UNIT 4 VIBRATIONAL SPECTRA OF

DIAMOTIC MOLECULES
Structure
4.1 Introduction
Objectives
4.2 Harmonic Oscillator
Hooke's Law
Equation of Motion
Expressions for Force Constant and Characteristic Frequency
Potential Energy Cume
Quant~sationand Energy Levels
4.3 Diatomic Molecule as Harmonic Oscillator
Zero Point Energy
Infrared Spectra and Selection Rules
Evaluation of Force Constant and Maximum Displacement
Isotope Effect
Vibrational Term Value
4.4 Anharmonicity
Morse Potential
Energy Levels of Anharmonic Oscillator and Selection Rules
Evaluation of Anharmonicity Constants
4.5 The Vibrating Rotator
Energy Levels
The IR Spectra and P.Q.R Branches
Symmetric Top Vibrating Rotator Model
4.6 Summary
4.7 Terminal Questions
4.8 Answers

4.1 INTRODUCTION
While going through Unit 7 of the course "Atoms and Molec,uIes" (CHE-Ol), you
might have appreciated the use of vibrational spectroscopy as an analytical technique
for the determination of molecular structure. In the last block of this course, two units
viz. Units 1and 3 have been devoted to atomic spectra and rotational spectra,
respectively. In this unit and Unit 5, we will discuss vibrational spectroscopy which is
another kind of spectroscopy dealing with molecules.

In this unit, the theory and applications of vibrational spectra of diatomic molecules
will be described. The vibrational spectra of polyatomic molecules is discussed in
Unit 5.

In this unit, we will start our di.scussion with the classical example of the vibration of a
single particle supported by a spring. The similarity of the vibration in a diatomic
molecule with the vibration of a single particle is then brought about and possible
transitions for the harmonic os;cillator model of diatomic molecules are discussed. This
is followed by the explanation of observed vibrational spectra of diatomic molecules,
the introductioli of anharlnonicity and the rotational- vibrational spectra of diatomic
molecules.
 Objectives
After studying this unit, you should be able to:
discuss Hooke's law and motion of a harmonic oscillator,
explain observed infrared spectra of diatomic molecules,
a evaluate harmonic frequency of diatomic oscillator, force constant and
anharmonicity constant from the observed infrared spectra,
predict vibrational frequencies of isotopically substituted molecules if the
vibrational frequencies of unsubstituted molecules are known,
evaluate zero point energies, and
explain rotational-vibrational spectra of diatomic molecules.

4.2 HARMONIC OSCILLATOR

Consider a particle of mass m held by a rigid support through a spring as shown in Fig.
4.l(a). When this particle is displaced from its equilibrium position (a) see Fig. 4.1 .

Rigid support -+ Particle of mass 111

(c)

(4

(b)

Flg. 4.1: Contractlon (c) and expanslon (b) of the spring showlng displacement of the par-
from Its equllibrlum posltlon (a). The restoring froce Facts h a dlreetlon opposltc Lo
the dlrectlon of dlsplaccment.

using some external force (like pushing or pulling by hand), it is observed that the
particle tends to go back to its equilibrium position after the force is withdrawn. As it
will be explained in sub-Sec.4.2.2, the particle not only goes back to its equilibrium
position but goes still further on the opposite side till the distance is equal to the initial
displacement and if there is no frictional loss or gravitational pull, the particle keeps
moving betwekn the two extremes in a periodic motion. Such oscillations are referred
to as Simple Harmonic Motion (SHM) and the particle is referred ais a Harmonic
Oscillator.

4.2.1 Hooke's Law

The motion of the particle referred above towards its equilibrium position after the
external force is withdrawn can be explained as follows. On giving a displacement (x)
to the particle, a force called restoring force (F) arises in the spring in the direction
opposite to that. of the displacement and acts to bring it back to its equilibrium
position. A spring which behaves in this manner is said to obey Hooke's law. Hooke's
id. 'hc negatlve SIP in Eq.
law states that the restoringforce (F)isproportional to tHs displacement (x) and acts in a
4 i .?d. L rhdt !f the
.- ., .* IS posrtive, the direction oppositt! to the direction of the displacement. This can be represented
,r :r.e I\ n~sattveand mathematically as:
c <- '
The proportionality constant, k is called the force constant of the spring. The force
constant k is a measure of the strcngth of the spring. Hence, a large value of k means a
stronger and less flexible spring. From Eq. 4.1,it may be further noticed that for a
given value ofx, a larger value of k will result into a larger restoring force.

