MOLECULAR

SPECTROSCOPY

B. R. THORAT
DEPARTMENT OF CHEMISTRY,
GOVT. OF MAHARASHTRA,

ISMAIL YUSUF COLLEGE OF ARTS, SCIENCE AND COMMERCE COLLEGE, JOGESHWARI

(E) -60.

 By using X-ray, the special arrangements of the structural units of

crystalline substances are determined. It is also used to determine
special arrangement of the atoms in a molecules & its inter atomic
distances. Such determination is possible in different ways.
The information about the molecular dimension and configuration is
available in case of simple molecules only. To find out the structure of
simple molecules- following two factors are taken in consideration.
(1) Arrangement of the atoms in the molecules, nature of bond, and
strength of molecule.
(2) Determination of actual size of the molecule i.e. distance between
constituent atoms.
A various physical methods are used for such study, some of these are
discusses here 1) Molar refraction
2) Dipole moment
3) Spectroscopy.

 Dipole moment and molecular structure

When covalent bond is formed between two unlike atoms (two atoms that
is differ in their electro negativity).e.g.- A:B, there is an accumulation of
negative charge on the more electronegative atom and positives charge is
developed on the more electropositive atom.
The bonding pair is delocalized towards the electronegative atom and
molecule became polar (the bond is called as polar bond) and the molecule
is called as polar molecules. E.g.:-HCl, HBr, H2O, NH3, PCl3, HF, CO, etc.

In polar molecules, the center of gravity of positive charge and that of

electrons (negative charge) do not co-inside with each others. The polarity
of molecules depends on the difference in electro negativity of constituted
atoms.
in case of nonpolar molecules the center of gravity of positive charge is coinside with center of gravity of negative charge then the molecules are
called as non polar molecules. e.g.H2, Cl2N2, CH4, C6H6, CCl4 etc.

 Dipole moment: In the polar molecules the positive charge (+q) and negative charge (q) are
separated by distance r from each other then it has permanent dipole
moments called as dipole moments and is denoted by latter .
Dipole moment is defined as the vector equal in magnitude to the product of
electric charge q and the distance r having the direction of the line joining
the positive and negative charge.

OR
The dipole moment of the molecule is defined as- it is vector quantity having
magnitude equal to the product of magnitude of charge and the distance
between the two charges (r), having the direction of line joining the positive
and negative centers.

=qr
(01)
a)

q+

q-

u
u1

q-

+u1

q+

u=0
e.g. CO2

c) SO 2

b)

u2

-u1

q-

 If polyatomic molecules containing two more bonds, the net

dipole moment is the vector addition of the individual moments
of each polar bond present in it.
In case of linear molecules, the individual bond moments may
be cancelled out with each other on vector addition and whole
dipole moment is zero or negligible.
But in case of nonpolar molecules, the distance r = 0, so that
the dipole moment is zero.
The charge on the atoms is given in the electrostatic unit (esu)
and the distance between them in angstrom unit. The charge
on the electron is 4.80 10-10 esu. If the electron is
separated from the unit positive charge by a distance one Ao,
then the dipole moment is given as

= 4.80 10-10 1 10-8 esu.cm

= 4.80 10-18 esu.cm

= 4.80 Debyes.
The units10-18 esu.cm being is celled the Debey unit.

Dipole moments and molecular structure

Dipole moment of a molecular structure is an important property used to
determination of a molecular structure because dipole moments measure the
electrical dissymmetry in molecule. Dipole moment is vector quantity and its value is
used to determine the percentage ionic character of the bond and the bond angle in
the molecule.

