Unit 4: Chemical Bonding & Molecular Structure

Chemical Bond:-

The attractive force which holds together the constituent particles (atoms, ions or molecules) in
a chemical species is known as chemical bond. The tendency or urge of atoms of various elements to
attain stable configuration of eight electrons in their valence shells results in chemical combination.

Lewis symbol:-

The electrons present in the outermost shell that take part in chemical combinations are called
valence shell electrons. G.N.Lewis introduced simple notations to represent valence electrons in atom.
These notations are called Lewis symbols or electron dot symbols.

The common valance of an element is either equal to number of dots in Lewis symbol or it is
equal to number of dots in the lewis symbol or it is equal to 8 minus the number of dots. Atoms
combine either by transfer of valence electrons from one another (gaining or losing) or by sharing of
valence electrons in order to have octet in their valence shells. This is called octet rule.

In relation to chemical bonding, W.Kossel drew attention to the following facts of the periodic
table.

1. In the periodic table, the highly electronegative halogens are placed on the right and the highly
electropositive alkali metals are present on the extreme left, and are separated by noble gases.
2. Halogens gain an electron to form a negative ion while alkali metals lose an electron to form a
positive ion.
3. The negative and positive ions so formed attain stable noble gas electronic configurations. The
noble gases have a stable outer electronic configuration of eight electrons.
4. The negative and positive ions thus formed attain stable noble gas electronic configurations. The
atoms attain noble gas configuration by sharing with other atoms. There are two main type of
bonds, these are
a. Ionic bond
b. Covalent bond.

Ionic bond or electrovalent bond:-

Electrovalent or ionic bond is formed between the atoms by the transference of one or more
valence electrons of one atom to the other atom so as to complete their outermost octets and acquire
stable nearest noble gas configuration. The electrostatic force of attraction which holds the oppositely
charged ions together is known as ionic bond. The compounds containing ionic bonds are ionic
compounds.

Na+ → Na+ + e-

1s22s22p23s1 1s22s22p2

Cl + e- → Cl-

(Ne) 3s23p5 (Ne) 3s23p6

Na+ + Cl- → Na+Cl-

In the formation of electrovalent bond, the number of electron lost or gained by an atom is
called its electrovalence. Atoms that readily lose electrons are called electropositive while those which
readily gain electrons are called electronegative.

Formation of ionic bond:-

The formation of ionic compounds would primarily depend upon.

i. The ease of formation of positive and negative ions from the respective neutral atoms.
ii. The arrangement of positive and negative ions in the solid. This is also called the lattice of
crystalline compound.

Covalent Bond:-

The bond formed by mutual sharing of electrons between the combining atoms of the same or
different elements is called covalent bond.

The dot represents electrons, such structure are referred to as Lewis dot structures. The main
conditions for writing the electron dot structure of covalent molecules are

1. Each bond is formed as a result of sharing of an electron pair between the atoms
2. Each combining atoms contribute at least one electron to the shared pair.
3. The combining atoms attain the outer-shell noble gas configurations as a result of the sharing of
electrons.
4. The formation of covalent bonds in water and carbon tetra chloride are as follows.
 Hydrogen atom contains duplet e- & oxygen attains octet e-
s

4Chlorine atoms & 1 carbon atom attains e-

When two atoms share one electron pair they are said to be joined by a single covalent bond. If two
atoms share two pairs of electrons, the covalent bond between them is called double bond.

When combining atoms share three electron pairs as in the case of two nitrogen atoms in the N2
molecule and the two carbon atoms in the ethyne molecule a triple bond is formed.