4.2.2 Equation of Motion

It is experimentally observed that if the particle is displaced from its equilibrium
position by a distance +xo (Fig. 4.lb) and the external force is withdrawn, the particle
returns to the equilibrium position (Fig. 4.la) and then continues to move to a
position, -xo, away from the equilibrium position (Fig. 4.1~).The state of the sprin,:
in Fig. 4.1(b) and 4.1 (c) corresponds to the stretched and the compressed states.
respectively. And as mentioned above, if there is no frictional loss or gravitational i.:.'I
the particle continues to move between these two extremes passing through the
equilibrium position. If the value of the maximum displacements (also called
amplitude) on the two extremes is denoted by -xo and +xo, then the value of the
displacement (or amplitude) x after time t sec is given by a cosine function (Fig. 4.2) as
shown below:

where vosc is the oscillation frequency in sec-' . Equation 4.2 represents the equation sin,ilar to E ~4.2,
.
of motion of the particle. .u can also be glveli
x = x o s ~ n2z I ,,.
You nust also relnt n )L t' I ? thr
\in functton is 90" c *
with respect tci thc . L - -1

timc. -r

Fit 4.2: A cosine functlon represents the equetlon of motion of the hermonlc oscillator.

4.2.3 Expressions for Force Constant and Characteristic Frequency

Now, the restoring force F in Eq. 4.1 can be represented in terms of Newton's second
law of motion as:

where a is the acceleration of motion which is denoted by second differential

d2x
ofx with respect to time, i.e. a = - This on combination with Eq. 4.1 gives
d t2'

Using Eq. 4.2 for x, we find

 The results of Eqs. 4.4 and 4.5 on combination give
-
dr
dr
=-~~2nv,,sin2nv~,r
-

ar
2 2 From the above equation, we can get the expression for the force constant, k as
= - 4 n v,, xocos2nv,,,,t

and that for the oscillation frequency, vo, as

Thus, for a given spring with force constant, k and a particle of mass, m there is only
one oscillation frequency possible, v,, ,which is independent of the maximum displace-
ment of the particle. This is called characteristic frequency of the harmonic oscillator.

4.2.4 Potential Energy Curve

If Fat is the external force applied to displace the particle by a distance dr, the work
done in doing so is stored as potential energy (P.E.), dV. Thus
dV = F,, dr ...(4.8)
Note that work is given as
~OIIOWE:
Since the external force is equal and opposite of the restoringforce (4)
exerted by
wort = fonr distance the spring, we can write

If equilibrium position is taken as that of zero potentialenergy,integrationof above

equation gives

Since potential energy varies linearly with the square of the displacement, a plot of V
vs. x gives a parabola as shown in Fig. 4.3.

Flg. 4.3 Potential en- curve of (be bormonlc osclllpbr.

Now let us imagine that the particle has been displaced by a distancexo and released. Vibrational Spectra
of D i a t o h i c Molecules
When it is displaced by a distancexo, at that point it has gained a potential energy of
-21 kxo.2 After its release, say at a time t if the displacement isx, ,then its potential
1 1. 1
energy will be -k x i . The difference,
. .
-k x i - -k x: represents the kinetic energy of the
2 2 2
1
particle which is given by -mv2 where v is the velocity of the particle at a displacement
2
x,. Thus,one can determine the velocity of the particle at a displacementx, if one knows
the values of m, k,xo andx,.

Thus,

Using v =-
dx wecanwrite
dt '

Total energy = k d = 2 mn2 v,x2o 2

2

4.2.5 Quantisation and Energy Levels

As you have been introduced in Unit 2 of the "Atoms and Molecules" Course
(CHE-Ol), the motion of a microscopic particle can be described in quantum
mechanics by Scbrodinger's wave equation. Similarly, the motion of a harmonic
oscillator, if the particle involved is microscopic in nature, can be discussed by solving
Schrodinger wave equation. We shall not go into the details of the solution, however,
we shall use the results obtained which are very interesting.

The wave equation of this system is given as

where tb is the wave function of the oscillator. h is Planck's constant and E is the total
energy of the oscillator. The solution of this equation gives the energy, E as given You may remember from Unit 2 of
'Atoms and Molecules' (CHE-01)
below: course that Schddinper Equation
-
-
for a varticle in one dimension
,/;
7
h k 1 can be given as follows:
E=- (V+ 7) ...(4.17)
&++(E-V)r-o
a2
where v is an integer and can take values 0, 1,2, .........etc. and is known as vibrational h
quantum number. nqforv=fk&rrget

Using Eq. 4.7, we can write Eq..4.17 as given below:

The expression for E given in Eq. 4.18 deserves some further analysis. It shows that E
has different values for different values of v . Increasing v by one integer increases the
IR nnd R n r n n ~Spectm
~ value of E by a quantity hv,, where v,,, is the characteristic frequency of the
oscillator. This shows that the energy of the oscillator cannot be changed at will but it
can be only changed by a multiple of hv,,. This is referred to as quantisation of
energy. By showing the values of E for varying values of v we can build up energy levels
as shown in Fig. 4.4.