1) Determination of percentage (%) ionic character

Dipole moment of molecules is useful to study the percentage ionic character of a
bond therefore molecule itself. Consider a simple heteronuclear diatomic molecule
HCl. Its dipole moment is 1.04 D, and the bind length is 1.27510-8cm. If the shared
pair of electrons are completed delocalized towards the chlorine atom i.e. the
molecule will be completely ionized and would have consider H+ and Cl- ions. In that
case the HCl molecule has 100 % ionic character. The dipole moment of HCl when it
is completely ionized is
ionic = q l
= (4.8010-10esu) (1.27510-8cm)
= 6.11 10-18esu.cm
= 6.11 D
But actual dipole moment (measured experimentally) of HCl is 1.04 D. If bonding pair
are at equidistance from the both atoms hydrogen and chlorine, then dipole moment
is zero. Hence percentage ionic character of the molecule is determined as
Percentage ionic character = observed /ionic 100
= (1.04/6.11) 100
= 17%
Therefore the percentage ionic character of HCl bond in hydrochloric acid is 17 %.

 2) Bond moment

Whenever two dissimilar atoms are linked by a covalent bond, the

bonding electrons are unequally attracted due to difference of electro

negativity between them. Hence polarity of the bond arises, i.e. bond
become polar. It is called as bond moment. It is very important to determine
the structure of the compound. Some bond moments are listed below
H-Cl - 1.9, C-H - 0.4, C-I - 1.2, H-F - 1.0, C=O - 2.3, C-O - 0.7, H-Br - 0.8, CCl - 1.5, C-N - 0.2, H-I - 0.4, C-Br - 1.4, O-H - 1.6.
With the help of this bond moment, expected dipole moment of a molecule
can be calculated for the most probable structure of the molecule i.e.
knowing the probable bond angles in the molecule for its various
confirmations. Compared the calculated dipole moment with the
experimentally determined value of the molecule. The possible geometry/
structure of the molecule are confirmed.
The expected or calculated dipole moment of a molecule is the resultant
vectorial sum of the individual bond moments.
e.g.:- CO2, S02, CS2.
O
C
O

= 0.00

= 0.00

O
S

= 1.63

 3) Determination of geometry of simple

molecules Dipole moment of a molecule is an important property
used in determination of molecular structure i.e.
arrangement of atoms of molecule in space. Dipole
moment is a vector quantity
1) hence it is used to determination of a bond angles.
2) The observed value of the dipole moment is used
to determine the charge separation in a molecule
result in resonating structure of molecule. This is due
to electron donating group and electron accepting
group. If presence in conjugation.
3) Dipole moment is used to determined the presence
of inter or intra molecular hydrogen bonding.

 a) Organic molecules
i) The hydrocarbon, CH4 and their homologues CnH2n+2 and aromatic
hydrocarbons have zero dipole moment or very negligible small value
because molecules has center of symmetry.
E.g. p,pdiphenyl compounds has zero dipole moment; indicate that the two
rings of diphenyl arranged in one plane.
R
R

p,pdiphenyl = 0
p,pdiphenyl is not zero.
ii) If one of the hydrogen atom of hydrocarbon is replaced by another atom
or a radical. A bond moment is produced which is characteristics of the
substituent in question. This moment is called group moment. The observed
dipole moment of a molecule is vector sum of all individual bond moments in
that molecule i.e. direction and magnitude are taken in account in the
addition.
e.g. CCl4, here each C-Cl bond has a dipole moment of 1.5 D in magnitude.
Cl
Cl

Cl
Cl

dipole moment is zero.

The molecule is symmetrical, so that the four bond moments cancel to each
other and hence molecule as whole has zero dipole moment.

iii) In multi-substituted benzene derivative, if N1 and N2 are the dipole moments

of the two groups substituted in benzene ring and O is the angle at direction of
moments are inclined, then dipole moment of the compound can be calculated
by using following formula = 12 + 22 +2 1 2cos
If it is assumed that the six carbon atoms in benzene are arranged as to form a
regular hexagon, the angle between the constituents areAt ortho position - = 60o
, cos =
At meta position - = 120o
, cos = -1/2
At para position - = 180o
, cos = -1
The above discussion shows that dipole moment of molecule increases
progressively as molecule becomes more unsymmetrical.
E.g. Dinitrobenzene-Here both the substituents are same hence in case of Para
substituted derivative Dipole moment is zero. For Ortho substituted derivative
dipole moment is 6.0 D and that of for Meta substituted derivative is 3.89D,
Practically.
NO2

NO2

NO2
NO2
NO2

NO2
ortho-

meta-

para-

(At ortho position, = 13, at Mata position, = 1, at para position, = 0 it is

calculated by using equation (35).)

