Chapter 13: Molecular Spectroscopy:

Rotational and Vibrational Spectra

ATKINS’ PHYSICAL
CHEMISTRY 8E

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Lecture 1A
Introduction
Energy of molecule change not only as a result of
electronic transition but also because it can undergo
changes of rotational and vibrational state.

Bond strength, length, angles, shapes and dipole

moments can be obtained.
 GENERAL FEATURES OF SPECTROSCOPY

Experimental techniques.
Emission spectroscopy, electromagnetic radiation arises from
molecules undergoing a transition from a state of high energy to a state
of lower energy, and its frequency analyzed .

Absorption spectroscopy, spectroscopy based on the detection of the

net absorption of nearly monochromatic incident radiation as the radiation
is monitored over a range of frequencies.
Raman spectroscopy, a technique in which molecular energy levels are explored
by examining the frequencies present in scattered radiation.
Vibration and rotational transition can be
induced in two ways:
1. Direct absorption or emission of infrared radiation –
vibrational changes
2. Absorption or emission of microwave radiation – rotational
changes.

 The frequency present in the radiation scattered can give

information on the rotational and vibrational energy levels.
 Layout of absorption spectrometer
A spectrometer is an instrument that detects the
characteristics of light scattered, emitted, or
absorbed by atoms and molecules.
The layout of an absorption spectrometer, used
primarily for studies in the ultraviolet and visible
ranges, is one in which the exciting beams of
radiation pass alternately through a sample and a
reference cell, and the detector is synchronized
with them so that the relative absorption can be
determined.
 Emission spectrometer

A simple emission spectrometer, where

light emitted or scattered by the sample
is detected at right angles to the
direction of propagation of an incident
beam of radiation.

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 Raman spectroscopy process
In Raman spectroscopy, an incident photon is
scattered from a molecule. Most photons are
scattered elastically and so have the same
energy as the incident photons. Some photos
loose energy to the molecule and so emerge as
Stokes radiation; others gain energy and so
emerge as anti-Stokes radiation.
The scattering can be regarded as taking place
by an excitation of the molecule from its initial
state to a series of excited states and
subsequent return to a final state. Any net
energy change is either supplied from or carried
away by the photon.
Stokes radiation, scattered radiation at a lower frequency
than the incident radiation.

Anti-Stokes radiation, scattered radiation at a higher

frequency than the incident radiation.

Rayleigh radiation, the component of radiation scattered into

the forward direction without change of frequency.
 Typical Raman spectroscopy experiment

Light transmitted, emitted or

scattered by the sample is
collected by mirrors.

The intensity of light at each

frequency is analysed by a
suitable detector.

A common arrangement adopted

in Raman spectroscopy.

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 The Beer-Lambert law
It is found empirically that when electromagnetic radiation passes
through a sample of length L and molar concertation [J] of the absorbing
species J, the incident and transmitted intensities, I0 and I, are related by
the Beer-Lambert law.

Beer-Lambert law:
ε – molar absorption coefficient (dm3mol-1cm-1) or (cm2mol-1)
The greater the cross-sectional area of the molecule for absorption,
the greater its ability to block the passage of the incident radiation.
The molar absorption coefficient:
depends on the frequency of the incident
radiation and is greatest where the
absorption is most intense.

The integrated absorption

The maximum value of the molar
absorption coefficient, εmax, is an indication
of the intensity of a transition.
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coefficient of a transition is
the area under a plot of the
molar absorption coefficient
against the wavenumber of
the incident radiation.
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 Absorbance of a sample:

The beer-Lambert law becomes:

To achieve sufficient absorption:

1. Path length through gaseous sample must be very long
(concentrations are low).
2. For liquid samples, path length can be shorter.

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 (a) Absorption intensities

Transition rate, w is the rate of change of probability of the molecule

being found in the upper state.

The constant B is the Einstein coefficient of stimulated absorption and

ρdν is the energy density of radiation in the frequency range ν to ν + dν,
where ν is the frequency of the transition.
The more intense the incident radiation , the greater the rate at which
transitions are induced. Hence, the stronger the absorption by the sample
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When the molecule is exposed to black-body radiation from a source
of temperature T, ρ is:

If B is large, radiation will induce transition strongly and the sample
will be strongly absorbing.
Total rate of absorption, W: is the transition rate of single molecule
multiplied by the number of molecules N in the lower state. W =Nw

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 (b) Selection rules and transition moments

For the molecule to be able to interact with the light rays and absorb or
create a photon of frequency v, it must posses at least transiently a
dipole oscillating at that frequency.

