UNIT 1

Electromagne c Radia on

Electromagne c radia on is a type of energy that is transmi ed (CLUTjy;) through space

(,ilntsp) at enormous (kpfg;ngupa) veloci es. Radiant energy has wave nature and being associated
(cldpUj;jy;) with electric as well as magne c fields, these radia ons are called electromagne c
radia ons.

Regions of Electromagne c Spectrum

 When a narrow beam of light is allowed to pass through a prism or gra ng, it is dispersed
(rpjWjy;) into seven colours from red to violet and the set of colours or band produced is
called spectrum.
 The arrangement obtained by arranging various types of electromagne c waves or radia ons
inorder of their increasing wavelengths or decreasing frequencies is called electromagne c
spectrum. The spectrum obtained by white light is called con nuous spectrum.
 Visible light is a form of electromagne c radia on which lies in the wavelength range of 3800 
(380 nm) - 7600  (760 nm). The region of 3800  wavelength corresponds to violet colour and
region of 7600  wavelength corresponds to red colour.

1  = 0.1 nm

 If the wavelength is less than 3800 , the radia on is called ultraviolet light and if the wavelength
is greater than 7600 , the radia on is called infrared light.
 Infrared as well as ultraviolet radia ons are not visible to the eyes and so these are known as
invisible radia ons.
 The frequency and wavelengths are related to one another as follows,

where,

ν is the frequency of the radia on

λis the wavelength of the radia on

c is the velocity of light (3 X 108 metre/sec)

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 The wavelength and frequency are inversely propor onal to one another, ie., if wavelength
increases the frequency decreases and vice versa.
 Visible radia ons cons tute only a very small por on of the total electromagne c spectrum.
Beyond the infrared region on the side of increasing wavelength are microwaves. Beyond
microwaves lie the radiowaves, which have the highest wavelength.
 Beyond ultraviolet waves, we have X-ray region of lower wavelength.

Regions of Electromagne c Spectrum

Region Limits
X – Rays 0.1 – 100 

Far ultraviolet 10 – 200 nm

Near ultraviolet 200 – 400 nm
Visible 400 – 750 nm
Near infrared 0.75 – 2.2 µm
Mid infrared 2.2 – 15 µm
Far infrared 15 – 200 µm
Microwaves 0.1 – 100 cm
Radiowaves 1 – 1000 m

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Wavelength (λ)

 Distance between two successive peaks of waves, i.e., length of one wave.
 It is usually expressed in cm, the units of wavelength are:

1. Angstrom  (1 = 10-8 cm = 10-10 m)

2. Nanometer nm (1nm = 10-7 cm = 10-9)

3. Micron µ (1µ = 10-4 cm = 10-6 m)

Frequency (ν)
 The number of waves per second is called frequency of an electromagne c radia on.

ℎ /
=
ℎ

 Velocity of light, c = 3.0 X 1010 cm/sec

 The unit of frequency is Hz.

Velocity (c)
 The distance travelled by the wave in one second is called velocity of the wave.

Wave number ( )
 Number of waves spread in a length of one cm. It is equal to the reciprocal of wavelength in cm.
Thus,
1
=

3
  The wave number is a direct measure of energy of radia on. Radia on with large wave number
has high energy.

Spectroscopy

Spectroscopy is the study of interac on of radia on with ma er and imparts informa on

regarding molecular structure (molecular symmetry, bond distances, bond angles), chemical proper es
(electronic distribu on, bond strength).

Uses of Spectroscopy

1. Used in physical and analy cal chemistry for the iden fica on of substances though the
spectrum emi ed from or absorbed by them.
2. Also used in astronomy and remote sensing.

Types of Spectroscopy

1. Atomic spectroscopy - Interac on of electromagne c radia ons with atoms which are most
commonly in their lowest energy state called the ground state.
2. Molecular spectroscopy - Interac on of electromagne c radia on with molecules results in
transi on between rota onal and vibra onal energy levels in addi on to electronic transi on.