 Ortho effect
In case ortho disubstituted benzene, the observed dipole moment is lower
than that of theoretical value of dipole moment. Calculated by the Vector
summation method. This is due repulsion between groups in ortho position,
the angle is increased than 60o and reduced the dipole moment. E.g. in
Ortho Dinitrobenzene, the observed dipole moment is 6.0D while its
theoretical value is 6,90D. Indirectly the values are used to determine the
steric strain at ortho position.
Resonance or Mesomeric effect
When electron donating and electron withdrawing groups are present in
conjugation i.e. in ortho and para position with each other, the charge
separation spreads over the entire length of molecule and due to resonance
structure, dipole moments increases in appreciable amount. E.g. in Para
Nitro aniline, theoretical value of Dipole moment is 5.65D while that of
observed value is 6-8D.
NH2

NH2

Hydrogen bonding
The Intra-molecular H-bonding results in decrease of dipole moments while
Intermolecular H Bonding increases it. Hence, observed dipole moments is
compared with theoretical dipole moments, may gives the possibility of such
Hydrogen bonding.

 Molecular spectra
Molecular spectroscopy may be defined as the study of the interactions of
electromagnetic radiation with the matter.
The field of spectroscopy can be divided in two main branches- emission
spectroscopy and absorption spectroscopy.
An emission spectrum can be obtained by the excitation of the electrons by
the thermal or electrical means and can be recorded by spectroscopically
analyzing the flame or a electrical spark or by some light source.
The absorption of energy by the electron causes the excitation of it from
ground state to excited state. The life time of the electron in higher energy
state is very less\short therefore it comes to the ground or lower energy state
by the loss of excess energy in the form of thermal energy or light.
The common example of emission spectroscopy is florescent light and
colors giving by the burning salts of same element in the flame.
There are some cases when the excited state has so much of life time, then
also the emission of light is continuous even after the excitation has stopped.
This phenomenon is called as phosphorescence.
E2

excited state

ISC

intermediate state
hv

hv
E1

excitation

hv1

v>v1
ground state

relaxation

Fig:- Florescence and Phosphorescence

 Different Regions of the Electromagnetic Spectrum

The electromagnetic spectrum can be divided into various
regions according to the frequencies. The molecular processes
associated with each region are quite different.
N.M.R.

micro wave

E.S.R.

Infra-red

. .
. .
change
of spin
of nucleus

Visible and
ultra-voilet

.. ..

or

change
of spin
of electron

change of
rotation

gyma and
cosmic rays

X-rays

...

change of electron distribution

change of nucleus
configuration

change of configuration or bond

length or bond
angle
10m

100m

1cm

100um

1um

10nm

Behaviour of molecules/atom in different region of electromagnetic spectrum.

100pm

Properties of lights:The light has two types of nature- wave nature and particle nature. Consider wave nature of lightelectric field
magnetic field

wavelength

dis. O

crest

crest

dis. O

direction of wave

270
360

180

90

time
p
A

trough

trough

y
o

wt

90/w

t
180/w

Electromagnetic radiation consists of energy associated with electric and magnetic fields resulting from the acceleration of the
electronic charge. The electric and magnetic fielding does not have any supporting media and propagating trough the space or
vacuum are at right angle to each other to the direction of propagation. The electronic radiation is considered as a simple
harmonic propagated from source and traveling in a straight line.
A simple harmonic wave has properties of sine wave given by the equation
y = A sin
Where y is vertical displacement, A is the maximum value of vertical displacement called amplitude; is the angle changing
from 0o to 360o.
Consider the point traveled with uniform velocity radian per second in a circular path from point 0. After some time t, the angle
which is equal to t radians. Then vertical displacement is given by equationy = A sin t
As amplitude increases vertically, the angle is also increases and the amplitude is maximum when the angle is \2. When
is , then amplitude become zero, also when is 3\2, again amplitude become maximum and when the cycle become
completed, the amplitude become zero, as shown in fig. the one cycle is completed at the time 2\ seconds.
The above discussion shows that, in one second the point completes the cycles \2 times is called as frequency of wave.
= \2 or = 2
Frequency is defined as the number of oscillation that occurs per second. The units of frequency are the hertz (Hz) or cycle
per second and it has dimensions of reciprocal of time.
The period T is the time interval required for the passage of successive maxima past at a fixed point in space.
T = 1\
Therefore, the basic equation of wave motion isy = A sin 2t
1
Suppose, x is the distance traveled by the wave at time t, then velocity of light is
c = x\t, or t = x\c
2
From equation 1 and 2, we have,
y = A sin 2x/c
3
But, c/ is the equation of wavelength (),
y = A sin 2x/
4
Where, is the wavelength and is defined as the distance between the two successive maxima or minima.

