Chapter 4

Chemical Bonding and Molecular Structure

Chemical Bond:The attractive force which holds various constituents (atoms,ions etc.) together in
different chemical species is called a chemical bond.

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(place a dot on Na) and for chlorine [17Cl -2,8,7],
the Lewis symbol is Cl (place seven dots around 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.
Valence Electrons
It is the outermost shell electron which takes part in chemical combination.
Facts Stated by Kossel in Relation to Chemical Bonding
— In the periodic table, the highly electronegative halogens and the highly electro-positive alkali metals
are separated by noble gases.
— Formation of an anion and cation by the halogens and alkali metals are formed by gain of electron and
loss of electron respectively.
— Both the negative and positive ions acquire the noble gas configuration.
— The negative and positive ions are stabilized by electrostatic attraction Example,

Ionic or Electrovalent Bond

Ionic or Electrovalent bond is formed by the complete transfer of electrons from one atom to another.
Generally, it is formed between metals and non-metals. We can say that it is the electrostatic force of
attraction which holds the oppositely charged ions together.
The compounds which is formed by ionic or electrovalent bond is known as electrovalent compounds. For
Example, ,
(i) NaCl is an electrovalent compound. Formation of NaCl is given below:

Na+ ion has the configuration of Ne while Cl– ion represents the configuration of Ar.
(ii) Formation of magnesium oxide from magnesium and oxygen.
Electrovalency: Electrovalency is the number of electrons lost or gained during the formation of an ionic
bond or electrovalent bond.Eg.In the formation sodium chloride ,the valency of sodium is +1 and chlorine
is -1
Factors Affecting the Formation of Ionic Bond
Low ionisation enthalpy of the electropositive atom (metal atom),High negative electron
gain enthalpy of the electronegative atom (non-metal atom),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.
Lattice enthalpy of an ionic compound depends upon following factors:
(i) Size of the ions: Smaller the size, greater will be the lattice energy.
(ii) Charge on the ions: Greater the magnitude of charge, greater the interionic attraction and hence higher
the lattice energy.

Covalent Bond—Lewis-Langmuir Concept

When the bond is formed between two or more atoms by mutual contribution and sharing of electrons, it
is known as covalent bond.
If the combining atoms are same the covalent molecule is known as homoatomic. If they are different,
they are known as heteroatomic molecule.
For Example,
• Lewis Representation of Simple Molecules (the Lewis Structures)
The Lewis dot Structure can be written through the following steps:
(i) Calculate the total number of valence electrons of the combining atoms.
(ii) Each anion means addition of one electron and each cation means removal of one electron. This gives
the total number of electrons to be distributed.
(iii) By knowing the chemical symbols of the combining atoms.
(iv) After placing shared pairs of electrons for single bond, the remaining electrons may account for either
multiple bonds or as lone pairs. It is to be noted that octet of each atom should be completed.

• Formal Charge
In polyatomic ions, the net charge is the charge on the ion as a whole and not by particular atom.
However, charges can be assigned to individual atoms or ions. These are called formal charges.
It can be expressed as
• Limitations of the Octet Rule
(i) The incomplete octet of the central atoms: In some covalent compounds central atom has less than
eight electrons, i.e., it has an incomplete octet. For example,

Li, Be and B have 1, 2, and 3 valence electrons only.

(ii) Odd-electron molecules: There are certain molecules which have odd number of electrons the octet
rule is not applied for all the atoms.

(iii) The expanded Octet: In many compounds there are more than eight valence electrons around the
central atom. It is termed as expanded octet. For Example,

Other Drawbacks of Octet Theory

(i) Some noble gases, also combine with oxygen and fluorine to form a number of compounds like XeF2 ,
XeOF2 etc.
(ii) This theory does not account for the shape of the molecule.
(iii) It does not give any idea about the energy of the molecule and relative stability.
Bond Parameters:
 Bond Length
It is defined as the equilibrium distance between the centres of the nuclei of the two bonded atoms. It is
expressed in terms of A. Experimentally, it can be defined by X-ray diffraction or electron diffraction
method.

• Bond Angle
It is defined as -the angle between the lines representing the orbitals containing the bonding – electrons.
It helps us in determining the shape. It can be expressed in degree. Bond angle can be experimentally
determined by spectroscopic methods.
• Bond Enthalpy
It is defined as the amount of energy required to break one mole of bonds of a particular type to separate
them into gaseous atoms.
Bond Enthalpy is also known as bond dissociation enthalpy or simple bond enthalpy. Unit of bond
enthalpy = kJ mol-1
Greater the bond enthalpy, stronger is the bond. For e.g., the H—H bond enthalpy in hydrogen is 435.8 kJ
mol-1.
The magnitude of bond enthalpy is also related to bond multiplicity. Greater the bond multiplicity, more
will be the bond enthalpy. For e.g., bond enthalpy of C —C bond is 347 kJ mol-1 while that of C = C bond
is 610 kJ mol-1.
In polyatomic molecules, the term mean or average bond enthalpy is used.
Bond Order
According to Lewis, in a covalent bond, the bond order is given by the number of bonds between two
atoms in a molecule. For example,
Bond order of H2 (H —H) =1
Bond order of 02 (O = O) =2
Bond order of N2 (N = N) =3
Isoelectronic molecules and ions have identical bond orders. For example, F2 and O22- have bond order =
1. N2, CO and NO+ have bond order = 3. With the increase in bond order, bond enthalpy increases and
bond length decreases. For example,