A transition will be active (and generate or absorb photons) only if the

accompanying charge redistribution is dipolar.

Gross selection rule: A molecule gives a rotational spectrum only if it

has a permanent electric dipole moment (nonzero transition moment).

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 Spherical migration of charge

When 1s electron becomes a 2s

electron, there is a spherical
migration of charge.

There is no dipole moment.

Therefore, electric dipole

forbidden.

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Non-spherical migration of charge

When 1s electron
becomes a 2p
electron, there is a
dipole moment.

Therefore, this
transition is allowed.

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 Concluding remarks
Three principal factors influence the intensity of a spectral
transition:
1. The transition probability
Determined by the nature of the initial and final quantum states of the
molecule.
2. The concentration of the initial state
The greater the concentration of molecules in the initial energy level of
a transition, the more intense the spectral transition.
3. The path length of the sample
For absorption transition, the more beam of radiation allowed to pass
through the sample, the more energy will be absorbed from it.
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Lecture 1B
Linewidths
Effects that contribute to width of spectroscopic
lines:
1. Doppler broadening
2. Lifetime broadening
 (a) Doppler broadening

Gaseous samples:
They are essential for rotational spectroscopy, for only in gases can
molecules rotate freely.

When a source emitting electromagnetic radiation of frequency v

moves with speed s relative to an observer, the observer detects
radiation of frequency:

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Doppler-broadened spectral line

Doppler broadening increases with

temperature, because the molecules
acquire a wider range of speeds.

Therefore, to obtain spectra of

maximum sharpness, it is best to work
with cold samples.

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 (b) Lifetime broadening

Even at low temperature the spectroscopic lines from gas-

phase samples are not infinitely sharp,

Due to quantum mechanical effects.

It is impossible to specify the energy levels exactly, for

Time-dependent Schrödinger equation.
lifetime, τ, the time for which a state persists.

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When the energy spread is expressed as a wavenumber through δE = hcδ(1/λ).

No excited state has infinite lifetime;

Therefore all states are subject to some lifetime broadening.

The shorter the lifetimes of the states involved in a transition the

broader the corresponding spectral lines.

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 Two processes responsible for the lifetimes of a state:
1. Collisional deactivation Շcol = 1/z

 The collisional linewidth can be minimized by working at low

pressures. δEcol = ħ/ Շcol

z = <c2>/λ where λ = mean free path

2. Natural linewidth
 The rate of spontaneous emission can not be changed. Hence it is a
natural limit to a lifetime of an excited state.
 It strongly depends on the transition frequency, so low frequency
transition have very small natural linewidths
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Rotational spectrum of Orion nebula spectral fingerprints of diatomic
and polyatomic molecules present in the
interstellar cloud.

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Electronic excited state of molecules often have short lifetimes due
to the high rate of spontaneous emission. A typical lifetime is about
10-8 s (10ns), natural width of 5 x 10-4 cm-1 (15 MHz).

Rotational state natural lifetime is about 103 s, natural width of 5 x

10-15 cm-1 (10-14 Hz)
 Vibrations of diatomic molecules

• In this section, we adopt the same strategy of finding

expressions for the energy levels, establishing the selection
rules, and then discussing the form of the spectrum.
• We shall also see how the simultaneous excitation of
rotation modifies the appearance of a vibrational
spectrum.

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 Molecular vibrations
Potential energy curve for diatomic molecule
In classical mechanics, a harmonic oscillator is a particle of mass
m that experiences a restoring force proportional to its
displacement, x, from the equilibrium position. The particle
oscillates about the equilibrium position at a characteristic
frequency, v. The first approximation to a parabolic or harmonic
potential energy of of the form:

K is the force constant of the bond, which characterizes the

strength of the restoring force and is expressed in newtons per
meter (Nm-1)
A typical potential energy curve
The steeper the walls of the potential (the stiffer the bond), the of a diatomic molecule
greater the force constant.
 Molecular vibrations

The steeper the walls of the potential (the stiffer the

bond), the greater the force constant.