Writing Lewis Structure:-

1. The total number of electrons required for writing the structure are obtained by adding the
valence electrons of the combining atoms (in CH4 4e- from C & 4 from H atoms)
 2. For anions each negative charge means addition of an e- to the valence e- and for cations each
positive charge means subtraction of one e- from the valence electron (CO32- ion has 2e-
additionally and NH4+ has loss of 1e-)
3. Knowing the chemical symbols of the combining atoms and having knowledge of skeletal
structure of the compound, it is easy to distribute the total number of electrons as bonding
shared pairs between the atoms in proportion to the total bonds.
4. In general the least electronegative atom occupies the central position in the molecule.
Hydrogen and fluorine occupies the terminal position.
5. After distributing the shared pairs of electron pair for single bond,the remaining electron pairs
are used either for multiple bonds or they constitute lone pairs.

Formal Change:-

The formal change of an atom in a polyatomic ion or molecule is defined a”the difference
between the number of valence electrons in an isolated (or free) atom and the number of electrons
assigned to that atom in Lewis structure”.

Formal charge on an atom in a Lewis structure =

1
Total no. of valence e- in free atom - Total no. of lone pair of e- - (total no. of shared e-)
2

1
FC = V- L - 2S

Ozone Molecule:-

1
Fc on O1 = 6-2-2(6) = 6-2-3 = +1

1
Fc on O2 = 6-4-2(4) = 6-4-2 = 0

1
Fc on O3 = 6-6-2(2) = 6-6-1 = -1
The formal charges help in the selection of the lowest energy structures from a number of possible
Lewis structure for a given molecule or ion. In general, the lowest energy structure is the one, which has
lowest formal charges on atoms.

Limitations of Octet rule:-

1. The incomplete octet of the central atom, the number of electrons surrounding the central atom
is less than eight. This is especially with elements having less than 4 valence e- LiCl, BeH2, BCl3
Li,Be,B have 1,2 and 3 valence e- only, some other such compounds are AlCl3 & BF3
2. Odd e- molecules. There are certain molecules which had odd number of electrons of electron,
like nitric oxide NO and nitrogen dioxide NO2. In these cases, octet rule is not satisfied for all the
atoms.

3. Expanded octet:- there are many stable molecules which have more than 8e- in their valence
shells. For example PF5 has ten, SF6 has 12 & IF7 has 14e- around the central atom. Similarly in
H2SO4 there is 12e- around sulphur atom.

These compounds in which the atom has more than 8e- around it are called hypervalent
compounds. For sulphurdi chloride and sulphur atom has an octet of electrons around it.
 4. Octet rule is based upon the chemical inertness of noble gases. However, it has been found that
some noble gases (especially Xenon & Krypton) also combine with oxygen and fluorine to form a
large number of compounds such as XeF2, KrF2, XeOF2, XeOF4, XeF6 etc.,
5. This theory doesn’t account for the shape of molecules.
6. It can’t explain the relative stability of the molecule in terms of energy.

Ionic or electrovalent bond:-

The formation of ionic compound depend upon

1. The ease of formation of +ve & -ve ions forms the respective neutral atoms
2. The arrangement of +ve & -ve in the solid. This is also called the lattice of crystalline compound.

Factors on which the formation of ionic bond depends:-

1. Low ionization enthalpy-lesser the ionization enthalpy of an atom, the greater is the ease of
losing the valence e- (Alkali & Alkaline earth metals)
2. High electron gain enthalpy- Higher the value of negative electron gain enthalpy greater will be
the ease of formation of anion. Halogen and oxygen group elements mostly form ionic
compounds.
3. High lattice enthalpies- higher the value of lattice enthalpy, greater will be the ease of formation
of the ionic compound. The amount of energy released when free ions combine together to
form one mole of s crystal is called lattice enthalpy

Lattice Enthalpy:-

The energy required to completely separate one mole of a solid ionic compound into gaseous ionic
constituents. This process involves both the attractive forces between ions of opposite charges and the
repulsive forces between ions of like charge. The solid crystal being three-dimensional, it is not possible
to calculate lattice enthalpy directly from the interaction of forces of attraction & repulsion only.

