a regular tetrahedron with bond angle 109028l. each of these sp3 hybrid orbitals overlap with 1s orbital of H
to form four C-H σ bonds.

ii) tion of ethane (C2H6)

Formation
In ethane, each C atom undergoes sp3 hybridisation. Out of the 4 sp3 hybrid orbitals, one of each C
C σ bond. The remaining 3 sp3 hybrid orbitals of each C atom overlap with 1s orbital of H
atom overlaps axially to form a C-C
atom to form 6 C-H σ bonds.

iii) Formation of Ammonia (NH3) molecule

In NH3, the central atom N has the electronic configuration 1s22s22p3.

orbitals of N undergo sp3 hybridisation to form 4 sp3 hybrid orbitals. One of this sp3
The one s-orbital and three p-orbitals
hybrid orbitals is occupied by a lone pair and the other three sp3 hybrid orbitals overlap with 1s orbital of hydrogen to
form 3 N-H
H bonds. Due to the greater repulsion between lone pair and bond pairs, the shape is distorted to pyramidal and
the bond angle becomes 1070.

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 iv) Formation of water (H2O) molecule
In H2O, the central atom O has the electronic configuration 1s22s22p4.

Now the one s-orbital

orbital and three p-orbitals
p of O undergo sp3 hybridisation to form 4 sp3 hybrid orbitals. Two of
these sp hybrid orbitals are occupied by lone pairs and the other two sp3 hybrid orbitals overlap with 1s orbital of
3

hydrogen to form 2 O-H H bonds. Due to the greater repulsion between lone pairs, the shape is distorted to angular shape or
d ‘v’ shape and the bond angle becomes 104.50.
bent structure or inverted

2. sp2 hybridisation:: It is the process of inter mixing of one ss-orbital and two p-orbitals
orbitals to form three new orbitals
having equivalent energy and shape. The 3 new orbitals formed are called sp2 hybrid orbitals. They are directed to the
three corners of an equilateral triangle. So the shape of the molecule is planar triangular or trigonal planar with bond
angle 1200. Each sp2 hybrid orbitals has 33% ss-character and 66% p-character.
e.g. i) Formation of BCl3
Here the central atom B has the electronic configuration 1s22s22p1. In the excited state, one of the 2s electrons is
promoted to vacant 2p orbital.. So the configuration becomes 2s12p2.
Now one s-orbital and two p-orbitals
orbitals undergo hybridisation.
hybridisation. The 3 hybrid orbitals formed overlap with 2p orbitals
Cl σ bonds. Since the hybridisation is sp2, the shape of the molecule is planar triangular with bond angle
of Cl to form 3 B-Cl
1200.

ii) Formation of ethane or ethylene (C2H4)

In ethane, each C atom undergoes sp2 hybridisation. Out of the 3 sp2 hybrid orbitals, one of each C overlaps axially
C σ bond. The remaining two sp2 hybrid orbitals of each C
to form a C-C
overlap with the 1s orbital of H to form 4 C-H
C σ bonds.
Now each C atom has one unhybridized p-orbital,
p which
hich overlaps laterally to form a π bond. Thus there are 5 σ
bonds and one π bond in ethane.

3. sp hybridisation:: It is the process of inter mixing of one ss-orbital and one p-orbital
orbital to fform two new orbitals
having equivalent energy and shape. The 2 new orbitals formed are called sp hybrid orbitals. They are directed in a line. So
the shape is linear with bond angle 1800. Each sp hybrid orbitals has 50% s-character
character and 50% pp-character.
e.g. i) Formation of BeCl2
in BeCl2, the central atom Be has the electronic configuration 1s22s2. In the excited state, one of the 2s electrons is
promoted to 2p level. So the configuration becomes 1s22s12p1.

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 Now one s-orbital and one p-orbital
orbital undergo sp hybridisation to form 2 new sp hybrid orbitals. Each of these
hybrid orbitals overlaps with the 2p orbitals of Cl to form 2 Be-Cl
Cl bonds. So the shape of the molecule is linear with
bond angle 1800.

ii) Formation
mation of ethyne or acetylene (C2H2)
In acetylene, each C atom undergoes sp hybridisation. Out of the 2 sp hybrid orbitals, one of each C overlaps
axially to form a C-C
C σ bond. The remaining two sp hybrid orbitals of each C overlap with the 1s orbital of H to form 2 C-H σ
bonds.
Now each C atom has 2 unhybridized p-orbitals,
p orbitals, which overlap laterally to form 2 π bonds. Thus the molecule has
linear shape with bond angle 1800. Here there are 3 σ bonds and 2 π bonds in ethyne.

4. sp3d hybridisation: It is the process of inter mixing of one s-orbital,

s three p-orbitals
orbitals and one d
d-orbital to form five
new orbitals having equivalent energy and shape. The 5 new orbitals formed are called sp3d hybrid orbitals. These are
directed to the five corners of a regular trigonal
tr bipyramid with bond angles 1200 and 900.
E.g. Formation of PCl5
In PCl5, the central atom P has the electronic configuration 15P – [Ne] 3s23p33d0
To satisfy the penta valency of P, one of the 3s electrons is promoted to 3d level.

Now, one s-orbital, three p-orbitals

orbitals and one d-orbital
d undergo sp3d hybridisation.
These 5 sp3d hybrid orbitals are directed to the five corners of a regular
trigonal bipyramid with bond angles 1200 and 900.
In PCl5, three P-Cl plane, at an angle of 1200. These three bonds are called equatorial bonds. The
Cl bonds lie in one plan
other two P-ClCl bonds lie one above and one below this plane. They are called axial bonds. The axial bond pairs suffer more
repulsion from the equatorial bond pairs. So the axial bond
bond length is greater than the equatorial bond length. So PCl5 is
highly unstable and is very reactive.

