Rotational Spectra 1

Chemistry Department University of Lagos

Rotational Spectroscopy

Rotational spectroscopy or microwave spectroscopy studies the absorption and emission of
electromagnetic radiation (typically in the microwave region of the electromagnetic spectrum) by
molecules associated with a corresponding change in the rotational quantum number of the
molecule. Rotational spectroscopy is only really practical in the gas phase where the rotational
motion is quantized. In solids or liquids the rotational motion is usually quenched due to
collisions.
Moment of force (often just moment) is a synonym for torque. The moment of inertia of a
molecule is a measure of how difficult it is to rotationally accelerate the molecule (SI units
kg m
2
). It is a measure of an object's resistance to changes in its rotation rate - the larger the
moment of inertia, the smaller the increase in angular momentum for a given applied torque and
the slower the rate of rotation. Mathematically it is given as

Where

is the mass of the atom/particle and

the distance from the rotation axis.

In quantum mechanics the free rotation of a molecule is quantized, that is the rotational energy
and the angular momentum can only take certain fixed values; what these values
are is simply related to the moment of inertia, I, of the molecule.
In general for any molecule, there are three moments of inertia: I
A
,
I
B
and I
C
about three mutually orthogonal axes A, B, and C with
the origin at the center of mass of the system. The general
convention is to define the axes such that the axis A has the
smallest moment of inertia (and hence the highest rotational
frequency) and other axes such that

.
Rotational spectrum from a molecule (to first order) requires that the molecule
have a dipole moment, i.e. 0, and that there be a difference between its
100GHz - 1GHz
mm 3 cm 30
=
=
v

Rotational Spectra 2

Chemistry Department University of Lagos
center of charge and its center of mass, or equivalently a separation between two unlike charges.
It is this dipole moment that enables the electric field of the light (microwave) to exert a torque
on the molecule causing it to rotate more quickly (in excitation) or slowly (in de-excitation).
Diatomic molecules such as dioxygen (O
2
), dihydrogen (H
2
), etc. do not have a dipole moment
and hence no pure rotational spectrum. However, electronic excitations can lead to asymmetric
charge distributions and thus provide a net dipole moment to the molecule. Under such
circumstances, these molecules will exhibit a rotational spectrum.

The rotational energy levels
Because I depends on both the mass of the atoms and the geometry of the molecule, the
rotational spectroscopy will provide us with information about bond lengths and bond angles.
The classical expression for a body rotating about a given axis with angular velocity (in
radian) per second is

A body free to rotate about three mutually perpendicular axes has an energy given by:

This equation can be transformed into

The analogous quantum mechanical expressions can be obtained by substitution of the quantum
expressions for angular momentum,

J is the total angular momentum. It tells the relative orientation of the spin and orbital angular
momentum for several electrons. The angular momentum of an object is defined relative to a
fixed point
Classification of molecules based on rotational behavior
The particular pattern of energy levels (and hence of transitions in the rotational spectrum) for a
molecule is determined by its symmetry. A convenient way to look at the molecules is to divide
them into four different classes (based on the symmetry of their structure). These are,
Rotational Spectra 3

Chemistry Department University of Lagos
1. Linear molecules (or linear rotors)

2. Symmetric tops (or symmetric rotors)

3. Spherical tops (or spherical rotors)

and
4. Asymmetric tops (asymmetric rotors)

Linear molecules:
A linear molecule is a special case. These molecules are
cylindrically symmetric and one of the moment of inertia
(I
A
, which is the moment of inertia for a rotation taking
place along the axis of the molecule) is negligible i.e.

. For most of the purposes, I

A
is taken to be
zero as all the atoms lie on the axis of rotation so are at zero
distance from it.