According to the increasing order of frequency, the regions are(i) Radiofrequency region: - 3106 -31010 Hz nuclear magnetic resonance
spectroscopy and electron spin resonance spectroscopy are studied in this region.
The energy change involved the change of spin of nucleus or electron is in the
order of 0.001-10 joules per mole.

(ii) Microwave region: - 31010 -31012 Hz the rotational spectroscopy is

studied in this region. Separations between the rotational energy levels of
molecules are of the order of hundreds of joules per moles.

(iii) Infrared region:- 31012 -31014 Hz the vibrational spectroscopy is studied

in this region. It very important region for the study of spectroscopy. Separations
between the vibrational energy levels of molecules are of the order of 104 joules
per mole.

(iv)Visible and ultra violet region: - 31014 -31016 Hz the electronic

spectroscopy is studied in this region. Separations between the valence shell
electron energy levels of molecules are of the order of some hundreds of kilojoules
per mole.

(v) X-ray region: - 31016 -31018 Hz the energy changes involving in the inner
electrons of an atom or a molecule which may be of order of ten thousand
kilojoules per mole.

(vi) -rays region: - 31018 -31020 Hz the energy change involving the
rearrangement of nucleus particles having energies of 109-1012 joules per gram of
atoms.

 (i) Radiofrequency region: The nucleus and electrons are considered as

tiny charge particles or tint bar magnet and it
spin along its axis produces the magnetic field
which can be interact with the magnetic field of
the electromagnetic radiation of particular
frequency.

. .
. .

change
of spin
of nucleus

change
of spin
of electron

 (ii) Microwave region: The molecules having permanent dipole moment are
microwave active. Such molecules are rotated along its axis
passing through its center of gravity and generate the electric
magnetic components which interact with electric and magnetic
component of light of particular frequency.
But those molecule does not have permanent dipole moment
are microwave inactive. It is used for the simple molecules but
not for the complex molecules because it having several dipole
moment of inertia.
+

+
+

- -

rotation of molecules

dis. O

time

dipole moment change

Fig:- Rotation of molecule.

(iii) Infra red region:In IR-region, the molecules are vibrates which causes the change in dipole moment
are IR-active. If during the vibrations the dipole moment remains constant or zero,
then such molecules are IR-inactive.
e.g. CO2, In CO2, the carbon possessing very small positive charge and oxygen
possessing partial negative charge. During symmetrical stretching vibration, the both
C-O bonds are stretch and compressed symmetrically and simultaneously, net dipole
moment remains constant or zero. Therefore, it is IR-inactive. But in
antisymmetrically stretching vibrations, the one C-O bond stretched while other
compressed simultaneously and vice-versa so that the net dipole moment of the
molecule is not equal to zero (i.e. dipole moment is induced in the molecule) and the
vibration is IR-active. Also the bending vibrations of the molecules are IR-active.
Symmetrically stretching vibration:streach

Asymmetrically stretching vibration:-

dipole
moment

no change in dipole moment

Bending vibrations:-

dipole
moment

compress

Fig:- Vibration of molecule.