Bond Parameters

1. Bond length:- Bond length is defined as the average distance between the centers of the nuclei
of two bonded atoms in a molecule.
 Bond lengths are measured by spectroscopic, X-ray and electron diffraction techniques. The
covalent radius is measured as the radius of an atom’s core which is in contact with the core of
an adjacent atom in a bonded situation. Vander Waals radius represents the overall size of the
atom which includes its valence shell in a non-bonded situation.

2. Bond angle:- Bond angle may be defined as the average angle between the orbitals containing
bonding electrons pairs around the central atom in a molecule.

3. Bond Enthalpy:- Bond enthalpy may be defined as the amount of energy required to break one
mole of bonds of a particular type between the atoms in the gaseous state.
H2(g) → H(g) + H(g) ∆aH= 435.8 KJ/mol
 In polyatomic molecules the term mean or average bond enthalpy is obtained by dividing total
bond dissociation enthalpy by the number of bonds broken as explained in case of water
molecule.
H2O(g) → H(g) + OH(g) ∆aH-1=502KJ/mol
OH(g) → H(g) + O(g) ∆aH-2=427KJ/mol
502+427
Average bond enthalpy = 2
= 464.5 KJ/mol
4. Bond Order:- the bonds between the two atoms in a molecule.
H:H Bond order=1
O::O Bond order=2
N:::N Bond order=3
C::O Bond order=3, Iso electronic species have same bond order
-
F2,O2 Bond order=1
+
N2,CO,NO Bond order =3, With increase in bond order, bond enthalpy increases
and bond length decreases.

Resonance

When a molecule cannot be represented by a single structure but its characteristic properties can
be described by two or more structure, then actual structure is said to be a resonance hybrid of these
structures.

Conditions for writing resonance structure:-

The following are essential conditions for writing resonating structure.

1. The contributing structures should have same atomic positions

2. The contributing structures should have same number of unpaired electrons.
3. The contributing structures should have nearly same energy.
4. The structures should be so written that negative charge is present on an electronegative atom
& positive charge is present on an electropositive atom.
 5. In contributing structures, the like charges should not reside on adjacent atoms. In general it
may be stated that
I. Resonance stabilizes the molecule as the energy of the resonance hybrid is less than the
energy of any single canonical structures.
II. Resonance averages the bond characteristics as a whole. Thus the energy of the O3
resonance hybrid is lower than either of the two canonical forms I and II

Characteristics of Resonance:-

1. The contributing structures do not have real existence. These are only imaginary proposed to
explain the properties of molecule. Only the resonance hybrid has the real existence.
2. Because of resonance, the bond length in a resonating structure becomes equal. For example
the two bond length if O-O in O3 are equal. All the C-C bonds in benzene are equal.
3. The resonance hybrid has lower energy and thus greater stability than any of the contributing
structures.
4. Greater is the resonance and resonance energy greater is the stability of the molecule.
5. The canonical forms have no real existence. The molecule exist for a certain fraction of time in
one canonical form & for other fractions of time in other canonical forms. The molecule as such
has a single structure which is the structure which is the resonance hybrid of the canonical
forms and which cannot as such be depicted by a single Lewis structure.

Polarity of Bonds:-

When a covalent bond is formed between two similar atoms, the shared pair of electrons is
equally attracted by two atoms. As a result of this electron pair is situated exactly in between two
identical nuclei as shown below.

But in HCl chlorine is more electronegative and attracts the electron cloud towards it & will
experience some negative charge around it & hydrogen atom will experience some positive charge.
These are represented as 𝛿 − and 𝛿 + such molecules are called polar molecules and the bond is said to
be polar covalent bond.

Greater the difference in the electro negativities of the atoms forming the bond greater will be
the charge separation and hence greater will be the polarity of the molecule.

Dipole moment:- (𝜇)

Dipole moment is defined as the product of the magnitude of the charge and the distance of
separation between the charges.