Examples of linear molecules: dioxygen (O=O), carbon monoxide (OC), hydroxy radical (OH),
carbon dioxide (O=C=O), hydrogen cyanide (HCN), carbonyl sulfide (O=C=S), chloroethyne
(HCCCl), acetylene (HCCH)
Diatomic molecule: For diatomic molecules this process of
bond/structure determination is trivial, and can be made from
a single measurement of the rotational spectrum.
Rigid rotor
The bond distance: R=r = r
1
+ r
2

The center of mass has a physical property: r
1
m
1
= r
2
m
2
The moment of inertia:
2
2 1
2
1 1
r m r m I + =
Figure 1: The rotation produces I
perpendicular to the plane of rotation.
Rotational Spectra 4

Chemistry Department University of Lagos
The radial distances from mass center can be given by bond length

Substituting r
1
and r
2
into we get for I

Where,

is called the reduced mass

From quantum mechanics equation, the energy levels of a rigid rotor is
given

where J = 0, 1, 2, and M
J
= 0, 1, 2, , J. the energy is
independent of M
J
and there are 2J + 1 values of M
J
for each J, making
each energy level to be (2J + 1) degenerate. M
J
describes the orientation
of J in space much like the magnetic quantum number. The angular
momentum can only be oriented in the direction in which it takes
integral values. this is defined by M
J
.
It follows that

The rotation energy is normally reported as the rotational term

Where B is called the rotational constant. It is given in wavenumber
terms, and a rotation constant B as

where B is the rotational constant of the molecule and is related to the moment of inertia of the
molecule I
B
= I
C
by,

Recall

Figure 2: Energy level spacing for linear
or spherical rotor
Rotational Spectra 5

Chemistry Department University of Lagos

If the velocity of light is given in cm/s units the unit of B is cm
-1
.
Selection rules dictate that during emission or absorption the rotational quantum number has to
change by unity i.e. J=J' - J'' = 1. M
J
= 0, 1, a rule which is important only if the molecule
is in an electric or magnetic field. The rotation constant of a molecule is characteristic to the
nature of molecule, and independent of J. In this notation J' and J'' mean the upper level and
lower level respectively with the relation J' - J'' =1
The transition

But

and

) (

The wavenumber can be phrased either by lower
rotation level

or by upper rotation level.

Alternatively, one can say that the locations of the lines in a rotational spectrum will be given by

This wavenumber equals to the peak position of one band in the vibrational spectrum.
The rotation spectra contains peak series with peak
separation equal to each other.

Table 1. for rotation levels and energy spacing



J (cm
-1
) (cm
-1
)
1 4B
2 6B 2B
3 8B 2B
4 10B 2B
Rotational Spectra 6

Chemistry Department University of Lagos
The rotational levels are not equidistant, which can be seen from the second column of Table 1.
Example for CO:
the transition (J=0 J=1) for
12
C
16
O is at 3.84235 cm
-1
.
Given that C = 12.0000 ; O = 15.9994 amu;1 amu = 1 atomic mass unit = 1.6605402 x 10
-27
kg;
h = 6.6260755 x10
-34
Js; c = 2.99792458 x 10
10
cm s
-1
; Find r(CO)

2
46
2
kgm
B
10 2.7992774
Bc 8
h
I

= =
= r
2

B = 1.921175 cm
-1
; = 1.1386378 x 10
-26
kg

I
r = = 1.131 x 10
-10
m
0.1131 nm
Answer: C-O bondlength is 0.1131 nm.
Rotational absorption lines from
1
H
35
Cl gas were found at the following wavenumbers: 83.32
cm
-1
, 104.13 cm
-1
, 124.73 cm
-1
, 145.37 cm
-1
, 165.9 cm
-1
, 186.23 cm
-1
, 206.60 cm
-1
, 226.86
cm
-1
. Calculate the moment of inertia and the bond length of the molecule.
u 96885 . 34 ) (
u 007825 . 1 ) (
) ( ) (
) ( ) (
.
4
2
2
~
35
1
2
35 1
35 1
=
=
+

=
= = A
Cl m
H m
r
Cl m H m
Cl m H m
I
cI
B
HCl
t
v

,
1 8
1 34
27
s m 10 9979 . 2
2
s J 10 62608 . 6
kg 10 1.66054 u 1

=
=
=
=
c
h
h
t

;
m 10 5 . 129
) ( ) (
) ( ) (
m kg 10 731 . 2
~
4
2
cm 50 . 20
~
~
4
2
4
2
2
~
12
35 1
35 1
2 47 1