A molecular potential energy curve can be

approximated by a parabola near the bottom of
the well. The parabolic potential leads to
harmonic oscillations. At high excitation energies,
the parabolic approximation is poor (the true
potential is less confining), and it is totally wrong
near the dissociation limit. A typical potential energy curve
of a diatomic molecule
 Force constant is a measure of curvature of the
potential energy close to the equilibrium extension
of the bond.

If the potential energy curve is sharply

curved close to its minimum, then Kf will
be large and the bond stiff. If the
potential energy curve is wide and
shallow, the kf will be small and the
bond easily stretched or compressed.

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The Schrodinger equation for the relative motion of two atoms of masses
m1 and m2 with a parabolic potential energy is:

Where meff is the effective mass:

The permitted vibrational energy levels (Harmonic motion):

(ω is the angular frequency)

The vibration in wavenumbers are G(v), with Ev = hcG(v) :

(vibrational terms).

meff = m2 (m2- mass of light atom) e.g HI, meff = mH.

For a homonuclear diatomic molecule m1 = m2, and
the effective mass is half the mass of an atom: meff = ½m.

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Calculating a vibrational wavenumber :

An HCl molecule has a force constant of 516 N m−1, a reasonably

typical value for a single bond. The effective mass of 1H35Cl is 1.63 ×
10−27 kg (note that this mass is very close to the mass of the hydrogen
atom, 1.67 × 10−27 kg implying that the H atom is essentially vibrating
against a stationary Cl atom). Calculate the vibrational frequency.

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The vibrational frequency is therefore:
 Selection rules

The gross selection rule for a change in vibrational

state brought about by absorption or emission of
radiation is that the electric dipole moment of the
molecule must change when the atoms are
displaced relative to one another.
Such vibrations are said to be infrared active.
The classical basis of this rule is that the
molecule can shake the electromagnetic field
into oscillation if its dipole changes as it
vibrates, and vice versa

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NB: Stretching motion of a homonuclear diatomic molecule, does not
affect the molecule’s dipole moment.

Therefore, infrared inactive.

Heteronuclear diatomic molecules are infrared active.

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Lecture 2A
 Specific selection rules
The specific selection rule, which is obtained from an analysis of the
expression for the transition moment and the properties of integrals over
harmonic oscillator wavefunctions is:

Transitions for which Δv = +1 correspond to absorption and those with Δv =

−1 correspond to emission.
It follows from the specific selection rules that the wavenumbers of allowed
vibrational transitions, which are denoted ΔGv+1/2 for the transition v + 1←v,
for a harmonic oscillator are:
At room temperature kT/hc ≈ 200 cm−1, and most vibrational wavenumbers are
significantly greater than 200 cm−1. It follows from the Boltzmann distribution that
almost all the molecules will be in their vibrational ground states initially.

Hence, the dominant spectral transition will be the fundamental transition,1

←0. As a result, the spectrum is expected to consist of a single absorption line.
Since the vibrational levels are equally spaced, any transition between two
neighbouring vibrational levels corresponds to the same energy change. Only
one absorption line will be obtained in the vibrational spectrum of a diatomic
molecule.
Therefore, spectrum has a single absorption line.
 In harmonic approximation, the transition 5 → 4, 4 → 3, appear in the same
frequency.
Hence, the spectrum is also a single line.
 The separation between energy levels

It is the same for all v.

 The energy separation is negligibly small for
macroscopic objects and is of great important
for atoms.
Harmonic oscillator has
a zero-point energy of:

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 Anharmonicity

At high vibrational excitations the swing

of atoms can no longer be represented
by a parabolic approximation.

The energy levels are less widely

spaced at high excitations.

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 The convergence of energy levels:
One approach to the calculation of the energy levels in the presence of anharmonicity
is to use a function that resembles the true potential energy more closely. The Morse
potential energy is

where De is the depth of the potential minimum. Near the well minimum the variation of V
with displacement resembles a parabola but, unlike a parabola, the morse potential equation
allows for dissociation at large displacements. The Schrödinger equation can be solved for the
Morse potential and the permitted energy levels are:

Xe – anharmonicity constant.
The number of vibrational levels of a morse oscillator is finite
v = 0, 1, 2, 3, ……, vmax.

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hcD0 is the energy
difference between the
lowest vibrational state
(v=0) and the infinitely
separated atoms and
hcDe id the depth of the
well potential
The Morse oscillator can be used to
find dissociation energy of the
molecule.