 Microwave spectroscopy (Rotational spectra)

The microwave region is concerned with the study of
rotating molecules. The rotation of the body three
dimensionally is quite complicated so that it is
resolved into rotational components about three
mutually perpendicular directions through center of
gravity (the principle axis of rotation). Therefore, body
has three moment of inertia one about each axis as
IA, IB, and IC.
+

+
+

- -

rotation of molecules

dis. O

time

dipole moment change

(a) Rigid diatomic molecule:Consider simple diatomic molecule AB having masses m1 of A and m2 of B, and are separated by a distance
ro (bond length).
ro=r1+r2
(1)
Where, r1 and r2 are the distance between A and B respectively from center of symmetry (c). At the center of
gravity momentum is balanced, therefore,m1r1 = r2m2
(2)
fig.
Y
Z

m1

r1

r2

C- center of gravity

During end over end rotation, at c the moment of inertia is

I = m1r12 + r2m22
(3)
= m1r1r1 + r2m2r2
= m2r2r1 + r2m1r1
= r2r1(m1 + m2)
(4)
However, from equation (1) and (2), we have,
m1r1 = r2m2 = m1(r0 r2) = m2 (r0 r1)
= r0m2 r1m2
r1(m1 + m2) = r0m2
r1 = [m2 /( m1 + m2)] r0
Similarly,
r2 = [m1 /( m1 + m2)] r0
Therefore from equation (4), (5), and (6), we haveI = [m2 m1/( m1 + m2)] r02
= r02
(8)
Where, is the reduced mass of the molecule AB.
= [m2 m1/( m1 + m2)]
gm per molecule
= [m2 m1/( m1 + m2)] .N gm per mole.

(5)
(6)
(7)

m2

By using the Schrdinger equation, the rotational energy levels of rigid diatomic molecules are given by the
equation as,Ej = [h2/82I].J(J+1) joules.
(9)
Where, J = 1,2,3,.= called rotational quantum number, h is the Planks constant, I is the moment of
inertia either IB or IC. by putting integral value of J, several discrete energy level values are obtained of the
molecules. These energy levels having energy in terms of joules, but we are interested it in terms of
frequency, and or wave number asj = Ej /hc = [h/82Ic].J(J+1) cm-1
(10)
Where, c is the velocity of light. The eq. (10) can also be written asj = B J(J+1) cm-1
(11)
Where, B is rotational constant = [h/82Ic] cm-1
(12)
For the various values of J = 0,1,2,3,4,.,calculate the values of j , they are as 0, 2B, 4B, 6B, 8B,
.. There is no limit for the rotational energy of the molecule upto centrifugal force of it is less than
strength of bond. When centrifugal force is greater than the bond strength, the molecule is disrupted.
Selection rule:J = 1
One of the sophisticated applications of the Schrdinger wave equation shows that for this molecule, we need
only consider transitions in which J changes by one unit, and all other remaining transitions are
spectroscopically forbidden. Such results are called as selection rule.
When J=0, equation (11) becomes j =0 called as ground rotational energy state in which no rotation occurs.
The molecule absorbed the energy from incident radiation and get excited to higher energy state J-1. The
energy absorbed by the molecule isj=1 - j=0 = 2B 0 = 2B cm-1
j=1
j=0 =2B cm-1
The absorption line is appearing at 2B cm-1. If the molecule is excited from J=1 to J=2 level by the absorption
of more energy and isj=1
j=2 = j=2 - j=1 = 6B 2B = 4B cm-1
In general absorption lines are appear from the excitation of molecule from J=J state to J=J+1 state, thenj=1
j=2 = B(J+!)(J+2) B (J+1) J
= B (J2+3J+2-J2-J)
= 2B (J+1) cm-1
Therefore spectral lines are appears at J = 0, 1, 2, 3, 4,.., spe. = 2B, 4B, 6B, 8B, and the distance
between two successive spectral lines is 2B.

 Fig:- Rotational spectra of simple diatomic molecule.