-cm-'
Absorption of radiation

FLg. 4.4: Energy levels of a harmonic oscillator.

4.3 DIATOMIC MOLECULE AS HARMONIC

OSCILLATOR
Let us now consider two particles of masses ml and mz joined together by a spring
having a force conitant k (Fig. 4.5a). The distance of separation between the particles
is re. The spring can be stretched and compressed by pulling the two particles apart
(Fig. 4.5b) or by pushing them to come closer (Fig. 4.5~).

- r1 '
i
i
,a
.
j COM
0
12 -a

Flg. 4.5: Strelchlng and compression of lwo partides Jolned togttber by a spring.

Point 0 in Fig. 4.5 indicates the centre of mass and il and r2 denote distances of the
 Vibrational Spectra
particles 1and 2, respectively, from the centre of mass 0. If the new distance of
of Diatomic Molecules
separation of the two particles in Fig. 4.5 (b or c) is referred to as r, the displacement
of ml with respect to m2 given by r - re (while keeping the centre of mass at 0 ) can be Note that the potential energy is
employed in the equations of motion (similar to Eq. 4.4) as follows: proportional to the square of
relative displacement of the
particle and is given by
--
m1&
- -k(f - re) ...(4.19) v = - k1( r - r e ) 2
d t2 2
and the restoring force is given as
and F = -k(r -re).
Thus, the equations of motion for
the two particles ml and mz are as
."(4.20) given by Eqs 4.19 and 4.20,
respectively.

Since r = rl + r2 and mlrl = m y 2 , we get From kl rl = mz rz, we can write

r1 = m2 r and r2 = r
...( A )
"'1 + 7
'2
'- "'1 + 7' 2'
rnlrl
and r =- ...(B)
Using these expressions for rl and r2, Eqs. 4.19 and 4.20 reduce to m2

We can take out m2 and (ml + mi) out of differentiation because they are constant. mlm2

From rl + r2 = r, we can say that

Thus, ...(4.22)
r1 = r - r2
Using this value of rl in Eq. A
Here ml m2/(ml + mi) can be denoted byp which is called the redueed mass. above, we get

Thus, Eq. 4.22 can be rewritten as

mlr
d2(r - re) d2r d2(r-re) d2r. or
(m2 + m l> = '2
Since = -because r is a constant, we substitute for -m
d? d? d t2 d? Similarly, from the Eq. B above,
Eq. 4.24 for )laving similarity in the variable on the two sides of the equation. Thus, we can derive

A comparison of Eqs. 4.4 and 4.25 shows that the two expressions are similar if m of
Eq. 4.4 is identified with p of Eq. 4.25 andx of Eq. 4.4 is identified with r - re of Eq.
4.25. This leads us to conclude that the oscillational motion for two particles joined
together can be identified to the simple harmonic vibration of a particle of mass equal
top and a displacement equal to r - re (called A r) in the above case. Going on similar
'
analogy, therefore, we can write equations similar to Eqs. 4.2,4.6,4.7,4.11 and 4.12 for
oscillations of the two particles joined by a spring viz.
IR and Rnnlon Spectrs

1
V = -k(r
2
- re)2 ... (4.29)
1
K.E. = ~p
-
v- ... (4.30)
where v,,, is the characteristic oscillational frequency of the system under
consideration, and v = d (A r)/dr.

The vibrations in diatomic molecule can be treated in a similar way. Instead of the
spring with force constant k, we have in the case of diatomic molecules binding of the
two nuclei through a bond with a force constant k and these nuclei oscillate with a
zt:aracteristic oscillational frequency, vow '

Extending the similarity further the wave equation for oscillation in diatomic molecule
can be given similar to Eq 4.16 viz.

and the expression for energy similar to Eq. 4.17 can be given as

4.3.1 Zero Point Energy

Let us study the above equation more carefully. You will realise that even for v = 0,
the energy E is not zero and the molecule oscillates with a definite value of frequency.
1
The energy at v = 0 is given by E,, = - h v,, and is referred to as zero point energy.
2
The zero point energy corresponds to the energy of the molecule in the vibrational
ground state.

4.3.2 Infrared Spectra and Selection Rules

If infrared radiations are passed through a sample of diatomic molecules in the gas
phase and the transmitted radiations are analysed through the monochromator and
detector of a spectrometer (for details of working see -,Unit 9) an infrared spectrum is
obtained. The infrared spectrum results from the ab'sorption of radiation causing
transition from one energy level to another. The observed line position in the spectrum
gives information about the difference between the energy levels. However, the
intensity of the spectral lines gives irdornytion about the population of levels involved
in the transition. The spectruni so obtamed is characteristic of the diatomic molecule
under investigation. The spectrum is employed to get information about the vibrations
of the molecule and interactions between the vibrational and rotational motions.