Different types of Molecular Energies

In addi on to the ordinary energy of transi onal mo on which is not of concern in molecular
spectroscopy, a molecule may possess internal energy which can be sub-divided into three classes:

1. Rota onal energy

2. Vibra onal energy
3. Electronic energy
4. Transla onal Energy

Energy is associated with the uniform mo on of a molecule as a whole. The energy due to
transla onal mo on is given by,

1
=
2

4
 Due to transla onal mo on the molecule is free to move in the three perpendicular direc ons. It
means that it has three degrees of freedom.

Rota onal Energy

Energy is associated with the overall rota on of the molecule with the atoms considered as fixed
point masses. The value of rota onal energy is given by,

1
=
2

Where, I is the moment of iner a.

w is angular velocity of rota ng molecule.

Vibra onal Energy

Energy is associated with the oscilla on of atoms which is considered as point masses. the
vibra onal energy of a molecule may be given as,

1
=ℎ ( + )
2

Where, is vibra onal frequency.

v is vibra onal quantum number.

Electronic Energy

Energy is associated with the mo on of electrons while considering the nuclei of atoms as fixed
points.

The increase in the electronic energy of a molecule occurs due to an increase in the kine c
energy and poten al energy of the electrons of the molecule.

Type of transi on Region of electromagne c spectrum

Electronic Ultraviolet and Visible

Vibra onal Infrared

Rota onal Far infrared and Microwave

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 Born Oppenheimer Approxima on

The atomic spectra arise from the transi on of an electron between the atomic energy levels,
whereas the molecular spectra arise from three types of energy changes (molecular rota on, molecular
vibra on and electronic transi on). According to Born Oppenheimer approxima on, the total energy of a
molecule is given by,

= + + +

This equa on indicates that the total energy E of the molecule is the sum of transla onal energy,
rota onal energy, vibra onal energy and electronic energy. All of these energies, except transla onal
energy, are quan zed. As the transla onal energy is not quan zed, it is negligibly small and so the Born
Oppenheimer approxima on can be represented as,

= + +

Here,

≫ ≫ ≫

Note:

In the case of a diatomic molecule, the molecule possesses transla onal energy when its centre
of gravity changes as a consequence of mo on.

Rota onal energy arises when the molecule undergoes rota on about an axis perpendicular to
the internuclear axis and passing through the centre of gravity of the molecule.

Vibra onal energy arises because of to and fro mo on of the nuclei of the molecule in such a
way that the centre of gravity does not change.

The electronic energy is associated with the transi on of an electron from the ground state
energy level to an excited state energy level of the molecule because of absorp on of a photon
of suitable frequency.

It should be noted that:

 The vibra onal spectra of a molecule is observed in the infrared region of the electromagne c
spectrum.
 The rota onal spectra of a molecule is observed in the microwave region of the spectrum.
 The electronic spectra of a molecule is observed in ultraviolet and/or visible region of the
spectrum.

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Interac on of Electromagne c Radia on with Ma er & Rota onal, Vibra onal and Electronic
Energy Levels

 Let us consider some energy levels for the neutral sodium atom.

Electronic configura on of 11Na – 1s2 2s22p6 3s1

 Under ordinary condi ons, all the atoms in sodium vapour are in the ground state, that is, their
valency electrons lie in the 3s level.
 When irradiated with radia on of wavelengths 589 and 589.59 nm, the outer valency electrons
of many atoms absorb photons and raised to the higher 3p states.
 The excited electrons have a tendency to return to its normal 3s state, hence emit photon of
energy.
 This process in which the outer electron is raised by one energy level and then returns is known
as resonance absorp on and radia on. The atomic absorp on spectroscopy is based on this
phenomenon.
 With a highly energe c source, not only the valency electrons, but many electrons can be excited
in any element to varying degrees. As a result, the resul ng radia on may contain even several
thousand discrete (njhlu;gw;w jdpj;jdpahd) and reproducible wavelengths, mostly in the
ultraviolet and visible regions. Emission spectroscopy is based on this fact.
 When electromagne c radia on passes from a vacuum to the surface of a por on of ma er, the
electrical vector of the radia on interacts with the atoms and molecules of the medium. As a
consequence the radia on may either be absorbed, transmi ed, reflected or sca ered.
 Absorp on is the process in which a beam of radia on is allowed to pass through a transparent
layer of a solid, liquid, or gas. When an atom or molecule absorbs energy, the atom or molecule
will move to a higher energy state or excited state. In this manner, the electromagne c energy is
transferred to the atoms or molecules comprising the sample.