The Morse potential energy curve

reproduces the general shape of a
molecular potential energy curve. The
corresponding Schrödinger equation can
be solved, and the values of the energies
obtained. The number of bound levels is
finite.

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 The Birge-Sponer plot

When several vibrational transition's are detectable, a graphic technique called a

Birge-Sponer plot can be used to determine the dissociation energy of the bond.

The basis of the Birge-Sponer plot is that the sum of successive intervals ΔGv +½

from the zero-point level to the dissociation limit is the dissociation energy.

D0 - dissociation energy

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The area under the plot of ∆Gv+½ against v + ½ is equal
to the sum, and therefore to D0.

The area under a plot of transition

wavenumber against vibrational quantum
number is equal to the dissociation energy
of the molecule. The assumption that the
differences approach zero linearly is the
basis of the Birge–Sponer extrapolation.

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Using a Birge–Sponer plot:
The vibrational levels of HgH converge rapidly, and successive intervals
are 1203.7 (which corresponds to the 1 ← 0 transition), 965.6, 632.4, and
172 cm-1. Estimate the dissociation energy of HgH.

∆Gν + 1 1203.7 965.6 632.4 172

2

ν + 12 0.5 1.5 2.5 3.5

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 1400
1
1200 Area = × base × height
2
1000
1
800 (
= × (4.60 )× 1321 cm −1
2
)
v

600
= 3038.3 cm −1
400

200
After linear extrapolation
0
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
v+0.5

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  1 kJ 
( ) (
D0 = hcv = 6.626 × 10 Js ×  3  × 2.999 × 1010 cm.s −1 × 3038.3 cm −1
−34
)
 10 J 
− 23
( 23
= 6.038 × 10 kJ × 6.022 × 10 mol −1
)
−1
= 36 kJ .mol

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 The vibrations of Polyatomic molecules

The analysis of vibrational spectra is a widely used analytical technique

that provides information about the identity and shapes of polyatomic
molecules in the gas and condensed phases.
Vibrational spectrum of a polyatomic molecule can be interpreted in terms
of its normal modes.
Diatomic molecule have one mode of vibration: The bond stretch. In
polyatomic molecules there are several modes of vibration because all
the bond lengths and angles may change and the vibrational spectra are
very complex.

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 Normal modes
The first step in the analysis of vibrations of a polyatomic molecule is to
calculate the total number of vibrational modes.
The total number of coordinates needed to specify the locations of N
atoms is 3N.
Each atom may change its location by varying each of its three
coordinates (x, y, and z) so that the total number of displacements available
is 3N.
For non-linear molecule that consists of N atoms, there are 3N – 6
independent modes of vibrations.
For linear molecule, there are 3N – 5 modes of vibrations
Fig. 13.39 (a) The orientation of a linear molecule requires the specification of two
angles and this is because only the latitude and longitude of the direction in which the
molecular axis is pointing need to be specified (b) The orientation of a nonlinear
molecule requires the specification of three angles, and this is because the orientation
of the molecule around the direction defined by the latitude and longitude also
needs to be specified.
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Determining the number of vibrational modes.

H2O, is a nonlinear triatomic molecule with N=3, and so has 3N-6=3

modes of vibration.
CO2 is a linear triatomic molecule, and has 3N-5=4 modes of
vibration.
Methylbenzene (C7H8) has 15 atoms and 39 modes of vibration.

Naphthalene (C10H8) has 48 modes of vibration.

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 Infrared absorption spectra of polyatomic
molecules

The gross selection rule for infrared activity: is that the motion
corresponding to a normal mode should be accompanied by a change of
dipole moment.

e.g. Symmetric stretch of CO2 leaves the dipole moment unchanged.

Therefore, this mode is infrared inactive.

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 Symmetric
stretch: left and
right vibrations
in phase
The antisymmetric stretch of
Asymmetric
CO2 is infrared active. stretch: add
left and right
vibrations
out of phase

Both bending modes are

Two Bending modes (v2) have the
infrared active. same frequency of 667cm-1. they
are degenerate and we can
transform one mode in to another
by rotating about the inter nuclear
axis. The fact that they are
degenerate explains why one band
is missing in the IR spectra.
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normal modes of CO2

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The three normal modes of H2O

The three normal modes of H2O.

The mode v2 is predominantly
bending, and occurs at lower
wavenumber and frequency than
the other two. It is generally the
case that the frequencies of
bending motions are lower than
those of stretching modes.

