Pure rotational spectra

Moment of inertia: I mi ri2

i
rotational axis through centre of mass.

key molecular parameter.

depends on molecular geometry.

information about bond lengths / angles.

In general, the rotational properties of any

molecule are expressed in terms of the
moments of inertia about three
perpendicular axes set in the molecule Ia,
Ib, and Ic (convention Ic Ib Ia ).

We initially suppose that molecules are rigid rotors (that is, no

distortion under stress of rotation).

Spherical rotors: 3 equal moments

of inertia (CH4, SiH4, and SF6).

Symmetric rotors: 2 equal moments

of inertia (NH3, CH3Cl, and CH3CN).

Linear rotors: 1 moment of inertia

(molecular axis) equal to zero (CO2,
HCl, OCS, HC CH ).

Asymmetric rotors: 3 different

moments of inertia (H2O, H2CO,
CH3OH).
 The rotational energy levels
1 Ja2
Energy of a body rotating around an axis a is: E Ia a
2
2 2Ia
a = angular velocity (rad/s), Ia = moment of inertia, and Ja =
angular momentum. Hence, taking into account the 3 rotational
axes:
Ja2 Jb2 Jc2
E This is the key equation!
2Ia 2Ib 2Ic

Spherical rotors (3 equal moments of inertia)

J a2 Jb2 J c2 J 2
E
2I 2I

J2 = square of the magnitude of the angular

momentum, and we established that:

J 2 J (J 1) 2 J = 0, 1, 2,

Rotational energy levels of a spherical rotor

are confined to:

2
E J J (J 1) J 0, 1, 2,...
2I

We define the rotational constant B of the

2
molecule: B , hence:
2I

E J BJ (J 1) J 0, 1, 2,...
 Separation of adjacent levels is: E J E J 1 2BJ

Because B decreases as I increases, large molecules have

closely spaced rotational energy levels.

Symmetrical rotors (2 equal moments of inertia)

Unique moment of inertia labelled: I|| , the other two: I .

The rotor is classified as: oblate (pancake) when I|| > I .

prolate (cigar) when I > I|| .

Jb2 Jc2 Ja2

E ; since J2 Ja2 Jb2 Jc2 , we can write:
2I 2I||
J2 Ja2 Ja2 J2 1 1 2
E Ja
2I 2I|| 2I 2I|| 2I

J2 J (J 1) 2 J 0, 1, 2,...
and we established that:
Ja2 K 2 2 K 0, 1,..., J

Rotational energy levels of a symmetrical rotor are confined to:

J (J 1) 2 1 1 2 2
E J,K K
2I
2I|| 2I
2 2
Using the rotation constants: A ,B , we have:
2I|| 2I
EJ,K BJ J 1 ( A B)K 2 J = 0, 1, ; K = 0,, J
 The equation for the rotational energy levels matches what we
should expect for the dependence of the energy levels on the
two distinct moments of inertia of the molecule:

K = J, almost all angular momentum

arises from rotation around the principal
axis, energy levels determined largely by
I|| . Sign of K does not affect the energy
(since K2) because independent on
sense of rotation.

K = 0: no component of angular
momentum about the principal axis,
energy levels depend only on I .

Linear rotors (1 moment of inertia equal to zero)

Nuclei treated as mass points

rotation occurs only about an axis to the line of atoms
zero angular momentum around the line
similar to the case of a symmetrical rotor BUT with K = 0.

Rotational energy levels of a linear rotor are confined to:

2
E J J (J 1) J 0, 1, 2,...
2I

Same expression as for spherical rotor but K = 0 and A = B!

Degeneracies

For a symmetric rotor: E E(J,K) and each level (except K = 0)

is 2-fold degenerate (K).

However, the angular momentum of the molecule has a

component on an external, laboratory-fixed axis. This
component is quantized with permitted values M J , with
quantum number MJ = 0, 1, 2, , J, giving 2J+1 values in
all.