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
Polar and Non-Polar Covalent bonds
Non-Polar Covalent bonds: When the atoms joined by covalent bond are the same like; H2, 02, Cl2, the
shared pair of electrons is equally attracted by two atoms and thus the shared electron pair is equidistant to
both of them.
Alternatively, we can say that it lies exactly in the centre of the bonding atoms. As a result, no poles are
developed and the bond is called as non-polar covalent bond. The corresponding molecules are known as
non-polar molecules.
For Example,

Polar bond: When covalent bonds formed between different atoms of different electronegativity, shared
electron pair between two atoms gets displaced towards highly electronegative atoms.
For Example, in HCl molecule, since electronegativity of chlorine is high as compared to hydrogen thus,
electron pair is displaced more towards chlorine atom, thus chlorine will acquire a partial negative charge
(δ–) and hydrogen atom have a partial positive charge (δ+) with the magnitude of charge same as on
chlorination. Such covalent bond is called polar covalent bond.
 • Dipole Moment
Due to polarity, polar molecules are also known as dipole molecules and they possess dipole moment.
Dipole moment is defined as the product of magnitude of the positive or negative charge and the distance
between the charges.

.
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).

• Applications of Dipole Moment

(i) For determining the polarity of the molecules.
(ii) In finding the shapes of the molecules.
For example, the molecules with zero dipole moment will be linear or symmetrical. Those molecules
which have unsymmetrical shapes will be either bent or angular.
(e.g., NH3with μ = 1.47 D).
(iii) In calculating the percentage ionic character of polar bonds.
• The Valence Shell Electron Pair Repulsion (VSEPR) Theory
Sidgwick and Powell in 1940, proposed a simple theory based on repulsive character of electron pairs in
the valence shell of the atoms. It was further developed by Nyholm and Gillespie (1957).
Main Postulates are the following:
(i) The exact shape of molecule depends upon the number of electron pairs (bonded or non bonded)
around the central atoms.
(ii) The electron pairs have a tendency to repel each other since they exist around the central atom and the
electron clouds are negatively charged.
(iii) Electron pairs try to take such position which can minimize the rupulsion between them.
(iv) The valence shell is taken as a sphere with the electron pairs placed at maximum distance.
(v) A multiple bond is treated as if it is a single electron pair and the electron pairs which constitute the
bond as single pairs.

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 1800.

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
 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.
• Valence Bond Theory
Valence bond theory was introduced by Heitler and London (1927) and developed by Pauling and others.
It is based on the concept of atomic orbitals and the electronic configuration of the atoms.
Let us consider the formation of hydrogen molecule based on valence-bond theory.
Let two hydrogen atoms A and B having their nuclei NA and NB and electrons present in them are eA and
eB .
As these two atoms come closer new attractive and repulsive forces begin to operate.
(i) The nucleus of one atom is attracted towards its own electron and the electron of the other and vice
versa.
(ii) Repulsive forces arise between the electrons of two atoms and nuclei of two atoms. Attractive forces
tend to bring the two atoms closer whereas repulsive forces tend to push them apart.
• Orbital Overlap Concept
According to orbital overlap concept, covalent bond formed between atoms results in the overlap of
orbitals belonging to the atoms having opposite spins of electrons. Formation of hydrogen molecule as a
result of overlap of the two atomic orbitals of hydrogen atoms is shown in the figures that follows:

Stability of a Molecular orbital depends upon the extent of the overlap of the atomic orbitals.
• Types of Orbital Overlap
Depending upon the type of overlapping, the covalent bonds are of two types, known as sigma (σ ) and pi
(π) bonds.
(i) Sigma (σ bond): Sigma bond is formed by the end to end (head-on) overlap of bonding orbitals along
the internuclear axis.
The axial overlap involving these orbitals is of three types:
• s-s overlapping: In this case, there is overlap of two half-filled s-orbitals along the internuclear axis as
shown below:

• s-p overlapping: This type of overlapping occurs between half-filled s-orbitals of one atom and half
filled p-orbitals of another atoms.

• p-p overlapping: This type of overlapping takes place between half filled p-orbitals of the two
approaching atoms.