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The three normal modes of H2O

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Typical vibrational wavenumbers

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Lecture 2B
PURE ROTATION SPECTRA
Moments of inertia

rigid rotor, a body that does not distort under the stress of
rotation.
 spherical rotor, a rigid rotor with three equal moments of
inertia.
 symmetric rotor, a rigid rotor with two equal moments of
inertia and a third that is different.
The moment of inertia of a molecule is a measure of how
difficult it is to rotationally accelerate the molecule - the larger
the moment of inertia, the smaller the increase in angular
momentum for a given applied torque.

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 Moments of inertia

Moments of inertia: is the

sum of the masses multiplied by
the squares of their distances
from the axis of rotation.

The definition of moment of inertia. In this molecule there are three

Rotational spectra give identical atoms attached to the B atom and three different but
information about bond length mutually identical atoms attached to the C atom. In this example,
the centre of mass lies on an axis passing through the B and C atom,
and bond angles. and the perpendicular distances are measured from this axis.

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An asymmetric rotor with three different
moment of inertia

An asymmetric rotor has

three different moments of
inertia; all three rotation
axes coincide at the centre
of mass of the molecule.

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 Classification of rigid rotors

Ic>Ib>Ia

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Linear rotor (diatomic or
triatomic molecule) is when
2 moment of inertia is the
same, and one is zero,
spherical rotor (octahedral or
tetrahedral molecule) is when all
moment of inertia are the same
asymmetric rotor (square
pyramidal e.g. ammonia ) is
when all three moment of inertia
are not the same.
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 Example

Calculate the moment of inertia of an H2O

molecule around the axis defined by the
bisector of the HOH angle (1). The HOH bond
angle is 104.5° and the bond length is 95.7
pm.

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 Solution

The bond angle of the molecule is 2Φ

The bond length is R.

Therefore rH = RsinΦ
Then I = 2mHR2sin2Φ

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The rotational energy levels
The classical expression for the energy of a body
about an axis a is

A body free to rotate in three axes (a,b,c) has

energy:

Since Ja = Iawa, therefore:

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 Spherical rotors
When all three moments of inertia are equal as in CH 4 and SF6 to some value I.

The energy of spherical rotors is confined to the values:

The energy is normally expressed in terms of the rotational constant, B, of the

molecule, where

The expression for the energy (which is a wave number) is then:

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The energy expression:
The energy of a rotational state is normally reported as the rotational
term, F( J), a wavenumber, by division by hc:

The separation of adjacent levels is:

Because the rotational constant decreases as I increases, we see that large

molecules have closely spaced rotational energy levels.

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The rotational energy levels
of a linear or spherical rotor.

The rotational energy levels of a linear or

spherical rotor. Note that the energy
separation between neighbouring levels
increases as J increases.
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 Example
Consider 12C35Cl4 which is a spherical rotor, given that C-Cl bond length
(Rc-cl) = 177pm) and the mass of the 35Cl nuclide (m(35Cl) = 34.97mu), find
moment of inertia (I) and rotational constant (B).
 Symmetric rotors

Two moments of inertia are equal, but different from the third (as in
CH3Cl, NH3, and C6H6).

Principal axis: the unique axis of the molecule.

Principal moment of inertia is represented by I║.

The other moment of inertia as I┴.
If I║ > I┴, the rotor is like a pancake (oblate), and C6H6.
If I║ < I┴, the rotor is like a cigar (prolate), and CH3Cl.
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 Energy levels
The classical expression for energy is:
Since
Therefore,

The quantum expression (rotational terms) is:

F(J, K) = BJ(J+1) + (A – B)K2 rotational terms of a symmetric
rotor
J = 0, 1, 2,….K = 0, ±1, ±2, ….±J.
(rotational constants)

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The energy levels depends on the two moment of inertia, of the
molecule:

When K = 0, no angular momentum about the principal axis.

Therefore, The energy level depends only on I┴.
i.e. F(J, K) = BJ(J+1)

When K = ±J, almost all rotation is around the principal axis.

Therefore, The energies are largely dependent on I║.

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 The significance of quantum number K

Fig. 13.13 The significance of the

quantum number K. (a) When |K| is
close to its maximum value, J, most
of the molecular rotation is around
the figure axis. (b) When K = 0 the
molecule has no angular
momentum about its principal axis:
it is undergoing end-over-end
rotation.