(a) (b) (c)

All drawings refer to a state with K = 0.

(a) MJ close to its max value J. Molecular rotation is mostly around the
laboratory z-axis
(b) Intermediate value of MJ.
(c) MJ = 0, no angular momentum about the z-axis.

E E(M J ) , but it is necessary for a complete specification of

the state of the rotor. Consequently, all 2J+1 orientations of the
rotating molecule have the same energy.

It follows that Erot is: 2(2J+1)-fold degenerate for K 0

(2J+1)-fold degenerate for K 0

For a linear rotor: K = 0, but the angular momentum may still

have 2J+1 components on the laboratory axis, so its
degeneracy is 2J+1.
 For a spherical rotor: seen as a symmetric rotor with A = B, the
quantum number K still takes any of 2J+1 values, but E E(K) .
Hence the degeneracy is:
2J+1 due to orientation in space.
2J+1 due to orientation about arbitrary molecular axis.

The overall degeneracy is therefore: (2J+1)2. Example: J=10

implies 441 states of same energy.

Centrifugal distortion

Atoms of rotating molecules are subject to centrifugal forces

distortion of the molecular geometry
stretching of the bond
moments of inertia increase
rotational constant decreases
energy levels are slightly closer than rigid predictions

Treated empirically by subtracting a term from the energy:

E J BJ J 1 D J J 2 (J 1) 2

DJ = centrifugal distortion constant = a

measure of a bond stiffness. Large
when the bond is easily stretched.

4B 3
For a diatomic molecule: D J
h2 2

Hence the observation of the convergence of the rotational

levels as J increases can be interpreted in terms of the rigidity
of the bond.
 Rotational transitions
Typical values of B B / hc for small molecules are in the
region of 0.1 to 10 cm-1 (for example, 0.356 cm-1 for NF3, and
10.59 cm-1 for HCl), so rotational transitions lie in the
microwave region of the EMR spectrum.

Selection rules for observing a pure rotational spectrum

Gross selection rule: polar molecule

(permanent electric dipole moment, hence, it
appears to possess a fluctuating dipole when
rotating).

Rotationally inactive molecules: non-polar, homonuclear

diatomic, symmetrical linear, spherical rotors (unless distorted
by rotation)

Specific selection rules: evaluation of the transition dipole

moment between rotational states. We can show (tedious!)
that, for a linear molecule, fi = 0 unless:

J 1 M J 0, 1

J 1 absorption
with
J 1 emission
 When the transition moment is evaluated for all possible
relative orientations of the molecule to the line of flight of the
photon, it is found that the total J 1 J transition intensity is
proportional to:

2 J 1 2 1 2
J 1,J
0 0 for J >> 1
2J 1 2

where 0 = permanent electric dipole moment of the molecule.

Hence, strongly polar molecules yield much more intense

rotational lines than less polar molecules.

The appearance of rotational spectra

For convenience< we use: B B / hc

Energy levels of a rigid symmetric or linear rotor expressed as

wavenumbers of the allowed J 1 J absorptions are:

J 1 J 2B(J 1)

for J = 0, 1, 2, Spectra consists of:

lines with 2B, 4B, 6B,...

line separation = 2B

line spacing gives B or B.

B gives moment of inertia.

 Intensities of spectral lines increase with J and pass through a
maximum because of the existence of a maximum in the
population of rotational levels. From Boltzmann (for a level J):

N J N g J e EJ / kBT

N = total number of molecules, gJ = degeneracy. Hence:

1/ 2
dNJ k T 1
0 J max B
dJ 2hc B 2

For a typical molecule (e.g. OCS, with B = 0.2 cm-1) at room

temperature, kBT 1000 hcB , so J max 30 .

Rotational Raman spectra

Gross selection rule: anisotropically

polarisable: = E with = molecules
polarizability.

Rotationally Raman inactive molecules: spherical rotors.