The infrared spectral bands observed for HCl are shown schematically in Fig. 4.6.
Notice a signal with a strong intensity followed by two more of weak intensity (Fig. 4.6
a). The positions of the signals are given in terms of frequency of radiation absorbed,
v (cm-'1.
The frequency, v (sec-I) = c t (cm-I), where c is the velocity of light.

Because of various broadening mechanisms as well as rotational fine .structure, these

signals do not appear as single lines but appear as bands. Depending on the resolution
of the equipment used, the bands show different type of features and fine structure as
shown in Fig. 4.6 (c). We shall try to understand salient points of this spectrum in the
following sections.
 Vibrational Spectra
of Diatomic Molecules

Internuclear distance

6) (iii)
Flg. 4.6 (a): Schematic representation of the posltiom and intensities of first tbrte ban& of HCI.
The numbers in notation 0- 1,O-2 and 0-3 indicate the initial and final levels of
each (ransltion.

(b) A typlcal potenUa1 energy C U I - V ~for a dlatomlc moltcole. The mlnlmum in thy c o n e
re, corresponds to the equilibrium distance between the atoms. Horlwntnl llnes
represent vibrational levels. Transitlolur shown by a, b and c art the fundpmentd,
f i s t overtone and second overtone, respectlvely. The devlaUon from equal spaclng
between energy levels I s due to anharmonicity, as you wlll study ln Stc 4.4.

(c) Fundamental band of HCI under (I) low, (11) moderate and (Ill) hlgh resolutlom.

As given in Fig. 4.4, the energy levels for diatomic molecules, when considered similar
to those of harmonic oscillator, are equidistant with an energy gap equal to h v,,
where v,,, is the vibrational frequency of the diatomic molecule in sec-' and h is
Planck's constant. A promotion of the diatomic oscillator from a lower level to an
upper level can take place if an external energy, equal to the energy gap between the
two levels, is supplied. If the energy supplied is in the form of an electromagnetic
radiation with frequency v sec-l, a transition will occur if E = E2 - El = h v where E2
and El denote energies of the final and the initial levels. Note the difference between v
and v,,, ; the former denotes the frequency of electromagnetic radiation whereas the
latter denotes the oscillational frequency of the diatomic molecule. If the quantum
numbers, v for final and initial levels are given by v, and v,, respectively', then

An absorption of radiation takes place and the oscillator flips from energy level with
quantum number vi to that with vf as shown in Fig. 4.7. The transitions'for which ,

A v = 1are called fundamental transitions and those with Av = 2,3,4 etc. are called
first, second, third etc. overtones respectively.

Eq. 4.33 shows that afundamental transition takesplace ifthe frequency of

electromagnetic radiation is equal to the oscillational frequency of the diatomic molecule:
The overtone transitions take place i f the frequency of electromagnetic radiation is an
integral multiple of the oscillationirl frequency.
IR nnd Rnmnn Spectra

Fig. 4.7: Absorption of rndltlon and vlbratlond (ransltlon.

As you have noticed in Eq. 4.33, the harmonic oscillator with different energy levels
defined by different values of v, has different wave functions. As mentioned in the
appendix of Unit 2, an electric dipolar transition from energy level v, to vfis only
allowed in case the transition moment integral given below is non-zero, i.e.

where. yl,. and yl,. are wave functions for vrand vi levels, d T, is volume element and M is
J- I
dipole mdnent operator. Without giving any further derivation, it can be stated that if
dipole moment is a linear function of internuclear distance of the diatomic molecule,
the above integral is nonzero only if Av = f1 and if the dipole moment is a non linear
function of internuclear distance, the above integial is nonzero for all integral values
of Av. However, in practice only transitions with Av = f 1 are allowed for harmonic
oscillator model of diatomic molecules where the dipole moment is known to be a
+
linear function of the internuclear distance. The " " sign for Av above refers to
transitions from lower energy levels to higher levels whereas the "-"sign refers to
transitions from higher energy levels to lower energy levels. The absorption of
+
radiations thus corresponds to " " sign and emission of radiations to "-"sign of the v
values given above. Further, expansion of dipole moment operator M in Eq. 4.34
shows that fundamental traniitions are allowed only if dpld(A r)is non zero, i.e. the
vibration should be accompanied by a change in the dipole moment to show a
fundamental transitibn. Thus, the homonuclear diatomic molecules do not show any
absorption in the fundamental vibrational spectrum. These rules regarding which
transitions are allowed and which are forbidden, are referred to as Selection Rules.