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 Example
A 14NH3 molecule is a symmetric rotor with bond length 101.2 pm and
HNH bond angle 106.7o. Calculate its rotational terms.

Method: calculate the rotational constants A and B using expression for

moments of inertia.
Then find rotational terms

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Therefore, F(J,K)/cm-1 = 9.977J(J+1) - 3.633K2
Multiply F(J,K) by c, to get:

F(J,K)/GHz = 299.1J(J+1) – 108.9K2

The energy of molecule is

16.32 cm-1 or 489.3 GHz (For J = 1, and K = ±J)
19.95 cm-1 or 598.1 GHz (For J = 0, and K = 0)

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 Linear rotors e.g. CO2, HCl & C2H2

Rotation occurs only about the axis perpendicular to the line of atoms.
No angular momentum around the line,
Therefore, K Ξ 0 from the expression of symmetric rotational terms:
F(J, K) = BJ(J+1) + (A – B)K2

The rotational terms of a linear molecules is:

F(J) = BJ(J+1) J = 0, 1, 2,…..

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 Rotational transitions
Typical values of B for small molecule are in the region of 0.1 to 10 cm-1.

e.g. 0.356 cm-1 (NF3) and 10.59 cm-1(HCl).

So rotational transitional lie in the microwave region at the spectrum.

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Lecture 3
 Rotational selection rules for
Microwave spectroscopy
Gross selection for the observation of a pure rotational
spectrum: is that a molecule must have a permanent electric dipole
moment.

That is, for a molecule to give a pure rotational spectrum, it must be

polar. The classical basis of this rule is that a polar molecule appears
to possess a fluctuating dipole when rotating, but a nonpolar molecule
does not. The permanent dipole can be regarded as a handle with
which the molecule stirs the electromagnetic field into oscillation (and
vice versa for absorption).

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Homonuclear diatomic molecules and nonpolar polyatomic molecules such
as CO2, CH2=CH2 and C6H6 do not give rise to microwave spectra. On the
other hand, OCS and H2O are polar and have microwave spectra.

Spherical rotors cannot have electric dipole moments unless they become
distorted by rotation, so they are rotationally inactive except in special cases.

e.g. special case exists such as a SiH4 (8.3 μD dipole moment by virtue of its
rotation when J ≈ 10). For HCl has permanent dipole moment= 1.1 μD.

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 Example

Identify the rotationally active molecules?

N2, CO2, OCS, H2O, CH2=CH2, C6H6.

Sol: Only OCS and H2O are polar, so only these two molecules have
microwave spectra.

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 Specific rotational selection rules

The specific rotational selection rules are found by evaluating the transition
dipole moment between rotational states.
For linear molecules, the transition moment vanishes unless the following
conditions are fulfilled:
ΔJ = ±1 ΔMJ = 0, ±1 (rotational selection rule of a linear rotor)
ΔJ = +1 (absorption transition)
ΔJ = -1 (emission transition)
The allowed change in J arise from the conservation of angular momentum when
a photon is emitted or absorbed.
The allowed changes in MJ, also arise from the conservation of angular
momentum when a photon is emitted or absorbed in a specific direction.

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If the molecule is rotating in the same sense as the spin of
the incoming photon, then J increases by 1

When a photon is absorbed by a

molecule, the angular momentum of
the combined system is conserved. If
the molecule is rotating in the same
sense as the spin of the incoming
photon, then J increases by 1.

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The total J + 1 ↔ J transition intensity is ∞ to |μ|2.

(i.e. I ∞ μ2, so strongly polar molecules give rise to more intense

rotational line, than less polar molecules).

For symmetric rotors: ΔK = 0.

It cannot be accelerated into different states of rotation around the
principal axis by the absorption of radiation, so ΔK = 0.

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 Appearance of rotational spectra
Selection rules applied to energy levels:
When these selection rules are applied to the expressions for the energy
levels of a rigid symmetric or linear rotor, it follows that the wavenumbers of the
allowed J + 1 ← J absorptions are:

1/λ(J+1 ← J) = 2B(J + 1) (Wavenumbers of rotational transitions: linear rotor)

For centrifugal distortion:

However, because the second term is typically very small compared with the first, the appearance
of the spectrum closely resembles that of wavenumbers of rotational transitions of a linear rotor

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 Example
Predict the form of rotational spectrum of 14NH ,
3 which is an oblate
symmetric rotor with B=9.977 cm-1.
Sol: the 14NH3 molecule is a polar symmetric rotor symmetric rotor, the
selection rules ΔJ = ±1, ΔK = 0 apply. For absorption ΔJ = +1.
Since B = 9.977 cm-1.
Table for J+1 ← J transitions:

Line spacing is 19.95 cm-1 (598.1 GHz)

It consists of series of lines with wavenumbers 2B, 4B, 6B,…. and the separation is 2B.