Dipole moment= charge (q) x distance of separation(d)

𝜇=𝑞𝑥𝑑

𝜇 = 𝑄𝑥 𝑑
Dipole moment is usually expressed in debye units (D). The conversion factor is

1D=3.33564 x 10-30 cm

The dipole moment is a vector quantity and represented by the crossed arrow the crossed arrow on

the positive end & arrow on negative end.

In case of polyatomic molecules the dipole moment not only depends upon the individual dipole
moments but also on the spatial arrangement of various bonds in the molecule.

(e.g) H2O Bond angle is 104.5ᵒ

The dipole moment in case of BeF 2 is zero. This is because the two equal bond dipoles in opposite
directions and cancel the effect of each other.

In tetra atomic molecule, for example in BF3, the dipole moment is zero although the B-F bonds
are oriented at an angle of 120ᵒ to one another, the three bond moments give a net sum of zero.

The dipole moment of NH3 4.9 x 10-30Cm is greater than that of NF3 (0.8 x 10-30Cm). This is because, in
case of NH3 the orbital dipole due to lone pair is in the same direction as the resultant dipole moment of
N-H Bonds, whereas in NF3 the orbital dipole is in opposite direction to that of three N-F Bonds.
Fajans rule:-

In the above example all the covalent bonds have some partial ionic character, the ionic bonds
also have partial covalent character. The partial covalent character of ionic bonds was discussed by
Fajans as follows.

1. Smaller the size of the cation, greater is its polarizing power.

2. Polarization increases with the increase in size of anion.
3. Larger the charge on cation greater is polarizing power and large the charge on anion greater is
its tendency to get polarized
4. Cations with 18e- shell configuration cause greater polarization than the cations with 8e- shell
configuration with the same size and charge.
5. The polarizing power of the cation, the polarisability of the anion and the extent of distortion
(polarization) of anion are the factors, which determine the % covalent character of the ionic
bond.

VSEPR Theory:-

Valence shell electron pair repulsion theory basic idea is that bonded atoms in a molecule adopt
that particular arrangement in space around the central atom which keeps them on an average as far
apart as possible. The main postulates are

1. The shape of a molecule depends upon the number of valence shell electron pairs (bonded )
around the central atom.
2. Pairs of electrons in the valance shell repel one another since their electron clouds are
negatively charged.
3. The electron pairs tend to occupy positions in space that minimize repulsions. Therefore they try
to stay as far apart as possible to acquire to a state of minimum energy or maximum stability.
4. The valence shell is taken as a sphere with the electron pairs localizing on the spherical surface
at maximum energy or maximum stability.
5. The valence shell is taken as a sphere with the electron pairs localizing on the spherical surface
at maximum diatances from one another.
6. 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.
7. If two or more resonance structure can represent a molecule, the VSEPR model is applicable to
any such structure.

The repulsive interaction of electron pairs decrease in the order

Lp-lp>lp-bp>bp-bp

VSEPR theory divides the molecules into 2 Categories.

 Molecules

Central atom
Central Atom
has one or more
has no lone-pair
lone-pairs
Valence Bond Theory:-

VSEPR theory gives the geometry of simple molecule but it doesn’t explain the geometry
theoretically, also has its limited applications. To overcome these limitations the following 2 theories
explains

1. Valence Bond Theory

2. Molecular orbital theory

The basic assumptions of valence bond theory are

1. Atoms do not lose their identity even after the formation of the molecule
2. The bond is formed due to the interaction of only the valence electrons as the two atoms come
close to each other. The inner electrons do not participate in the bond formation.
3. During the formation of bond, only the valence e- from each bonded atom lose their identity.
The other electrons remain unaffected.
4. The stability of bond is accounted by the fact that the formation of bond is accompanied by
release of energy. The molecule has minimum energy at a certain distance between the atoms
known as internuclear distance. Larger the decrease in energy, stronger will be the bond
formed.