A simple energy level diagram for either atoms or molecules is given in the Fig.

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 The two horizontal lines reprsent two energy levels within the species. E represents the ground
energy state and E*, the excited electronic state. An electron is capable of undergoing transi on
from E to E* state, if energy in the form of light or heat is absorbed. This absorp on of radia on
causes the molecule or atom to be in an excited state.
 Excited atoms or molecules are rela vely short lived, and tend to return to their ground state
a er approximately 10-8 sec.
 Hence from the excited level, the electron may return to its normal posi on either directly or in
steps with the emission of certain amount of energy .
 When this emission of light is instantaneous, the phenomenon is known as fluorescence, but
when a er some me lag, it is known as phosphorescence.
 When the absorbed energy is stored y the atom or molecule and used in producing some
chemical reac on, fluorescence and phosphorescence become absent and the resul ng
chemical reac on is called photo-chemical reac on.
 Atoms, molecules or ions have a limited number of discrete, quan zed energy levels. For
absorp on to occur, the energy of the exci ng photon must match the energy difference
between the ground state and one of the excited states of the absorbing species.

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 When atoms absorb electromagne c radia on, there is an increase in their electronic energy.
The absorp on takes place only when the energy of the a acking photon of electromagne c
radia on is equal to the energy difference between two quan zed energy levels of the absorbing
species.
 In the absorp on by polyatomic molecules, the number of energy states is greatly enhanced and
the total energy is given by Born Oppenheimer approxima on,

= + +

 When the molecule absorbed energy, the transi on of an electron occurs from an orbit of low
energy to one of higher energy and on returning to the orbit of lower energy, the electron emits
spectral lines of frequency determined by the difference in two energy levels involved in the
process.
 The spectral lines or bands are characteris c of the molecule concerned and hence it is also
called as molecular spectra.
 The electronic spectrum of molecule would be a line spectrum similar to that of atom. But it has
been observed that a molecule can u lise the absorbed energy in other ways also.
 The absorbed energy may rotate the molecule or to cause vibra on of the atoms of molecules.
 The vibra onal and rota onal mo ons are quan zed and are superimposed upon the kine c
mo on of the molecule.
 It should be noted that transla onal mo on is dissipated (tPzhf;Fjy;, tpuak; nra;jy;) as
heat and is not involved in molecular spectra. Hence the spectrum obtained from molecules is a
band spectra.
 The equilibrium posi ons of the atoms in a molecule are determined by the forces which hold
the atoms together.
 Any departure from these equilibrium posi ons gives rise to vibra on of the molecule, known as
molecular vibra on.
 The vibra ons are simple harmonic. The energy E of such a vibra on is quan zed, according to
the equa on,

1
= + ℎ
2

where, is the frequency of vibra on

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 is vibra onal quantum number ( may have values 0, 1, 2, 3, ……)

 In addi on to its vibra on, a molecule can also have rota onal energy I (I is the moment of

iner a, and is angular velocity) about the axis of rota on, known as molecular rota on.

This rota on is also quan zed and energy is given by,

1 ℎ
= I = ( + 1) ×
2 8

= = ( + 1) ×

The rota onal quantum number J can have values 0, 1, 2, 3, ……..

 The energy required for exci ng emission will be least for rota onal and higher for vibra onal
and s ll greater for electronic transi ons.
 If excita on energy is kept so small as to produce only transi ons from one rota onal quantum
level to another within a given vibra onal level, the emission spectra observed would
correspond to changes in the rota onal quantum numbers. Such type of spectrum is called
rota onal spectrum.
 Since the energy involved is small, these spectra are found in the far infrared region.
 If the energy required for excita on is s ll higher and sufficiently large to cause transi on from
one vibra onal quantum level to another within a given electronic level, emissions are observed
corresponding to the change in vibra onal quantum numbers.
 Since change in vibra onal levels involves also changes in rota onal levels, the resul ng
spectrum is called vibra onal rota onal spectrum. As the energies involved are s ll higher, such
type of spectra are found in near infrared region.
 Finally, if s ll higher energies are applied, electronic transi ons may take place which are
accompanied (cld; nry;Yjy;) by vibra onal level change and each vibra onal level change
in turn will be accompanied by rota onal level change. The resul ng spectrum will be complex
consis ng of lines due to electronic, vibra onal and rota onal transi ons.
 Such type of spectrum is called electronic band spectra. Electronic bands are found in the visible
and ultraviolet regions.