Since the frequency of the electromagnetic radiation which satisfies the condition
Remember that according to the given in Eq. 4.33 falls in the infrared region, these transitions are referred to as
Boltman distribution, the number infrared transitions and are observed in the infrared region of the spectrum. The
of molecules present in' the excited intensity of the band corresponds to the amount of radiation absorbed and is related
state (fi)are related to the to the square of the transition moment integral (Eq. 4.34). The frequency at which the
number of molecules in the maximum absorption is observed corresponds to the frequency of electromagnetic
ground state (N1)by the following radiation responsible for transition as defined by Eq. 4.33. According to the Boltzman
expression: distribution, the number of oscillators in v w 0 level are expected to be very small at
room temperature; hence only transitions from v = 0- v = 1are observed where
the v0, for the oscillator is equal to the frequency of the electromagnetic radiation
absorbed to give the fundamental transition. At higher temperatures v = 1
etc. transitions may also be observed. Such transitions are referred to as hot
v =2 -
transitions (or hot bands in the spectrum).

4.3.3 Evaluation of Force Constant and Maximum Displacement

'
As we have noticed above, the frequency of electromagnetic radiation at which
absorption takes place can give the value of oscillational frequency of the diatomic
molecule, e.g. for a transition vi = 0 to vr= 1.
 Vibrational Spectra
and if we know the reduced mass of the diatomic molecule, we can calculate the value of Diatomic Molecuies
of force constant, k by using Eq. 4.27 and 4.28. Eqs. similar to 4.15 and 4.17 for
diatomic molecule can be employed to evaluate maximum displacement A ro for
various values of v as follows:

Totalenergy = ?LAG
1
=~ P J ? V & , A ~

giving Aro =

SAQ 1
HCl molecule shows an absorption at 2886 cm-l. Determine its force constant and
maximum displacements (changes in internuclear distance) for v = 0,1,2,3.

4.3.4 Isotope Effect

We have noted above that the HCl molecule absorbs radiation of 2886 cm-I frequency.
Let us see what changes we expect in the infrared spectrum, if HC1 is changed to DCI.
This brings change in the reduced mass, i.e.

Thus, we can say that

PDCI ~PHCI

The force constant is a property of the bond which in turn depends on the number of
electrons in H and D. Since number of electrons in H and D h e equal it is assumed
that to a good degree of approximation that the force constant for HCI and DCl are
equal.

Using the above argument in Eq. 4.28, we can conclude that

Thus,
.m
IR n r , i Rnmnn Spectra And since the fundamental transition takes place with electromagnetic radiation of
frequency equal to oscillational frequency, we can write that
In gcri . al, we can say that

. f r ere vi and pi denote the

Thus,when HCl is changed to DCl, the fundamental transition in infrared spectrum is
frequency and the reduced mass observed at a lower frequency of electromagnetic radiation than that for HCl and the
for the isotopically substituted ratio between these frequencies is given by Eq. 4.40.
molecule.

SAQ 2

If the fundamental transition for 0-H species is observed at 3735 c m l , find out the
position of the corresponding transition for 0-D species.

SAQ 3
Calculate the ratio between the zero point energies of HCl and DCl.
.......................................................................................................................................................

4.3.5 Vibrational Term Value

Eqs. 4.28 and 432 give expression for energy of diatomic oscillator as follows:

If we divide both sides of Eq 4.41 by hc, we get

The term E/hc is referred to as the term value G(v) and the term voJc, the harmonic
.
frequency Yo, Both G(v) and Vmc have the units of wave number i.e. cm-', thus giving
the new expression for energy of the vibrational levels in term values as follows.

This is a convenient expression for equating the frequency of the oscillator, Po, with
the frequency of the electromagnetic radiation absorbed for fundamental transition of
the harmonic oscillator, P as given below:

For

and for
Thus,

It may be further noted that Eq. 4.44 represents the zero point-energy in cm-'
 Yibratlonsl Spectra
of Diatomic Molecules
4.4 ANHARMONICITY
As was shown in Fig.4.3, the potential energy curve of a harmonic oscillator is a
parabola. Increase of displacement xo continuously shows an increase in the energy. In
a diatomic molecule where change in the internuclear distance, A ro is equated to the
displacement,xo of harmonic oscillator, it is not realistically possible to expect higher
and higher potential energy with:increasing value of A ro since after a certain'increase
in bond distance, dissociation takes place and the molecule breaks into the.constituent
atoms. The true variation of the potential energy with internuclear distance and the
potential energy function for harmonic oscillator model of diatomic molecule are Also note that in an anhannonic
shown in Fig. 4.8. oscillator, the energy levels are not
Parabola
equally spaced in contrast to the
case of a harmonic oscillator shown
in Fig. 4.4.

