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4. 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 and for chlorine [17Cl -2,8,7] is
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 an octet of electrons in the valence shell. Or, atoms
containing 8 electrons in their valence shell are stable.
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:

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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 released 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.
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.

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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 with incomplete octet (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.

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 H 2, 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.

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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 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 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.

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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) The valence shell is taken as a sphere with the electron pairs localising on the
spherical surface at maximum distance from one another.
5) A multiple bond is treated as if it is a single electron pair and the two or three
electron pairs of a multiple bond are treated as a single super pair.
6) If a molecule has resonance structures, the VSEPR model is applicable to any such
structure.
7) Presence of lone pairs of electron causes distortion in the expected geometry of
the molecule.
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8) 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.
9) 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 1800. Thus the shape of the molecule is linear with bond angle 180 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

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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
AB2E 3 2 1 Bent SO2, O3
Trigonal Pyramid NH3
AB3E 4 3 1

AB2E2 4 2 2 Bent H2O

AB4E 5 4 1 See-saw SF4

AB3E2 5 3 2 T-Shape ClF3

AB5E 6 5 1 Square Pyramid BrF5

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 triangular pyramid 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 109 028l to
104.50.

Orbital overlap concept

Orbital overlapping is the process of partial interpenetration of atomic orbitals. The important
characteristics of orbital overlapping are:

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1. A covalent bond is formed by the overlapping of half-filled atomic orbitals present in the valence
shell of atoms.
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.

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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 corners of a regular
tetrahedron with bond angle 109028l. Each sp3 hybrid orbitals has 25% s-character and 75% p-
character.
E.g. i) Formation of methane (CH4)
In CH4, the central 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 109 028l. Each of these sp3 hybrid orbitals
overlap with 1s orbital of H to form four C-H σ bonds.

ii) Formation of ethane (C2H6)

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

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The one s-orbital and three p-orbitals of N undergo sp3 hybridisation to form 4 sp3 hybrid orbitals. One
of this sp3 hybrid orbitals is occupied by a lone pair and the other three sp 3 hybrid orbitals overlap with
1s orbital of hydrogen to form 3 N-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.

iv) Formation of water (H2O) molecule

In H2O, the central atom O has the electronic configuration 1s22s22p4.

Now the one s-orbital and three p-orbitals of O undergo sp3 hybridisation to form 4 sp3 hybrid
orbitals. Two of these sp3 hybrid orbitals are occupied by lone pairs and the other two sp3 hybrid orbitals
overlap with 1s orbital of hydrogen to form 2 O-H bonds. Due to the greater repulsion between lone
pairs, the shape is distorted to angular shape or bent structure or inverted ‘v’ shape and the bond angle
becomes 104.50.

2. sp2 hybridisation: It is the process of inter mixing of one s-orbital and two p-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% s-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 undergo hybridisation. The 3 hybrid orbitals formed overlap with
2p orbitals of Cl to form 3 B-Cl σ bonds. Since the hybridisation is sp2, the shape of the molecule is planar
triangular with bond angle 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 to form a C-C σ bond. The remaining two sp2 hybrid orbitals of each C
overlap with the 1s orbital of H to form 4 C-H σ bonds.

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Now each C atom has one unhybridized p-orbital, which 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 s-orbital and one p-

orbital to form 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 and 50% p-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.
Now one s-orbital and one p-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 bonds. So the shape of
the molecule is linear with bond angle 1800.

ii) Formation of ethyne or acetylene (C2H2)

In acetylene, each C atom undergoes sp hybridisation. Out of the 2 sp hybrid orbitals, one of the
sp hybridized orbitals of each carbon, overlaps axially to form a C-C σ bond. The remaining one sp hybrid
orbital of each carbon overlap with the 1s orbital of hydrogen atoms to form 2 C-H σ bonds.
Now each C atom has 2 unhybridized p-orbitals, which overlap laterally to form 2 π bonds. Thus
the molecule has linear shape with bond angle 1800. Hence 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, three p-

orbitals and one 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 bipyramid with bond angles 1200 and 900.
E.g. Formation of PCl5
In PCl5, the central atom P has the electronic configuration 2 3 0
15P – [Ne] 3s 3p 3d
To satisfy the penta valency of P, one of the 3s electrons is promoted to 3d level.

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Now, one s-orbital, three p-orbitals and one d-orbital 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 bonds lie in one plane, at an angle of 1200. These three bonds are
called equatorial bonds. The other two P-Cl 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 length is greater than the equatorial bond length. So PCl5 is
highly unstable and is very reactive.

5. sp3d2 hybridisation: It is the process of inter mixing of one s-orbital, three p-

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 3s 23p4. In the
exited state one electron each from 3s and 3p orbitals are promoted to 3d level.

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

VALENCE BOND THEORY

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.

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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 operate.
Attractive forces arise between nucleus of one atom and electron of other atom i.e., NA– eB and NB– eA.
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 stage, 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)
The potential energy diagram for the formation of H2 molecule is as shown below:

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.