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 5. sp3d2 hybridisation: It is the process of inter mixing of one s-orbital,
s three p-orbitals
orbitals and two d-orbitals to form six
new orbitals having equivalent energy and shape. The 6 new orbitals formed are called sp3d2 hybrid orbitals. These are
directed to the six corners of a regular octahedron with bond angle 900.
e.g. Formation of SF6
In SF6 the central sulphur atom has the ground state outer electronic configuration 3s23p4. In the exited state one
electron each from 3s and 3p orbitals are promoted to 3d level.

orbitals and two d-orbitals

Now one s-orbital, three p-orbitals d undergo sp3d hybridisation.
ation. These hybrid orbitals overlap with p-
p
orbitals of fluorine atoms to form 6 S–FF sigma bonds. Thus SF6 molecule has a regular octahedral geometry with bond
angle 900.

Valence bond theory (VBT)

This theory was introduced by Heitler and London and later developed by Linus Pauling in order to explain the
shape of molecules theoretically. VBT can be explained by considering the formation of H2 molecule.
Consider 2 hydrogen atoms A and B with nuclei NA and NB and electrons eA and eB respectively. When the two
atoms are at large distance from each other, there is no interaction between them. So their potential energy is zero. When
the two atoms approach each other, new attractive and repulsive forces begin to operat
operate.
Attractive forces arise between nucleus of one atom and electron of other atom i.e., NA– eB and NB– eA.
Similarly repulsive forces arise between electrons of two atoms i.e., eA – eB, and the nuclei of two atoms NA – NB.
Attractive forces bring the two atoms close to each other whereas repulsive forces push them away.
Experimentally it has been found that the magnitude of new attractive force is more than the new repulsive
forces. So the two atoms approach each other and potential energy decreases. At a particular stage, the net attractive
force balances the net repulsive forces and the energy becomes minimum. At this stagestage, the hydrogen atoms are said to
be bonded together to form a stable molecule. The distance between the two atoms at this stage is called bond length (74
pm). The amount of energy liberated at this stage is called bond enthalpy(435.8kJ/mol)
(435.8kJ/mol)
The potential energy diagram for the formation of H2 molecule is as shown below:

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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 are 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.
Energies of various M.Os
The various M.Os are filled in the increasing order of their energies (Aufbau Principle). The increasing order of
energy is:
σ1s < σ*1s < σ2s < σ*2s < (π2px = π2py) <σ2pz < (π*2px= π*2py) < σ*2pz
For O2, F2 and Ne2, the order is:
σ1s < σ*1s < σ2s < σ*2s < σ2pz < (π2px = π2py) < (π*2px= π*2py) < σ*2pz
Bond Order
It is defined as the half of the difference between the number of bonding electrons (Nb) and the number of anti-bonding
electrons (Na).
i.e. Bond order (B.O) = ½ [Nb –Na]
A molecule is stable only if the bond order is positive. (i.e. Nb >Na). a negative bond order (i.e. Nb < Na or Nb = Na) means
an unstable molecule.
For a single bond, B.O = 1, for a double bond B.O = 2 and so on. Bond order gives an approximate measure of the bond
length. In general, as the bond order increases, bond length decreases and bond enthalpy increases.

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Magnetic nature
If all the M.Os in a molecule are doubly occupied, the substance is diamagnetic. i.e. that substance is repelled by
an external magnetic field. If one or more M.Os are singly occupied, it is paramagnetic. i.e. it is attracted by an external
magnetic field. E.g. O2 molecule.
Molecular orbital Diagram
The representation of various M.Os in the increasing order of energy is called M.O diagram.
Hydrogen Bonding
The weak attractive force between Hydrogen atom of one molecule and electronegative atom (like F, O or N) of the
same or different molecule is termed as Hydrogen bond. It is weaker than a covalent bond but stronger than van der
Waal’s force. It is represented by dotted line (……….).
Cause of H bonding: When H is bonded to a strongly electronegative atom X, the shared electron pair is shifted more
towards X. So H atom gets a slight positive charge (δ+) and the electronegative atom gets a slight negative charge (δ-). This
results in the formation of a polar molecule. The electrostatic force of attraction between these polar molecules is termed
as H-bonding.
δ+ δ- δ+ δ - δ+ δ- δ+ δ-
…….. H-X …….. H-X ……… H-X ………. H-X ……
Types of H bond
There are two types of H bonds- inter molecular H-bonding and intra molecular H-bonding.
1) Inter molecular H bonding: It is the H bond formed by H atom of one molecule and the electronegative atom of
another molecule.
e.g. i) H bonding in HF
….H-F …….. H-F ……… H-F …… H-F ……

ii) H2O H–O ….. H–O…….H–O……H–O…

H H H H

iii) NH3
H H H H
….H –N…..H–N…… H–N ....H– N….
H H H H
Inter molecular H bonding influences the physical properties of the compounds. For example water (H2O) is a
liquid with high boiling point but hydrogen sulphide (H2S) is a gas. This is because in water inter molecular H bonding is
possible which is not possible in H2S.
2) Intra molecular H bonding: It is the H bond formed between H atom and the electronegative atom of the
same molecule.
e.g. H bonding in ortho-nitrophenol

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Chemical Bonding and Molecular Structure Page 13