(anharmonic curve of
the diatomic molecule)

I
1,
Internuclear distance -
Figure 4.8 : The variation of potential energy with Internuclear dlstance for a dlatomlc molecde
is shown by solld Ilne. The potential energy function for a harmonic oscillator h
shown by broken Ilne.

The deviation from harmonic oscillator behaviour is termed as anharmonicity. Note

that the minimum in the curve occurs at re, the equilibrium internuclear distance. You
can also see that in the vicinity of re, the curve very closely approximates the harmonic
oscillator. However, at larger internuclear separation, the anharmonic curve shows
significant deviation from the harmonic curve.

You will now study about the Morse Potential function which gives a better agreement
with the real curve.

4.4.1 Morse Potential

A mathematical equation for expressing the potential energy of diatomic molecule was
given by P.M. Morse and is called Morse potential. This can be written as follows.

Unlike a parabola, Mom c u m

-
where A r = r re,De is dissociation energy of the molecule measured from the allows for diuodation at high
energy.
minhum of the curve and /3 a constant is given by
The dissociation energy, D,
measured at the minimum of the
...(4.48) P.E c u m is called the
equitibrhm dirrocirrtion energy.
However. the sprcm9oopic
dirrociaribn a&, Eenergy of
where n,c, h have their usual meaning and p, De and v, are respectively the reduced the vibmtional
mass, dissociation energy and oscillational frequency. (v = o).'~NIs,

Do = D , - r1h ~ ,
4.4.2 Energy Levels of Anharmonic Oscillator and Selection Rules
Since in our analysis of IR transitions, we are mainly concerned with bond distance 17
 6
IR and Rnnlnn Spectre near th&equilibrium value, re, therefore, instead of using Morse potential, the
Maclaurian series expansion of potential energy is used for inclusion of anharmonicity
in the oscillator as follows:

Maclaurian rice is givcn as

follow . ,

If we include higher terms like t k 3 (A r)3 etc. in the potential energy expression, the
oscillator is referred to as anharmonic oscillator and such additional terms are
referred to as anharmonicity terms of potential energy expression. Inclusion of
anharmonicity terms leads to an improved version of energy levels, transition energies
and selection rules.

The vibrational energy levels of the anharmonic oscillator can be expressed as

X and Yare functions of constants k2, k3 etc. of Eq. 4.49 and are referred to as
anharmonicity constants. Usually the expression is turncated after two terms as Y is
far lesser in value thanX. However, the equation of motion obtained by using a cubic
potential energy function is not easy to handle. One approximate solution to the
Schrodinger equation that may be formed expresses the energy in terms
of the fundamental vibrational frequency, v, and anharmonicity constant
Noh that Xin Eq.!45O a iE equal to
%sex.in Eq. 450 b. xe, as follows.

Even with a linear dipole moment function, the anharmmic wave fuictions yield
selection rules A v = f1, +-2,+3 etc.! thus overtone bands get allowed due to
anharmonicity. The intensities of the overtone bands are, however, quite small in
comparison to the intensity of the fundamental band (Fig. 4.6 a). Due to added terms
in the energy expression (Eq. 4.50), the energy levels are no more equidistant and they
are found to converge.

Thus, the anharmonic correction reduces the energy of every level. The reduction is
greater for the higher energy levels. Thus, the spacing between the energy levels,
E(,, + -Ev ,gets smaller as v gets larger. This was shown in Fig. 4.8 and the extent of
reduction is shown in the margin.

4.4.3 Evaluation of Anharmonicity Constants

The term values G (v) for v = 0,1,2,3 for anharmonic oscillator are given below:
1 1 1
Effect of anhannonicityon the
Go=-Few--X+-Y
2 4 8
...(4.51)
vibrational energy levels of a
diatomic molecule. 3, 9 27
GI =-v0,--X+-Y
2 4 8
...(4.52)
5- 25 125
G2 = - v , - - X + Y
2 4 8
...(4.53)
7, 49
G3 = -V~,,--X
2 4
+ Y343
8
... (4.54)
The energies of radiation in cm-' for fundamental, first and second overtones can be
given as

Thus, by knowing the frequencies of electromagnetic radiation absorbed for

fundamental and overtone transitions, one can evaluate the oscillational frequency and
anharmonicity constants.

Also, the equilibrium dissociation energy, D, of a molecule can be calculated from its
spectroscopicdissociation energy, Do by using the following relation:

4.5 THE VJBRATING ROTATOR

In Unit 3, the pure rotations of diatomic molecules have been discussed and in the
preceding sections of this unit we have discussed pure vibrations of diatomic molecule.
The two motions have been discussed independent of each other. In reality, of course,
the rotational andxibrational motions take place simultaneously. In this section, we
now-see how the spectrum gets modzed because of this mixing.