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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 2p z 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 or zero
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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Molecular orbital configuration and Bond order of some Homonuclear diatomic molecules

Molecule M.O configuration No. of No. of Anti- Bond Order =

Total no.
Bonding bonding ½ [Nb –Na]
of
Electrons electrons
electrons
(Nb) (Na)
H2 σ1s2 2 2 0 = ½ [2 – 0] = ½ x 2 = 1
He2 σ1s2 σ*1s2 4 2 2 = ½ [2 – 2] = ½ x 0 = 0
Li2 σ1s2 σ*1s2 σ2s2 6 4 2 = ½ [4 – 2] = ½ x 2 = 1
Be2 σ1s2 σ*1s2 σ2s2 σ*2s2 8 4 4 = ½ [4 – 4] = ½ x 0 = 0
B2 σ1s2 σ*1s2 σ2s2 σ*2s2 = ½ [6 – 4] = ½ x 2 = 1
10 6 4
π2px1 π2py1
C2 σ1s2 σ*1s2 σ2s2 σ*2s2 = ½ [8 – 4] = ½ x 4 = 2
12 8 4
π2px2 π2py2
N2 σ1s2 σ*1s2 σ2s2 σ*2s2 = ½ [10 – 4] = ½ x 6 = 3
14 10 4
π2px2 π2py2 σ2pz2
O2 σ1s2 σ*1s2 σ2s2 σ*2s2 = ½ [10 – 6] = ½ x 4 = 2
σ2pz2 π2px2 π2py2 16 10 6
π*2px1 π*2py1
F2 σ1s2 σ*1s2 σ2s2 σ*2s2 = ½ [10 – 8] = ½ x 2 = 1
σ2pz2 π2px2 π2py2 18 10 8
π*2px2 π*2py2
Ne2 σ1s2 σ*1s2 σ2s2 σ*2s2 = ½ [10 – 10] = ½ x 0 = 0
σ2pz2 π2px2 π2py2 20 10 10
π*2px2 π*2py2 σ*2pz2

He2, Be2 and Ne2 molecules do not exist, since their Bond orders are zero. H2, Li2, B2 and
F2 molecules contain a single bond, since their bond order = 1, C2 and O2 molecules contain a double
bond, since their B.O = 2 and for N2, there is a triple bond since its bond order = 3.
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 Diagrams
The representation of various M.Os in the increasing order of energy is called M.O diagram.

Bonding in Some Homonuclear Diatomic Molecules

1. Hydrogen (H2) Molecule
H2 molecule is formed by the combination of two Hydrogen atoms.
i.e. 1H + 1H H2
1s1 1s1
Total no. of electrons in H2 molecule = 2
So its M.O configuration is σ1s2
M.O diagram for H2 molecule is:

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Due to the absence of unpaired electrons in M.Os, H2 molecule is diamagnetic.

2. Helium (He2) Molecule
He2 molecule is formed by the combination of two Helium atoms.
i.e. 2He + 2He He2
1s2 1s 2

Total no. of electrons in He2 molecule = 4

So its M.O configuration is = σ1s2 σ*1s2
Its M.O diagram is:

Since Nb = Na, B.O = 0 and hence He2 molecule does not exist.
3. Lithium (Li2) Molecule
Li2 molecule is formed by the combination of two Lithium atoms.
i.e. 3Li + 3Li Li2
2
1s 2s 1 2
1s 2s 1

Total no. of electrons in Li2 molecule = 6

So its M.O configuration is = σ1s2 σ*1s2 σ2s2
Its M.O diagram is:

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4. Carbon (C2) Molecule

C2 molecule is formed by the combination of two Carbon atoms.
i.e. 6C + 6C C2
2 2
1s 2s 2p 2 2 2
1s 2s 2p 2

Total no. of electrons in C2 molecule = 12

So its M.O configuration is = σ1s2 σ*1s2 σ2s2 σ*2s2 π2px2 π2py2
Its M.O diagram is:

Energy

5. Nitrogen (N2) Molecule

N2 molecule is formed by the combination of two Nitrogenbon atoms.
i.e. 7N + 7N N2
1s2 2s2 2p3 1s2 2s2 2p3
Total no. of electrons in N2 molecule = 14
So its M.O configuration is = σ1s2 σ*1s2 σ2s2 σ*2s2 π2px2 π2py2 σ2pz2
Its M.O diagram is:

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6. Oxygen (O2) molecule

O2 molecule is formed by the combination of two Oxygen atoms.
i.e. 8O + 8O O2
1s2 2s2 2p4 1s2 2s2 2p4
Total no. of electrons in O2 molecule = 16
So its M.O configuration is = σ1s2 σ*1s2 σ2s2 σ*2s2 σ2pz2 π2px2 π2py2 π*2px1 π*2py1
Its M.O diagram is:

Due to the presence of unpaired electrons, O2 molecule is paramagnetic.

7. Fluorine (F2) molecule
F2 molecule is formed by the combination of two Fluorine atoms.
i.e. 9F + 9F F2
2 2
1s 2s 2p 5 2 2
1s 2s 2p 5

Total no. of electrons in F2 molecule = 18

So its M.O configuration is = σ1s2 σ*1s2 σ2s2 σ*2s2 σ2pz2 π2px2 π2py2 π*2px2 π*2py2
Its M.O diagram is:

Due to the absence of unpaired electrons, F2 molecule is diamagnetic.

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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 Hydrogen bonding: When hydrogen is bonded to a strongly electronegative atom X, the shared
electron pair is shifted more towards X. So Hydrogen 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 Hydrogen bonding

There are two types of H bonds- inter molecular hydrogen bonding and intra molecular hydrogen
bonding.
1) Inter molecular Hydrogen bonding: It is the hydrogen bond formed by H atom of one molecule and
the electronegative atom of another molecule.
e.g. i) Hydrogen 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 Hydrogen bonding: It is the hydrogen bond formed between H atom and the
electronegative atom of the same molecule.
e.g. Hydrogen bonding in ortho-nitrophenol

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