Rotational (Microwave spectroscopy)

We will begin with a simple diatom. That is a linear rotor.

If we convert the two body problem to a C.M. and relative coordinate framework and assume that
the bond is rigid, then we need not worry about the C.M. motion and consider only the equivalent
problem of rotation of a free particle on a sphere.
The Hamiltonian for the system is H =

p2
2m

J2
2I

, (no potential energy). We can show that the

kinetic energy (xed r),

~2 2
~2

=
2m
2mr2

1 2
1
sin
+
sin
sin2 2



1
~2
( part) +
( part))
=
2I
sin2

1. The solutions for this are written as

1
(, ) = Yjm (, ) = N.Pjm (). eim
2

where j is a non-negative integer and m can take 2j + 1 values starting from l all the way to l
in increments of +1.
For j = 0, there is only one value of m, namely m = 0. It turns out that P00 () = 1.
Thus, Y00 (, ) = N. 12
On normalising, we ndN =

1
2

. Hence, Y00 (, ) =

1
4

2. For j = 1, m can take three values, m = 1, 0, 1. It turns out that P10 () cos and P11 ()
sin .

Thus
1
1
Y10 (, ) = N. cos and Y11 (, ) = N. sin ei
2
2

After normalising,
r
Y10 (, )

3
. cos
4

and

r
Y11 (, )

m (, ) = Ej Y m (, );
3. The energy states are, HY
j
j

3
. sin ei
8

Ej = Bj(j+1) and B =

~2
2Ihc

(in cm1 )= 8h2 Ic .

Each state has a gj = 2j + 1 fold degeneracy.

Thus the transition energy, Ej+1j = B[(j + 1)(j + 2) j(j + 1)] = 2B(j + 1)
Thus the rst line corresponding to 1 0, will appear at 2B , the second one at 4B , the next
at 6B , etc. And, the dierence between the consecutive lines, (Ej+1j ) = 2B .

Thus the spectrum will consist of a bunch of lines equally separated at intervals of 2B. The rst
line j = 1 j = 0 for the CO rotational spectrum appears at 3.84235 cm1 .
4. What about the intensities of the lines in the absorption spectrum? This will depend on the
population of the lower level, from where the excitation is taking place. The gure on the right
2

above shows typical intensities calculated theoretically for a linear rotor. Since the population
depends on temperature, so will the intensities and the location of the largest peak.
Ej
BT

Iabs Njlower = N0 gj e

= (2j + 1)e

or, Iabs = I0 (2j + 1)e

Bj(j+1)
kB T

Iabs = Iabsmax , when



T (o K)
0.59
1 .
B(in cm )

dIabs
dj

Bj(j+1)
kB T

, where kB is the Boltzmann constant.

We can nd the value of j for which the intensity will be maximum,

= 0 = (2jmax + 1)2 =

2kB T
Bhc

, or, jmax is the integer nearest to

Further modication comes from symmetry restrictions on nuclear-spin states. For permutation
of coordinates of any two particles, a quantum mechanical wavefunction must be anti-symmetric
for half-integral spin systems (Fermi Dirac statistics) and symmetric for integral spin systems
(Bose Einstein statistics).
On an average, at high temperature, exactly half the levels expected for a diatomic molecule will
be missing in the spectrum due to this symmetry restriction.
5. A more general treatment requires a detailed analysis involving moments of intertia for rotation w.r.t. the three principal axes of rotation. The gure below taken from Atkins' Physical
Chemistry, shows how dierent molecular systems can be categorized and the moment of inertia
calculated (m=total mass):

6. Selection rules: Time dependent quantum mechanics gives us an expression for the rate of
transition between energy states (hf | hi| of a Hamiltonian, H 0 , caused by a perturbation
0 as the celebrated Fermi Golden rule (http://en.wikipedia.org/wiki/Fermi%27s_golden_rule;
H

http://hyperphysics.phy-astr.gsu.edu/hbase/quantum/fermi.html):
Rf i =

2
0 |ii|2
|hf |H
~

~.
where is the density of nal states. Within dipole approximation, H 0 = ~.E

The matrix element involved is then,

0 |ii = E.
~ ~f i , where ~f i = hf |~|ii
hf |H
~ = x Ex + y Ey + z Ez
is called the transition dipole moment. And,
~ .E