H2 Molecule:-

Let us consider two hydrogen atoms A and B approaching each other having nuclei NA and NB
and electrons present in them are represented by eA and eB. When the two atoms approach each other
new attractive and new repulsive forces as follows.

Attractive forces arises between:-

I. Nucleus of one atom and its own electron that is NA-eB and NB-eB
II. Nucleus of an atom and electron of other atom NA-eB and NB-eA.

Repulsive forces arise between

I. Electrons of two atoms like eA- eB

II. Nuclei of two atoms NA-NB
 Attractive forces tend to bring the two atoms close to each other whereas repulsive forces tend to
push them apart. A stage is reached where the net force of attraction balances the force of repulsion
and system acquires minimum energy. At this stage 2 hydrogen atoms are said to be bonded together to
form a stable molecule having the bond length of 74pm. Bond enthalpy is the energy that gets released
when bond is formed between 2 hydrogen atoms. Hydrogen molecule is more stable than isolated
hydrogen atoms.

Orbital overlap concept:-

When two atoms approach each other partial merger of two bonding orbitals, known as
overlapping of the orbital occurs.

The overlapping of orbitals results in the pairing of electron. The strength of a covalent bond
depends upon the extent of overlapping. The greater the overlapping, the stronger is the bond formed
between two atoms.
Types of overlapping & Nature of Covalent bond: -

Depending upon the type of overlapping the covalent bonds may be divided into two types

I. Sigma bond 𝜎
II. Pi bond 𝜋

Sigma Bond:-

This type of covalent bond is formed by the end to end hand on overlapping of bonding orbitals
along the internuclear axis. This overlap is known as head on overlap or axial overlap.

I. s - s overlapping- s orbitals overlap along the internuclear axis

II. s – p overlapping:- half filled s-orbital & p-orbitals overlap on internuclear axis

III. p – p overlapping:- 2 half filled p-orbitals overlap with each other on internuclear axis

Pi Bond:-

This type of covalent bond is formed by the sidewise overlap of the half-filled atomic orbitals of
bonding atoms. Such an overlap is known as sidewise or lateral overlap.

The atomic orbitals overlap in such a way that their axes remain parallel to each other and
perpendicular to the internuclear axis.
Strength of sigma & pi bonds: -

The strength of a covalent bond depends upon the extent of overlapping of atomic orbitals
forming the bond. In sigma bond the overlapping takes place to a larger extent & in pi bond the
overlapping occurs to a smaller extent, thus a sigma bond is stronger than a pi bond.

Hybridization: -

The process of intermixing of the orbitals of slightly different energies so as redistribute their
energies resulting in the formation of new set of orbitals of equivalent energies and shape. The new
orbitals formed as a result of hybridization are called hybrid or hybridized orbitals.

Characteristics of Hybridization: -

1. The number of hybridized orbitals formed is equal to the number of the orbitals that get
hybridized.
2. The hybridized orbitals are always equivalent in energy and shape.
3. The hybrid orbitals are more effective in forming stable bonds than the pure atomic orbitals.
4. The hybrid orbitals are directed in space in some preferred directions to have stable
arrangement. Therefore, the type of hybridization indicates the geometry of the molecule.

Conditions for hybridization: -

1. Only the orbitals present in the valence shell of the atom are hybridized
2. The orbitals undergoing hybridization should have only a small difference in energy. The orbitals
which differ largely in energy cannot take part in hybridization
3. Promotion is not an essential condition prior to hybridization.
4. It is not essential that only half-filled orbitals participate in hybridization. In certain cases, even
filled orbitals of valance shell participate in hybridization.

Sp-hydrisation:-

In sp hybridization one s-orbital a one p-orbital mix to form two equivalent sp hybrid orbitals.
The orbitals suitable for sp hybridization are s and pz orbital, if the orbitals lie along z-axis.