-1

42B cm

-1
30B cm

-1
20B cm

12B cm-1

6B cm-1

-1
2B cm

J=0

2B

4B

6B

8B

10B

12B

cm-1

Applications of microwave spectroscopy:Determination of bond length:The distance between two consecutive spectral lines in the rotational
spectra of simple diatomic molecule is 2B.
From the value of B, inter-nuclear distance (r0) can be calculated as2 B = h/82Ic
(1)
or
I = h/16B2c
(2)
From the molecular formula of the compound and isotope present in it,
reduced molecular weight can be calculated as1/ = 1/m1 + 1/m2
or
= [m2 m1/( m1 + m2)]
gm per molecule
= [m2 m1/( m1 + m2)] .N

gm per mole.

(3)

Calculate the value of I by using equation (2) and (3), the value of r0 can
be calculated asr0 = (I/)1/2.

*** The effect of isotopic substitution***

Isotopes- The nuclei of same element having different atomic masses are called
isotopes.
E.g.:- 12C6 and 13C6, 1H1 and 2H1 and 3H1, 16O8 and 18O8, etc.
When particular atom in the molecule is replaced by its isotope, the resulting substance
is identical chemically with original molecule except total mass.
Also inter atomic distance remains unchanged on isotopic substitution. Therefore due to
change in total mass of molecule, moment of inertia and B-value of the molecule is also
changed. Consider the simple molecule 12CO and 13CO. as we go from 12CO to
13CO, the mass goes on increase and hence decrease the value of B.
Suppose B is the rotational constant for 12CO and that of 13CO is B, then B<B i.e.
the spacing between the two energy levels goes on decreasing in 13CO than the 12CO.
This indicates that the heavier species will show a smaller separation between the lines
(2B) than that of lighter molecules (2B). In the following fig. the transition in heavier
molecule is shown by the dash. From the values of B, B, and , can be calculated
i.e. atomic mass of the isotope is calculated.
(B/B) = (h/82Ic)/(h/82Ic) = I/I = r2/ r2 = /
(13)

 Spectrum
12

spectrum of CO
42B cm

-1
30B cm

20B cm-1

12B cm-1

-1
6B cm

2B cm-1

13

spectrum of CO

-1

J=0

2B

4B

6B

8B

10B

12B cm-1

 **** Merits and Demerits of Microwave spectra. ****

The microwave spectroscopy is useful for only those molecules
which possess permanent dipole moment. Thus heteronuclear
diatomic molecules like CO, HCl, HCN, HBr, etc. are microwave
active while homonuclear diatomic molecules like H2, He, N2,
O2, etc. does have permanent dipole moment and therefore are
microwave inactive and studied by using the microwave
spectroscopy.
Microwave spectra is useful for calculation of internuclear
distances in a simple molecules, but linear polyatomic
molecules having several internuclear distances, therefore is
not used to calculated such internuclear distances or bond
length.
The microwave spectra are useful for such substances which
are in either in a gaseous state or which can be easily
converted into vapour state at low pressure. At low pressure,
collision between the molecules is less and hence it can be
rotate freely. It is not applicable for the liquid and solid state
substances.

 ****** Infrared spectroscopy *****

The bond between the atoms are elastic in nature, therefore
atoms in the molecule does not remains in fixed relative
positions but vibrate about same mean position in presence of
IR-radiations.
****The vibrating diatomic molecules****
(a) Energy of diatomic molecules: When two atoms combined to form a stable molecule in which
the repulsion between the positively charged nuclei of both
atoms and between there electrons clouds and the attraction
between the nucleus of one atom and electrons of other and
vice-versa are balanced and two atoms are settle at a mean
internuclear distance. Therefore energy of the molecule was
minimum. When the atoms are closed together, the repulsive
force was increased whereas they pulling apart from each
other, attractive forces are increased, and therefore molecule
can absorb the energy as shown in following

 Vibration of simple diatomic molecule:HCl molecule

Cl

Cl

H
normal

Cl

Cl

Higher energy state

H
compression

energy
H

Cl
Cl

Lower energy state

equlibrium bond length

Inter atomic distance

stretching

 In the fig. the chlorine atom is fixed on one axis

and hydrogen atom is vibrating along its mean
position. The energy of HCl was minimum at
some internuclear distance called as
equilibrium distance and denoted by req. The
molecule behaves just like a spring; therefore it
obeys Hookes low
f = - k (r req.)
(1)
Where, f is restoring force, k is force constant,
and r is the internuclear distance.
Therefore, energy of parabolic curve is
E = [ k (r req.)2]
(2)
This model of vibrating diatomic molecule is
called as simple harmonic oscillator model.