4.5.1 Energy Levels

The total energy is given as a sum of the rotational and vibrational energies defined by
the quantum numbers v and J.

forv = 0,1,2... a n d J = 0,1,2 ... etc.

where Eq. 4.59 represents rotational vibrational energy for harmonic oscillator and
rigid rotator whereas Eq. 4.60 represents the rotational vibrational energy for
anharmonic oscillator and nonrigid rotator.

4.5.2 The IR Spectra and P,Q,R Branches

The selection rules for transitions in vibrating rotator are same as given for rotations
and vibrations of diatomic molecules (Unit 3 and Sec.4.3.2) which state A v = 21 and
A J = 21. Thus, for a fundamental vibrational transition A v = +1,we shall have a

-
series of transitions where A J = +1and another series where A J = -1. The series
with A v = +land A J = +1defines the transitions (00)- (ll), (01) (12), (02)-.

- - -
(13), (03) -. (14), ... etc; whereas the series with A v = +land A J = -1 defines the
transitions (01) 4 (lo), (02) (1I), (03) (12), (04) (13) etc. Here, the fust
number in the parenthesis denotes vibrational quantum number (v) and the second
IR and Rnrnon Spectrn number corresponds to the rotational quantum number (4.The transitions described
above are shown in Fig. 4.9.
AI = +1 (R branch) AI = -1 (Pbranch)
, Aw==SYI AwsSY1

F i e 4.9: The aeries of transitions 4 t h A v = +1 and A J 2 I.

For the vibrational transition A v = + 1, the series of transitions with A I = -1 is called

+
P branch and the series of transitions with A J = 1 is called R branch. For harmonic
oscillator and rigid rotator model

AEV,,= Evl, j , -Evt, J , ,

= h vo, (v' - v") + Bhc [I'(J' + 1) -J1' (I" + I ) ] ...(4.61)
For v' = 1and v" = 0, the R branch is represented by J ' = J " + 1and P branch is
represented by J ' = J " -1. The energy expressions for the two branches are given
below and they are shown schematically in Fig. 4.10.

-
and A Ev, = h vow 2 Bhd", P branch

- where J" = 1 , 2 , 3...

R b&h

I
*
P branch

Fig. 4.10: P and R branches showing energies of transitlo& with varying J " values.
 Vibrational Spectra
Since AJ = 0 is not allowed, the transition with AEv, = h v,, is not observed uader of Diatomic Molecules
these conditions. This is referred to as Q branch. The infrared spectrum of a diatomic
molecule with this model will have two rotational vibrational bands with a dip in the
centre corresponding to AJ = 0 as shown in Fig. 4.11. In working out the expressions
for AE;, given by Eqs. 4.62 and 4.63, it is assumed that the diatomic molecule
behaves like a rigid rotator and harmonic oscillator and also that the rotational
constant B does not vary with the vibrational quantum number. In practice, however,
these assumptions are not true and the expressions get slightly modified when these
assumptions are taken into consideration.

- cm4-
0,
low resdution

-U, cm4-
high resolution

Fb 4.11: The vlbra!loml mt.Uond lnf'rared spectrum 01. dlatomtc m o l r d e wlth rigid
rotator oed hannonlc oscillator model.

4.5.3 Symmetric Top Vibrating Rotator Model

As mentioned in Unit 3, a diatomic molecule can be considered as linear rotator if
mass of electrons is ignored. The moment of inertia in the direction of the internuclear
axis is zero and the moments of inertia in the other two directions (x, y) perpendicular
to this axis are equal and nonzero. In case the mass of the electrons is also considered.
the moment of inertia in the z-direction is small but finite and therefore, I, = I,, > > I,.
This is referred to a symmetric top model. The selection rules under these conditions
for vibrational-rotational transitions get modified as Av = +I and AJ = 0 , 21. The
molecules belonging to this category thus will have all the three (P, Q;R) branches
allowed and the infrared spectrum has a central branch (Q) surrounded by two
branches P and R on the low and high energy side of the Q branch. It is fouad that for
HCl molecule only P and R branches are observed in the vibrational rotational .
infrared spectrum whereas for NO molecule, all the three branches are observed.
IR and Rnmnn Spectra
SAQ 4
See Fig.4.6 carefully now and note down the various features of the infrared spectrum
you can explain.