Each sp hybridized orbital has 50% s-character & 50% p-character. These two sp hybrid orbitals
point in opposite directions along the z-axis with the bigger positive lobes & very small negative
 lobes. This provides possibility for more more effective overlap resulting ie formation of stronger
bonds. The two sp hybrid orbitals lie along linear arrangement and is therefore called as linear
hybridization.

(e.g) BeCl2, BeF2,BeH2

BeCl2:-

The ground state 1s22s2

The excited state 1s22s22p hybridize

2sp orbitals formed

BeCl2 is a molecule in which the central atom is sp-hybridized and linked directly to two other atoms
which possess linear geometry.

Sp2 hybridization:-

One s and two p orbitals hybridize to form three sp2 hybridized orbitals (e.g) BCl3

Ground state 1s22s22p1

Exited state 1s22s12s22p1 orbital

The three hybrid orbitals so formed are oriented in a trigonal planar arrangements & overlap with 2p
orbitals of chlorine to form three B-Cl bonds.

Geometry of BCl3- trigonal planar

Bond angle of BCl3= 120°

Sp3 hybridization: -

Mixing of one s-orbital and three p-orbitals of equivalent energies and shape hybridize to form
4sp hybrid orbitals, which are 25% s-character and 75% p-character. The four sp3 hybrid orbitals so
3

formed are directed towards four corners of tetrahedron.

Geometry of CH4- tetrahedron

Bond Angle of CH4- 109.5°

NH3 & H2O also undergo sp3 hybridisation, in NH3 three bond pairs & one lone pair of electron pair are
present. The three bond pairs combine with 1s orbital hydrogen.

Lp-bp repulsion > bp-bp repulsion

Angle distorts to 107° from 109.5°

In water molecule (one s & three p) oxygen forms 4 sp3 hybrid orbitals oxygen atom has two
lone pairs, due to this the bond angle is reduced to 104.5o from 109.5o.

C2H6:- sp3 Hybridization

In ethane both carbon atoms are sp3 hybridised and one sp3 orbital overlaps axially with similar orbitals
of other atom to form sp3-sp3 sigma bonds and other 3 orbitals undergo sp3-s sigma bonds with 3
hydrogen atoms.

C-C bond length 154pm

 C-H bond length 109pm

C2H4:-sp2 Hybridization

One sp2 hybrid orbitals of carbon atom overlaps axially with sp2 hybridized orbital of another
carbon atom to form C-C sigma bond, the other two sp2 hybrid orbitals form sp2-s sigma bond with two
hydrogen atoms.

The unhybridised orbital of 2px or 2py of one carbon atom overlaps sideways to form pi bond.

C-C Pi bond 134pm

C-H sigma bond 108pm

C2H2:-sp-hybridisation

Both carbon atoms undergo sp hybridization having two unhybridised orbital 2py and 2px. One
sp hybrid of one carbon atom overlaps axially with sp hybrid orbital of another carbon atom to form
sigma bond. Other hybridised orbital & unhybridised orbital combines with hydrogen atom & orbital &
unhybridized orbital of another atom respectively.
PCl5:- sp3d hybridization

One s, three p & one d orbital hybridise to form 5sp3d hybridised orbital which direct towards 5 corners
of trigonal bi pyramidal.

Three P-Cl bond angle-120° (one plane) equatorial bonds

Two P-Cl bond angle-90° (lying above eq. bonds) Axial bonds.

Axial Bond Equatorial Bond

More repulsive interaction from eq. bonds Less repulsive interaction
Slightly longer Shorter
Slightly weaker Stronger
SF6:- SP3d2 Hybridization.

One S, three P and two d orbitals hybridize to form six new sp3d2 hybrid orbitals which are
projected towards the six corners of a rectangular octahedron in SF6.

These six orbitals form 6𝜎 fonds with six fluorine atoms.