Specific selection rules:

Linear rotors: J 0, 2
Symmetric rotors: J 0, 1, 2 K 0

The J = 0 transitions do not lead to a shift of the scattered

photons frequency and contribute to the unshifted Rayleigh
radiation.
 Prediction of the form of the Raman spectrum of a linear rotor
by applying the selection rule J 2 to the rotational levels:

J 2 : the molecule is left in a higher rotational state,

hence a decrease in i :
J 2 J i 2B(2J 3)

Stokes lines < i and at displacements of 6 B ,

10 B , 14 B ,... from i for J = 0, 1, 2,

J 2 : the molecule is left in a lower rotational state,

hence a decrease in i :
J 2 J i 2B(2J 1)

Anti-Stokes lines > i and at

displacements of 6 B , 10 B , 14 B ,... from
i for J = 2, 3, 4, (notice that J 2 is
the lowest state that can contribute under
this selection rule).

Separation of both Stokes and anti-

Stokes lines is 4 B , hence I can be
extracted and used to find the bond
lengths as in microwave spectroscopy.
An example of application:

Lets predict the form of the rotational absorption spectrum

and the rotational Raman spectrum (when exposed to
monochromatic 336.732 nm laser radiation) of 14NH3.

First, we calculate the moment of inertia for 14NH3

Symmetric rotor with bond length 101.2 pm and HNH bond

angle of 106.7. Using trigonometry, with the bond angle and
bond length r, one shows that for a symmetric molecule:
I|| 2mH (1 cos )r 2
mHmN
I mH (1 cos )r 2 (1 2 cos )r 2
m H mN

Numerically, with:mH = 1.0078 u and mN = 14.0031 u,

I|| 4.413 10 47 kg m 2 & I 2.806 10 47 kg m 2 .

Second, we calculate the rotational energy levels of 14NH3

Rotational constants: A = 6.344 cm-1 and B = 9.977 cm-1.

Energy levels: E 9.977 J J 1 3.633 K 2 cm-1.

Upon multiplication by c (speed of light) E acquires units of

frequency: E 299.1 J J 1 108.9 K 2 GHz.

For J = 1, the energy needed for the molecule to rotate mainly

about its figure axis (K = J) is equivalent to 16.32 cm-1 (489.3
GHz). But end-over-end rotation (K = 0) corresponds to 19.95
cm-1 (598.1 GHz). Not a surprise, it is microwaves!
 Finally, we can predict the form of the rotational spectrum:

Since NH3 is a polar symmetric rotor, the following selection

rules apply:
J 1 and K 0

For absorption, J 1 and we can use

J 1 J 2B(J 1) . Because B = 9.977 cm-1, we can draw
up the following table for the J 1 J transitions:

J 0 1 2 3
(cm-1) 19.95 39.91 59.86 79.82
(GHz) 589.1 1197 1795 2393

The line spacing is 19.95 cm-1 (589.1 GHz).

The molecule is Raman active since non-spherical. i =

336.732 nm corresponds to i = 29697.2 cm-1. We use the
equations defined to obtain the following line positions:

J 0 1 2 3
Stokes lines:
(cm-1) 29637.3 29597.4 29557.5 29517.6
Anti-Stokes lines:
(cm-1) 29757.1 29797.0

EXAM

Of the molecules N2, CO2, OCS, H2O, CH2=CH2, C6H6, only OCS
and H2O are polar, so only these two molecules have microwave
spectra. Which of the molecules H2, NO, N2O, CH4 can have a pure
rotational spectrum?

For symmetric rotors, an additional selection rule states that K =

0. To understand this rule, consider the symmetric rotor NH3, where
the electric dipole moment lies parallel to the figure axis. Such a
polar molecule cannot be accelerated into different states of
rotation around the figure axis by the absorption of radiation, so K
= 0.

From a rot spectrum, because the masses of the atoms are known,
it is a simple matter to deduce the bond length of a diatomic
molecule.