4.6 SUMMARY
In this unit, you have learnt the properties of the motion of a single particle joined by
a spring fixed to a rigid wall. The motion follows Hooke's lawwhich states that the
restoring force is proportional to the displacement and acts in a direction opposite to
the direction of the displacement. The displacement of the partick follows simple
harmonic motion and is represented by a cosine function of time, t and characteristic
frequency v,. The expressions for the Hooke's law, Newton's second law of motion
and simple harmonic motion are combined to obtain relationship between the
oscillational frequency v,, and force constant of the spring, k (Eq. 4.7). The variation
of the potential energy of the motion of the particle with the displacement is shown by
a parabola. Expressions for the potential energy, kinetic energy and the total energy of
the particle at a displacement x are then derived on the basis of the parabolic variation
of the potential energy. It was shown how the use of Schrodinger wave equation for
harmonic oscillator gives expression for energy of the motion which is quantised giving
various energy levels with different values of quantum number v = 0,1,2,3 ... etc. It is
observed that the energy levels ar equidistant with a consecutive gap of h v,,. The
B
motion of two particles joined by a spring was then dealt with. The mathematical
derivation showed that the motion is equivalent to that of a harmonic oscillator
mentioned above such that its displacement is equal to the change in internuclear
distance and its mass is equal to the reduced mass of the two particles. The vibrations
of the diatomic molecule were treated in a way similar to the vibrations of two
particles joined by a spring, the internuclear bond made through the sharing of
electrons replaces the spring. Energy levels and other expressions similar to those .
obtained for harmonic oscillator were used for studying the vibration of diatomic
molecule.

Absorption of radiation in the infrared region led to transition of the diatomic

oscillator from ground state energy level with (v = 0) to excited state. The frequency
of the electromagnetic radiation at which absorption takes place is characteristic of
the molecule, and is also equal to the frequency of oscillation of the diatomic
harmonic oscillator. The selection rules for the vibrational transition shows that only
transitions with A v = +1 are allowed. Also such transitions are allowed if there is a
change in the dipole moment during the vibration. These rules restrict such transitions
to be possible only for heteronuclear diatomic molecules from v = 0 to
v = 1 levels. Due to Boltman's distribution, population in v > 0 is found to be very
small at room temperature for most of the common diatomic molecules; therefore,
transitions for v = 1to v = 2 etc. are not observed. Evaluation of force constant and
maximum displacement, effect of isotopic substitution on oscillational frequency and
expression for zero point energy were discussed.

The observed behaviour of diatomic molecules regarding their dissociation at higher

internuclear distances is introduced in the form of anharmonicity in the potential
energy expression. This led to some correction in the quantum mechanical energy
leading to a convergence in energy levels. Selection rules allow the observation of
overtones in the absorption spectrum of anharmonic oscillator which can be employed
to evaluate anharmonicity constants. The last section on vibrating rotator showed that
simultaneous existance of vibrations and rotations in the diatomic molecules leads to Vibrational Spectra
of Diatomic Moiecules
observation of fine structure in the absorption bands of IR spectra in terms of P, Q, R
branches.

4.7 TERMINAL QUESTIONS

1. What is the energy difference between energy levels of a harmonic oscillator?
2. Define zero point energy.
3. What are the selection rules for
(i) a harmonic oscillator to show vibrational spectrum and
(ii) an anharmonic oscillator to show vibrational spectrum ?

4. Calculate Defor H:, if Do = 21374.9 cm-'

v,, = 2321.7 cm-'

v,,xe = 66.2 cm-'

vMCye:= 0.6 6'

4.8 ANSWERS

Self Assessment Questions

1. p = 1.627 x 10-~'k~

Given u = 2886 cm-I. To get u osc from it, we have to multiply it by the velocity
of light, c.

A ro = 1.08 x I .87 x 2.42 x ,2.86 x for v = 0, l , 2 , 3,

respectively.

2. 0-D=2718cm-'

By using rno = 15.9949 x kg

~ 1.007825 x 1o - ~kg
r n=

rn=
~ 2.014101 x kg

and then calculating p and using Eq. 4.39.

3. Eo HCIIEoDCI = fi
4. Fundamental, I and I1 overtones at 2886,5668 and 8346 cm-'

-i (i) Overtones are weaker than fundamentals.

(ii) Harmonic oscillators - only fundamental transitions are allowed, (A v = d).

Anharmonic oscillators - fundamental and overtones are allowed,
. (A v = 0, 1,2, etc).
 IR nnd Rnmnn Spectm
(iii) At high resolution, rotational fine structure shows P and R branches and
a dip is observed in the place of Q branch since transitions with A J = 0
I are not allowed.

I Terminal Questions
1. hv,,

2. The energy of the molecule at v = 0, i.e. at vibrational ground leve'lis

. .
called zero point energy.
3. A v = &1 for harmonic oscillator
A v = f1, f2, &3etc. for an anharmonic oscillator.

4. - 22,540 cm-'.