Molecular Orbitals Theory:

The salient features of molecular orbital theory:

i. Electrons of atoms are present in atomic orbitals and electrons of molecules are present in
molecular orbitals.
Same like atoms, molecules have orbitals of definite energy levels.
ii. Molecular orbitals are found by the combination of atomic orbitals of proper symmetry and
comparable energies.
iii. An atomic orbital is monocentric whereas molecular orbital is polycentric (e- in molecular orbital
is under the influence of two or more nuclei)
iv. The e- probability distribution around a nucleus in an atom is given by an atomic orbital, the
electron probability distribution around a group of nuclei in a molecule is given by molecular
orbital.
v. The number of molecular orbitals formed is equal to the number of combining atomic orbitals.
When two atomic orbitals combine they form two molecular orbitals bonding molecular
orbital 𝜎 & antibonding molecular orbital 𝜎 ∗
 vi. The bonding of molecular orbitals has lower energy and hence greater stability than the
corresponding antibonding molecular orbitals.
vii. The molecular orbitals are filled in accordance to aufbau principle, Pauli’s exclusion principle and
Hund’s rule same as that of atomic orbital.

Formation of Molecular Orbitals:

The atomic orbitals of 2 hydrogen atoms A and B be represented by ᴪA and ᴪB. Now when these
atomic orbitals are brought closer they form molecular orbitals

ᴪMO = ᴪA ± ᴪB

i. Molecular orbitals by the addition of wave functions of atoms – bonding molecular orbitals

𝜎 = ᴪA+ᴪB

ii. Molecular orbitals by the subtraction of wave function of atoms – antibonding molecular
orbitals.
𝜎 ∗ = ᴪA-ᴪB

In the formation of bonding molecular orbitals, the two-electron wave of the

bonding atoms reinforce each other due to constructive interference. Due to this e- density is located
between the nuclei of bonded atoms & thus the repulsion between the nuclei is very less.

Electrons placed in a bonding molecular orbital tend to hold the nuclei together
and stabilize a molecule. ∴ a bonding molecular orbital always posses lower energy than its atomic
orbitals.

In the formation of antibonding molecular orbital, the two-electron wave of the

bonding atoms cancel each other due to destructive interference. Due to this e- density is located away
from the space and hence the repulsion between the nuclei is very high.

The electrons placed in antibonding molecular orbitals destabilize the molecule as the
mutual repulsion of e- is more than attraction between the e- & cause a net increase in energy.

The total energy of two molecular orbitals however remains the same as that of two
original atomic orbitals.

Conditions for combination of Atomic Orbitals:

1) The combining atomic orbitals must have the same or nearby the same energy.
 1s can combine with 1s orbital of another atom only and not with 2s orbital of another
atom.
2) The extent of overlapping between the atomic orbitals of two atoms should be large.
3) The combining atomic orbitals must have the same symmetry about the molecular axis
(2pz & 2pz) (2px & 2pz can’t)

Types of Molecular Orbitals:

The sigma (𝜎) molecular orbitals are symmetrical around the bond axis while pi(𝜋) molecular
orbitals are not symmetrical.

The linear combination of1s orbitals centered on two nuclei produces two molecular orbitals
which are symmetrical around the bond axis. Molecular orbitals of type are 𝜎1s and 𝜎 ∗1s.

If the internuclear axis is taken to be in Z- direction, it can be seen that a linear combination
of 2pz orbitals of two atoms also produces two 𝜎2pz and 𝜎 ∗2pz molecular orbitals.

2px and 2py orbitals are not symmetrical around the bond axis because of the presence of
+ve lobes above and -ve lobes below the molecular plane, such modular orbitals are 𝜋 & 𝜋 ∗

A 𝜋 bonding MO has larger e- density above and below the inter-nuclear axis. The 𝜋 ∗
antibonding MO has a node between the nuclei.