 (b) The simple harmonic oscillator: In above fig. chlorine is consider to be stationary on r = 0 axis, the other
atom (hydrogen) will oscillate between H and H. If energy is increased to
the 1, the oscillation become more vigorous i.e. degree of compression and
stretching will be greater but vibrational frequency will not changed. In
general intrinsic vibrational frequency depends on the mass of the vibrating
system and the force constant but not depends on the amount of distortion.
The oscillation frequency is given by the equation
osc = (1/2). k/ Hz
(3)

Or
= (1/2c). k/ cm-1
(4)
Where, is reduced mass of the vibrating molecule.
The vibrational energy of the molecule is quantized and it can calculated by
using Schrdinger equation of simple harmonic oscillator is Ev = (v + ) hosc joules (v = 0, 1, 2, 3, 4,..)
(5)
Where, v is called the vibrational quantum number. The energy can be
obtained in cm-1 by dividing hc to the equation (5) v = Ev/hc = (v + ) osc cm-1
(6)
The lowest vibrational energy of the molecule (ground state energy) can be
obtained by putting v = 0 in equation (6) v = osc cm-1
(7)
It indicates that the diatomic molecules can never have zero vibrational
energy i.e. atoms are not completely at rest relative to each other. The
quantity osc cm-1is called as zero point energy which depends on the
strength of the chemical bond and the atomic masses.

 The selection rule for harmonic oscillator is

v = 1
(8)
During the vibration, if vibration involves a change in dipole moment of the
molecule is IR-active while which does not involve such change is IRinactive. Therefore energy changes during the vibrations

spect. = v+1 - v

= (v +1 + ) osc - (v + ) osc

= osc cm-1
(9)
Such result shows that vibrational energy levels are equally spaced and
spectral lines are obtained at osc cm-1.
v = 10
v=9
v=8

Cl

H
normal

v=7
v=6
Cl
v=5
energy

11/2 w o

v=4

H
compression

9/2 w o
7/2 w o

v=3
v=2
v=1
v=0

5/2 w o
3/2 w o
1/2 w o
equlibrium bond length

Inter atomic distance

Cl
stretching

 Fundamental vibrations and their symmetry: Consider the molecule having N-atoms and specific symmetry
in space. The total numbers of vibrations of the molecule are
3N (degree of freedom). They are called as fundamental mode
of vibrations.
The molecule is moving in three dimensional space as whole,
without change of shape i.e. changing the position of center of
gravity to do this requires a statement of three coordinate
values. The translation motion uses three of the 3N degree of
freedom leaving 3N-3. The non-linear molecules resolve into
three components about the three perpendicular axes.
Therefore, number of mode of vibrations of non-linear molecule
is 3N-6.
On the other hand, no rotations about the bond axes in linear
molecules, therefore number of mode of vibrations of linear
molecule is 3N 5.
These vibrations are classified into two types stretching
vibrations and bending vibrations.

Stretching vibration:A molecule containing N atoms having N-1 bonds

between its atoms therefore, N-1 of the vibrations is
bond stretching motions. During such vibrations the
distance between two atoms increases or
decreases, but two atoms remains on the same
bond axis. There are two types of stretching
vibrations- (i) symmetrical stretching, and (ii)
asymmetrical stretching.
Symmetric
compressed

Asymmetric

normal

normal

stretching

 (b) Bending vibration: The remaining (2N-4) for linear and (2N-5) for
nonlinear molecules are bending vibrations. In these
vibrations the distance between the atoms does not
change but the positions of the atoms are changed
with original bond axes. The different types of bending
vibrations are listed below+

Scissoring

Rocking

Wagging

Twisting

The various stretching and bending vibrations of a

bond occurs at the certain frequency and when IRlight of the same frequency is incident on the
substance (molecule), energy is absorbed and the
amplitude of the vibrations increased. When the
molecule is come to its ground state, the absorbed
energy is given out in the form of heat.