In space xed coordinates,

x = 0 sin cos ;

y = 0 sin sin ;

z = 0 cos

Thus for a transition hj 0 , m0 | hj, m|, the matrix element involved is,
~ 0 , m0 i| =
|hj, m|~.E|j

|Ei |.|hj, m|i |j 0 , m0 i|; i = x, y, z

(You may skip the next few lines of algebraic detail and go directly to the last sentence of this
section)
hj, m|x |j 0 , m0 i = 0 hj, m| sin cos |j 0 , m0 i;
hj, m|y |j 0 , m0 i = 0 hj, m| sin sin |j 0 , m0 i;

hj, m|z |j 0 , m0 i = 0 hj, m| cos |j 0 , m0 i

Using |j, mi = |Yjm (, )i |Pjm (cos )eim i; and sin cos

1
2

Y11 + Y11

we have, hj, m| sin cos |j 0 , m0 i

0
d(cos )Pjm P11 Pjm0

i(m+1+m0 )

de

0
d(cos )Pjm P11 Pjm0

dei(m1+m )
0

It is easy to see from the integral that unless m = m0 + 1, the rst integral is zero. And unless
m = m0 1, the second integral is zero.

For the integral, we take help from handbooks and we nd that unless j = j 0 1 the integral
is zero. We can similarly prove the same conditions for y component. For z component, the
condition is that unless m = m0 or j = j 0 1, the integral is zero.
Notice that in each case, the magnitude of the dipole moment, 0 , is obviously non-zero.
Thus, the selection rules can be written as, (i) the molecule must have a permanent dipole
moment; (ii) j = 1 and (iii) m = 0, 1.
7. The eect of isotopic substitution: Isotopes have dierent masses, but the same number of electrons. Thus the internuclear distance that depends on the number of electrons will not change
5

signicantly, but the mass changes signicantly.

12

C16 O vs.

13

C16 O

B
>
B'
all the levels except j = 0 will decrease in energy and hence the spectral lines will appear at
smaller frequencies as we go to the larger mass.
2B 0 2B

4B 0 4B

6B 0 6B

8B 0 8B

Prob. Given that the rst lines in rotational spectrum of 12 C16 O and 13 C16 O appear at respectively 1.92118 cm1 and 1.83669cm1 . Given the mass of 16 O to be 15.9994 and of 12 C to be
12.00, nd the atomic mass of 13 C.
8. Nonrigid rotor: Centrifugal distortions:
The real molecule is not a rigid rotor.
Vibrations can change the bond lengths. Another way the bond lengths can change is the
stretching away from the equilibrium position by centrifugal force in the rotating molecule. The
eect of the centrifugal force stretching on the energy levels can be found by calculating the
new equilibrium bond length in the presence of rotation, and thus can be done by equating the
centrifugal force Fc to the restoring force.
(The eect will be prominent as j increases, because increase of j indicates increase of angular
momentum, which means faster rotation). It can be shown,
Erot /hc Bj(j + 1) D (j(j + 1))2

where D ==

B3
2

; B and the vibrational frequency (angular), =

, are evaluated at equilib-

rium internuclear distance.

For typical values, B = 1cm1 , = 1000cm1 , and for j = 30, we nd that the centrifugal
distortion is 1 cm1 out of a total of 900cm1 .


Ej+1j = B [(j + 1)(j + 2) j(j + 1)]D (j + 1)2 (j + 2)2 j 2 (j + 1)2 = 2B(j+1)4D(j+1)3

in cm1 .
Thus all the lines will be shifted to lower frequencies.
2B

4B

6B

8B

10B

12B

14B

16B

9. Eect of vibration on the rotational levels: The eect of vibration is quantied by the following
empirical relation:
1
E = eq (v + )
2

where eq is about

1
100

of Beq.