Energy Level Diagram for MO:

 The increasing order of energies of various molecular orbitals of O2 & F2

𝜎1s˂ 𝜎*1s˂ 𝜎2s˂𝜎*2s˂𝜎2pz˂ (𝜋2px= 𝜋2py)˂ (𝜋*2px= 𝜋*2py)˂𝜎*2pz

But in Li2, Be2, B2, C2, N2 for instance it has been observed the molecules of B2, C2, N2 the energies are in
the order of

𝜎1s˂ 𝜎*1s˂ 𝜎2s˂𝜎*2s˂ 𝜋2px= 𝜋2py˂ 𝜎2pz˂ 𝜋*2px= 𝜋*2py ˂𝜎*2pz

The energy of 𝜎2pz is higher than 𝜋2px & 𝜋2py.

Electronic Configuration & Modular Behavior:

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

Stability of Molecules:
 The electrons in the bonding molecular orbitals will give stability to the molecule
whereas the electrons in antibonding molecule orbitals will decrease the stability.

If Nb represents the number of electrons in bonding molecular orbital & Na represents

the number of electrons in antibonding molecular orbitals, then

I. The molecule is stable Nb˃Na,

II. The molecule is unstable Na˃Nb,
III. The molecule is unstable Na=Nb

Bond Order:

Bond order is defined as one half the difference between the number of
electrons present in the bonding and antibonding orbitals.

Bond Order = ½ (Nb-Na)

Information from Bond Order:

I. The bond order 1,2 or 3 correspond to single,double or triple bond.

II. The bond length decreases as bond order increases.
III. All MO’s are doubly occupied – Diamagnetic repelled by magnetic field(all electrons are
paired).
One or more MO’s are singly occupied- Paramagnetic(O2) attracted by magnetic
field.(presence of unpaired e-)

Bonding in some Homonuclear diatomic molecules:

1. Hydrogen Molecule(H2): -
Formed by the combination of 2 hydrogen atoms having 1s electron one each 2e -
are present in 𝜎1s molecular orbital.
H2 (𝜎1S)2
𝑁𝑏−𝑁𝑎 2−0
The bond order of H2 molecule is 2
= =1
2
 Single bond, bond length 74pm,diamagnetic

2. Helium Molecule He2 – Hypothetical.

Formed by the combination of 2 helium atoms having two 1se- each.

These 4e- present in 𝜎1s & 𝜎*1s.
𝑁𝑏−𝑁𝑎 2−2
Bond order = 2
= =0
2

no bonding

3. Lithium Molecule: Li2

Formed by the combination of 2 Lithium atoms having 3e- each 1s22s1. these 2
atoms will have 6e- 𝜎1s2 𝜎*1s2 𝜎2s2.
𝑁𝑏−𝑁𝑎 4−2
Bond order= 2
= = 1. Sigma bond, bond length= 265pm diamagnetic.
2

4. Carbon Molecule: - C2
Electronic configuration of carbon 1s22s22p2

There 12 e- in C2. Thus 𝜎1s2 𝜎*1s2 𝜎2s2 𝜎*2s2(𝜋2𝑝𝑥2 = 𝜋2𝑝𝑦2 )

𝑁𝑏−𝑁𝑎 8−4
Bond order= 2
= = 2. Bond order 2, double bond,π bond diamagnetic.
2

5. Oxygen Molecule: O2
Oxygen atom 1s2 2s2 2p4 has 8e-, thus 2 two oxygen atoms will have 16e-. thus e-
configuration.

𝜎1s2 𝜎*1s2 𝜎2s2 𝜎*2s2 𝜎2𝑝𝑧2 (𝜋2𝑝𝑥2 = 𝜋2𝑝𝑦2 ), (𝜋*2𝑝𝑥1 = 𝜋*2𝑝𝑦1 ).

 𝑁𝑏−𝑁𝑎 1
Bond order= 2
= 2 [10-6] = 2. Double bond, 2unpairede-, paramagnetic,

bond length 121pm.Hydrogen Bonding: (Done in L-9)

Inter Molecular Inter Molecular

Hydrogen bonding Hydrogen bonding

(e.g) HF O - nitrophenol