+
=
=
A
= = A
A
= = = A
Cl m H m
Cl m H m
I r
c
I
c
I
cI
B
HCl
v t
v
v t t
v

Rotational Spectra 7

Chemistry Department University of Lagos
Intensities of rotation spectral lines
Now we understand the locations (positions) of lines in the microwave spectrum, we can see
which lines are strongest. The height of the lines is determined by the distribution of the
molecules in the different levels and the probability of transition between two energy levels.
Apart from depending on the numerical value of the square of the transition moment varies
relatively little with J, intensities depend on the population of the lower state of a transition. The
population N
J
of the Jth level relative to N
0
is obtained from Boltzmanns distribution law

where (2J + 1) is the degeneracy of the J
th
level. This degeneracy arises from the fact that, in the
absence of an electric or magnetic field, (2J + 1) levels, resulting from the number of values that
M
J
can take, are all of the same energy: in other words they are degenerate. Values of (2J + 1),
exp(-E
r
/kT) and N
J
/N
0
are given for CO below, and illustrate the point that there are two


Rotational Spectra 8

Chemistry Department University of Lagos
opposing factors in N
J
/N
0
. The (2J + 1) factor increases with J whereas the exp(-E
r
/kT) factor
decreases rapidly, so that increases at low J until, at higher J, the exponential factor wins and N
J

/N
0
approaches zero.
The population therefore shows a maximum at a
value of J = J
max
corresponding to

Which gives

for B having dimensions of frequency.
Therefore intensity depends on population of state, the degeneracy and energy of the state.
Effect of Isotopes
Isotopes are atoms of the same element (that is, with the same number of protons in their atomic
nucleus), but having different numbers of neutrons. Consequently, changing a particular atom in
the molecule changes the atomic mass and therefore the total mass. This in turn changes the
moment of inertia and hence the rotational constant, B. There is usually no appreciable change in
the internuclear distance. For example consider carbonmonoxide, going from
12
C
16
O to
13
C
16
O,
there is a mass increase, therefore a reduction in B ( 1/I). This gives rise to lower energy levels.

Rotational Spectra 9

Chemistry Department University of Lagos
Generally, the spectrum of heavier species gives rise to smaller separation between the lines than
that of the lighter species.
From this information one can determine: (i) isotopic masses accurately, to within 0.02% of
other methods for atoms in gaseous molecules; and (ii) isotopic abundances from the absorption
relative intensities.
Example:
Given : the below information
For
12
CO J=0 J=1is at 3.84235 cm
-1
and at 3.67337 cm
-1
for
13
CO (
12
C = 12.0000 ; O =
15.9994 amu).What is isotopic mass of
13
C ?
B(
12
CO) = 1.921175 cm
-1
and B(
13
CO) = 1.836685 cm
-1

Now

1
I
1
B
1.04600
1.836685
1.921175
CO) (
CO) (
12
13
= = and
15.9994 12
15.9994 12
15.9994 C) (
15.9994 C) (
1.046
13
13

=
(
13
C) = 13.0006 amu
Is the bond length in
1
HCl the same as in
2
HCl? The wavenumbers of the J = rotational
transition for
1
HCl and
2
HCl are 20.8784 cm
-1
and 10.7840 cm
-1
, respectively.
u 96885 . 34 ) (
u 007825 . 1 ) (
4
2
2
~
35
1
2
2 1
2 1
0 1
=
=
+