(ii) pi (π bond): π bond is formed by lateral overlapping or side wise overlapping of atomic orbitals.
• Strength of Sigma and pi Bonds
Sigma bond (σ bond) is formed by the axial overlapping of the atomic orbitals while the π-bond is formed
by side wise overlapping. Since axial overlapping is greater as compared to side wise. Thus, the sigma
bond is said to be stronger bond in comparison to a π-bond.
Distinction between sigma and n bonds

Hybridization
Hybridization is the process of intermixing of the orbitals of slightly different energies so as to redistribute
their energies resulting in the formation of new set of orbitals of equivalent energies and shape.
Salient Features of Hybridization:
(i) Orbitals with almost equal energy take part in the hybridization.
(ii) Number of hybrid orbitals produced is equal to the number of atomic orbitals mixed,
(iii) Geometry of a covalent molecule can be indicated by the type of hybridisation.
(iv) The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals.
Conditions necessary for hybridization:
(i) Orbitals of valence shell take part in the hybridisation.
(ii) Orbitals involved in hybridisation should have almost equal energy.
(iii) Promotion of electron is not necessary condition prior to hybridisation.
(iv) In some cases filled orbitals of valence shell also take part in hybridisation.
Types of Hybridisation:
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
6C – 1s 2s 2p
2 2 2

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

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) 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.

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 sp3 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.

1. 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
atom overlaps axially to form a C-C σ bond. The remaining two sp2 hybrid orbitals of each C atom
overlap with the 1s orbital of H to form 4 C-H σ bonds.
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.

2. 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 each C
overlaps axially to form a 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, 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.

3. 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 15P – [Ne]
3s 3p33d0 To satisfy the penta valency of P, one of the 3s electrons is
2

promoted to 3d level.

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.
 4. 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 3s23p4. 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.

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)
The formation of molecular orbitals can be explained by the linear combination of atomic
orbitals. Combination takes place either by addition or by subtraction of wave function
The molecular orbital formed by addition of atomic orbitals is called bonding molecular
orbital while molecular orbital formed by subtraction of atomic orbitals is called
antibonding molecular orbital.
Conditions for the combination of atomic orbitals:
(1) The combining atomic orbitals must have almost equal energy.
(2) The combining atomic orbitals must have same symmetry about the molecular axis.
(3) The combining atomic orbitals must overlap to the maximum extent.
• Types of Molecular Orbitals
Sigma (σ) Molecular Orbitals: They are symmetrical around the bond-axis.
pi (π) Molecular Orbitals: They are not symmetrical, because of the presence of positive
lobes above and negative lobes below the molecular plane.

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

• Electronic configuration and Molecular Behaviour

The distribution of electrons among various molecular orbitals is called electronic
configuration of the molecule.
• Stability of Molecules

• Bond Order
Bond order is defined as half of the difference between the number of electrons present in
bonding and antibonding molecular orbitals.
Bond order (B.O.) = 1/2 [Nb-Na]
The bond order may be a whole number, a fraction or even zero.
It may also be positive or negative.
Nature of the bond: Integral bond order value for single double and triple bond will be
1, 2 and 3 respectively.
Bond-Length: Bond order is inversely proportional to bond-length. Thus, greater the
bond order, smaller will be the bond-length.
Magnetic Nature: If all the molecular orbitals have paired electrons, the substance is
diamagnetic. If one or more molecular orbitals have unpaired electrons, it is paramagnetic
e.g., 02 molecule.
• Bonding in Some Homonuclear (Diatomic) Molecules
(1) Hydrogen molecule (H2): It is formed by the combination of two hydrogen atoms.
Each hydrogen atom has one electron in Is orbital, so, the electronic configuration of
hydrogen molecule is

This indicates that two hydrogen atoms are bonded by a single covalent bond. Bond
dissociation energy of hydrogen has been found = 438 kJ/mole. Bond-Length = 74 pm
No unpaired electron is present therefore,, it is diamagnetic.
(2) Helium molecule (He2): Each helium atom contains 2 electrons, thus in He2 molecule
there would be 4 electrons.
The electrons will be accommodated in σ1s and σ*1s molecular orbitals:
Hydrogen Bonding
When highly electronegative elements like nitrogen, oxygen, flourine are attached to
hydrogen to form covalent bond, the electrons of the covalent bond are shifted towards
the more electronegative atom. Thus, partial positive charge develops on hydrogen atom
which forms a bond with the other electronegative atom. This bond is known as hydrogen
bond and it is weaker than the covalent bond. For example, in HF molecule, hydrogen
bond exists between hydrogen atom of one molecule and fluorine atom of another
molecule.
It can be depicted as

• Types of H-Bonds
(i) Intermolecular hydrogen bond (ii) Intramolecular hydrogen bond.
(i) Intermolecular hydrogen bond: It is formed between two different molecules of the
same or different compounds. For Example, in HF molecules, water molecules etc.
(ii) Intramolecular hydrogen bond: In this type, hydrogen atom is in between the two
highly electronegative F, N, O atoms present within the same molecule. For example, in
o-nitrophenol, the hydrogen is in between the two oxygen atoms.