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 In a molecule it is possible to have transi ons from many vibra onal and rota onal energy levels
within the ground electronic state to corresponding vibra onal and rota onal levels within the
excited electronic state.
 Due to this, the spectrum otained from molecular species appears to be broad and this type type
of spectra are known as band spectra.
 In the case of an atom, the species can not vibrate or rotate as a molecule does. As a
consequence, the atom does not have vibra onal or rota onal energy levels. A transi on
between energy levels of an atomic species results in very sharp lines. Such type of spectra are
called line spectra.

Microwave Spectroscopy

 The study of the interac on of ma er and electromagne c radia on in the microwave region of
the spectrum.
 It is a type of absorp on spectroscopy. The inerac on of microwaves with ma er can be
detected by observing the a enua on (Nja;T) of a microwave field as it passes through ma er.

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 These are determined by the imaginary or real parts of the microwave suscep blity (vspjpy;
khWgLk; jd;ik).
 Microwave spectroscopy o en called as rota onal spectroscopy because the rota onal changes
are happens in the microwave region.
 Rota onal spectroscopy is only really prac cal in the gas phase, where the rota onal mo on is
quan zed that is the rota onal energy can only take certain fixed values. In solids or liquids the
rota onal mo on is usually quenched (jzpj;jy;, to sa sfy) due to collisions.
 For a molecule to have a rota onal spectrum, it is necessary that it have a permanent dipole
moment, so that it can interact with the electromagne c radia on and and absorb or emit a
photon.
 Thus, pure rota onal spectrum is given only by polar molecules. Consequently, homonuclear
diatomic molecules like H2, N2 etc., and symmetrical linear molecules like CO2, C6H6 do not give
rota onal spectra.
 Thus, polar molecules like H2O, NO, N2O etc., give pure rota onal spectra.

Theory of Rota onal Spectroscopy

The rota on of a three dimensional body is complex. It is convenient to resolve it into rota onal
components about three mutually perpendicular direc ons through the centre of gravity. Thus abody
has three principal moments of iner a are usually designated as IA, IB and I C. Molecules can be classified
into groups according to rela ve values of IA, IB and IC.

Linear Molecules

e.g., H-Cl ; O-C-O

The three direc ons of rota on may be taken as,

(a) About the bond axis.

(b) End over end rota on in the plane of the paper.
(c) End over end rota on in the rigid angles of the plane.

It is clear that for linear molecules, IA is very small because atoms do not move away from their
posi ons. We may say that IA = 0. Also IB = IC, because ene over end rota ons (b) and (c) are iden cal.

Symmetric Top

Here IB = IC ≠ IA

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 H

H C F

Let us consider CH3F.

The end over end rota ons (b) and (c) are iden cal. IA is not zero because when we rotate
molecule about C-F axis, the hydrogen atoms change their posi ons, since the hydrogen atoms are light
IA < IB = IC. Such a molecule is called prolate symmetric top molecule.

In some symmetric top molecules IA > IB = IC. Such a molecule is called oblate symmetric top
molecule. E.g., BCl3.

Spherical Top

Here all the three moments of iner a are iden cal i.e., IA = IB = IC.

e.g., Methane

C
H H
H

Asymmetric Top

Here the three moments of iner a have three different values. IA ≠ IB ≠ IC.

e.g., water, vinyl chloride (CH2=CH-Cl)

Energy level of a rigid rotator

 Masses m1 and m2 are joined by a rigid bar (the bond) whose length is

13
 = + − − − − − − − −1

 Centre of gravity of a diatomic molecule is the point which sa sfies the following condi on:

= − − − − − − − −2

 The moment of iner a of the diatomic molecule is given by

= +

= +

= ( + ) − − − − − − − −3

But from equa ons 1 and 2,

= = ( − )

therefore,

= −

+ =

( + ) =

=
+

and

=
+

Subs tute the values of r1 and r2 in equa on 3,

= × × ( + )
+ +

= = − − − − − − − −4
+

where,

=
+

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 µ is called the reduced mass of the system.