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The rotational energy levels of a
linear rotor, the transitions allowed
by the selection rule ∆J = +−1, and a
typical pure rotational absorption
spectrum (displayed here in terms of
the radiation transmitted through
the sample). The intensities reflect
the populations of the initial level in
each case and the strengths of the
transition dipole moments.
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The measurement of line spacing gives B and hence moment of
inertia perpendicular to the principal axis of the molecule.

For known mass of atoms, it is simple to find the bond length of

a diatomic molecules.

The intensities of spectral lines increases with increasing J and

pass through a maximum before tailing of as J becomes large.

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 Rotational Raman spectra

The gross selection rule for rotational Raman transitions: is that the molecule
must be anisotropically polarizable.
The distortion of a molecule in an electric field is determined by its polarizability, α.
More precisely, if the strength of the field is E, then the molecule acquires an
induced dipole moment of magnitude
μ = αE α – polarizability.
An atom is isotropically polarizable, if the same distortion is induced whatever the
direction of the applied field.
e.g. spherical rotors are isotropic.

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None spherical rotors are anisotropically polarizable.

e.g. Electron distribution in H2, is more distorted when the field is

applied parallel to the bond than when it is applied perpendicular to it (α2
> α1).

All linear molecules and diatomic (whether Homonuclear or

Heteronuclear) have anisotropic polarizabilities.
So are rotationally Raman active.
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An electric field applied to a molecule
results in its distortion, and the distorted
molecule acquires a contribution to its
dipole moment (even if it is nonpolar
initially). The polarizability may be
different when the field is applied (a)
parallel or (b) perpendicular to the
molecular axis (or, in general, in different
directions relative to the molecule); if that
is so, then the molecule has an anisotropic
polarizability.

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Spherical rotors such as CH4 & SF6 are rotationally
Raman inactive as well as microwave inactive.

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Specific rotational Raman selection rules

Linear rotors: ΔJ = 0, ±2,...

Symmetric rotors: ΔJ = 0, ±1, ±2 ΔK = 0.
The ΔJ = 0 transitions do not lead to a shift of the scattered
photon’s frequency in pure rotational Raman spectroscopy, and
contribute to the unshifted Rayleigh radiation.

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 Appearance of rotational Raman spectra

Selection rule (ΔJ = +2) applied to energy levels:

For ΔJ = +2, the wavenumber of the incident radiation, initially vi is
decreased.

2
The stokes lines appear to low frequency, at 6B, 10B, 14B,…..from
vi (J = 0,1, 2,…)

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For ΔJ = -2 transition, the scattered photons emerges with
increased energy.

The separation of adjacent lines is 4B.

Therefore, I┴ can be determined and used to find bond length.

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 Example
Predict the form of the rotational Raman spectrum of 14N2, for which
B = 1.99 cm-1, when it is exposed to monochromatic 336.732 nm
laser radiation.
Method: the molecule is rotationally Raman active. Stokes and Anti-
stokes lines are: λi = 336.732 nm, line positions are:

There will be strong central line at 336.732 nm

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 Raman spectroscopy process
In Raman spectroscopy, an incident photon is
scattered from a molecule. Most photons are
scattered elastically and so have the same
energy as the incident photons. Some photos
loose energy to the molecule and so emerge as
Stokes radiation; others gain energy and so
emerge as anti-Stokes radiation.
The scattering can be regarded as taking place
by an excitation of the molecule from its initial
state to a series of excited states and
subsequent return to a final state. Any net
energy change is either supplied from or carried
away by the photon.
The rotational energy levels of a
linear rotor and the transitions
allowed by the ∆J = +-2 Raman
selection rules. The form of a
typical rotational Raman spectrum
is also shown. The Rayleigh line
is much stronger than depicted in
the figure; it is shown as a weaker
line to improve visualization of the
Raman lines.
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