 ***The Diatomic vibrating rotator***

In a diatomic molecule, the rotational energy separation is in
the order of 1 10 cm-1 while vibrational energy separation is
of the order of 3000 cm-1 in case of HCl. Since the energies of
the two motions are different, therefore it is assume that, it can
be change independently is called as Born-Oppenheimer
approximation.
Total energy of the molecule = Etotal = Erot + Evib joules or
total = rot + vib cm-1
(19)
Taking separate equations for the rot and vib respectively as
vj = j + v cm-1

= [B J (J+1) D J2 (J+1)2 + ] +

[e [1 - (v +) Xe] (v +)] cm-1

Ignore the small centrifugal distortion constants D, H, etc.
vj = B J (J+1) + [e [1 - (v +) Xe] (v +)] cm-1
(20)

The rotational and vibrational energy levels are sketched in following fig.-

4
v=0
3
2
1
0 = j'
.
5

energ
y

4
3
2
1
0 = j''

Inter nuclear distan.

distance distance

v=0

The lowest vibrational energy level v = 0 and v = 1 and the separation between the two
rotational energy levels is same in the v = 0 and v = 1 states. In between two vibrational energy
levels, thousands of the rotational energy levels are placed (spaced).
Selection rule:- v = 1, 2, 3, 4, and J = 1
The selection rule v = 0 also present along with above, but it gives purely rotational
transitions. But J = 0, indicates that the rotational energy change also occurs along with
vibrational energy change (because energy of IR-radiations is higher than that of microwave
radiations; which causes the vibrational energy changes in the molecule).
The rotational quantum in the v = 0 state is J and in v = 1 state is J. The population of the
molecules in rotational energy level J are different and hence we obtained a spectral lines with
different intensities. The analytical equation for the spectrum is obtained by applying the
selection rule.
Consider only the v = 0 to v = 1 transitionjv = Jv=1 Jv=0
= [B J(J+1) + 3/2e 9/4eXe] - [B J(J+1) +1/2e 1/4eXe]
= e (1 2Xe) + B(J-J)(J+J+1) cm-1
= o+ B(J-J)(J+J+1) cm-1
(21)
The value of B is identical in lower and upper vibrational state.
Now we have1) J = 1, i.e. J=J + 1 or J J = 1, hencespect = jv = o+ 2B (J+1)
= o+ 2BJ cm-1 where J= 0,1,2,3,
(23a)
(2) J = -1, i.e. J=J + 1 or J J = -1, hencespect = jv = o- 2B (J+1)
= o- 2BJ cm-1 where J= 0,1,2,3,
(23b)
These two equations are combined asspect = jv = o+ 2Bm cm-1
(23c)
Where, m = 1, 2, 3= (J+1) and (J+1).

 The value of m is positive for the J = +1 and negative for the

J = -1 and it is cannot equal to the zero. The frequency o is
called as the bond origin or bond center. The vibrationalrotational spectrum consist the equally spaced spectral lines on
both side of bond origin o but m0, therefore bond origin
does not appear in the spectrum.
(a) The line appears at low frequency side of o is called as Pbranched lines. (b) The lines appears at the high frequency side
of o is called R-branched lines. (c) If the value of the J = 0
gives Q-branched lines, J = 2, gives S-branched lines (J =
+2) and O- branched lines (J = -2).

Lines arising from J = -2

Called
= O

-1
P

0
Q

1
R

2
S

branches lines.

If we consider the centrifugal distortion constant D, the equation

for the lines become
spect = jv = o+ 2Bm Dm3 cm-1
(24)
The value B ranges from 1-10cm-1, D is in the order of 0.01
cm-1 and the resolving power of the instrument is 0.5, therefore
the value of D can be neglected to a very degree of accuracy.

j=0

j = -1

j = +1

v=1

3
2
1
j' = 0
6

5
v=0
4
3
2
1
j'' = 0
4B
2B
P6

P4

P
3

P2

-w
0

R0

R1

R4

R5