 Equa on 4 defines the moment of iner a in terms of the atomic masses and the bond length.
 By the use of the Schordinger equa on it may be shown that the rota onal energy levels
allowed to the rigid diatomic molecule are given by the expression,

ℎ
= ( + 1) − − − − − − − −5 ℎ = 0,1,2,3 … ..
8

where,

h is Planck’s constant

I is the moment of iner a

J is the rota onal quantum number.

∆
 We know that wave number, ̅ =

Hence the equa on 5 becomes,

ℎ
= = ( + 1) − − − − − − − −6
ℎ 8

where, c is the velocity of the light.

 Equa on 6 is usually abbreviated as,

= ( + 1) − − − − − − − −7

where, B is the rota onal constant,

ℎ
= − − − − − − − −8
8

 From equa on 7 we can show the allowed energy levels diagramma cally.

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 For J = 0 we have ƐJ = 0 and we would say that the molecule is not rota ng at all.
 For J = 1 the rota onal energy is ƐJ = 2B.
 We may con nue to calculate ƐJ with increasing J values.
 If we imagine the molecule to be in the J = 0 state (the ground rota onal state, in which no
rota on occurs), we can let incident radia on be absorbed to raise it to the J = 1 state. The
energy absorbed will be,

− = 2 − 0 = 2

and therefore,

 J  0  J 1  2 B cm1

 In other words, an absorp on line will appear at 2B cm-1.

 If now the molecule is raised from the J = 1 to the J = 2 level by the absorp on of more energy,
we have,

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  J 1 J  2   J  2   J 1

 6 B  2 B  4 B cm 1

 In general to raise the molecule from the state J to J+1, we would have,

 J  J 1  2B( J  1) cm1 ----------9

 Thus a stepwise raising of the rota onal energy results in an absorp on spectrum consis ng of
lines at 2B,4B, 6B,……… cm-1.

Selec on Rules

According to selec on rules, the transi on take place only between those rota onal energy
levels for which,

∆ = ±1

That is change in the rota onal quantum number is unity.

 The transi on ∆ = +1 corresponds to absorp on and ∆ = −1 correspond to emission.

 In other words, a transi on can take place from a par cular rota onal level to just the next
higher or just the lower rota onal level, all other transi ons are forbidden.

Stark Effect

 The Stark effect is the shi ng and spli ng of spectral lines of atoms and molecules due to the
presence of an external sta c electric field.
 The amount of spli ng and or shi ing is called the Stark spli ng or Stark shi .
 The Stark effect is responsible for the broadening of spectral lines.

Applica ons of Microwave Spectroscopy

1. Rota onal spectroscopy is employed to es mate the rela ve abundance (kpFjp) of isotopes.
2. It is used to detect the conforma onal isomers since they have different moments of iner a.
3. The symmetry and geometry of molecules is also determined from microwave spectroscopy.
4. It is used to determine the dipole moment of linear and symmetric top molecules.
5. Microwave spectroscopy has also played a moajor role in the chemical study of interstellar
space.

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Calcula on of moment of iner a and bond length

1. The moment of iner a of CO2 as determined from its rota onal spectrum is 43.217 amu. Determine
the bond length of CO2.

Solu on:

The geometrical configura on of CO2 is O=C=O.

We know that the moment of iner a,

= = + =2

= 2 × 16 ×

= 32 ×

Since I = 43.217 amu

43.217
∴ =
32

= 1.1621 

2. Determine the moment of iner a of 13CS2 if the bond length of 12CS2 is 1.2151 .

Solu on:

We know that isotopic subs tu on does not affect the bond length of molecule.

The geometrical configura on of 13CS2 is

Given rCS = 1.2151 .

We know that the moment of iner a,

= = + =2

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 = 2 × 32 × (1.2151)

∴ = 94.49

3. The spectroscopically measured values of moments of iner a of the molecules HCN and DCN are
11.403 and 13.947 amu respec vely. Determine the bond lengths ofHCN.

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