=
= =

Cl m
H m
r
m m
m m
I
cI
B
t
v


1 8
1 34
27
2
s m 10 9979 . 2
2
s J 10 62608 . 6
kg 10 1.66054 u 1
u 2.0140 ) (

=
=
=
=
=
c
h
h
H m
t

0 1
Rotational Spectra 10

Chemistry Department University of Lagos
HCl HCl HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
HCl
r r r
r
r
r
r
r
r
Cl m H m
Cl m H m
Cl m H m
Cl m H m
I
I
I
I
cI cI
1 1 2
1
2
1
2
1
2
1
2
1
2
2
1
2
2
1
1
99795 . 0
94400 . 1
93605 . 1
93605 . 1 94400 . 1
94400 . 1
) ( ) (
) ( ) (
) ( ) (
) ( ) (
93605 . 1
~
~
4
2
~
;
4
2
~
2
2
2
2
2
2
35 1
35 1
35 2
35 2
= = =
=
+

=
= =
= =
v
v
t
v
t
v


Non rigid rotor
We observe that, for a rigid rotor, the transition lines are equally spaced in the wavenumber
space. However, this is not always the case, except for the rigid rotor
model. For non-rigid rotor model, we need to consider changes in the
moment of inertia of the molecule. Two primary reasons for this are,
Centrifugal distortion
Equation for E
rot
(J) is only approximate. When a molecule rotates, the
centrifugal force pulls the atoms apart. (Centrifugal force (from Latin centrum "center" and
fugere "to flee") represents the effects of inertia that arise in connection with rotation and which
are experienced as an outward force away from the center of rotation. )As a result, the moment
of inertia of the molecule increases, thus decreasing the rotational constant B. In order to provide
a better description of the energy levels of a diatomic molecule, a centrifugal distortion term is
added to the energy.

D
J
is called the centrifugal distortion constant, and is several orders of magnitude smaller than B.
It is a measure of stiffness of the molecule to rotation. The effect of rotation on a molecule. The
centrifugal force arising from rotation distorts the molecule, opening out bond angles and
stretching bonds slightly. The effect is to increase the moment of inertia of the molecule and
hence to decrease its rotational constant. It takes into account of the fact that as a real molecule
rotates faster and faster (i.e. with more energy), the bond stretches a little (if you swing a weight
attached to a piece of elastic in a circle, you can observe the same effect on a macroscopic scale).
It is large when the bond is easily stretched.
Accordingly the line spacing for the rotational mode changes to,
Rotational Spectra 11

Chemistry Department University of Lagos

The centrifugal distortion constant, D
J
is related to the wavenumbers approximately by

1
2 2 4
3
cm
kc r I 32
h
D

=


Effect of vibration on rotation:
A molecule is always in vibration. As the molecule vibrates, its moment of inertia changes.
Further there is a fictitious force, Coriolis coupling, between the vibrational motion of the nuclei
in the rotating (non-inertial) frame. However, as long as the vibrational quantum number does
not change (i.e. the molecule is in only one state of vibration), the effect of vibration on rotation
is not important, because the time for vibration is much shorter than the time required for
rotation. The Coriolis coupling is often negligible, too, if one is interested in low vibrational and
rotational quantum numbers only. (More on this later)
Polyatomic linear molecules
For linear molecules with more atoms, Things get much more complicated, but the general
principles are the same. e.g. OCS HCCCl I
c
= I
B
; I
A
= 0
The moment of inertia is greater than for diatomic molecule, B will be smaller and lines will
be more closely spaced. As usual, the molecule must have dipole moment for microwave
spectrum.
For a poly atomic molecule with N atoms, there are N-1 bond lengths to be determined and not
just 1 as in a diatomic molecule, so for OCS we must determine r
CO
, r
CS
i.e. two bondlengths are
unknown we need 2 values for I
B
- the second can come from an isotopically substituted
molecule, which has same bondlength (almost), but different mass.

Rotational Spectra 12

Chemistry Department University of Lagos

More work is required, and it is necessary to measure molecules in which more than one isotope
of each atom have been substituted (effectively this gives rise to a set of simultaneous equations
which can be solved for the bond lengths). e.g. consider
16
OC
34
S,
18
OC
34
S .
O C S
Fro the center of mass moments m
o
r
o
+ m
C
r
C
= m
S
r
S

I = m
o
r
o
2
+ m
C
r
C
2
+ m
S
r
S
2

After several manipulations we obtain

Where m is the total mass of the molecule.
We may write

for the isotopic molecule, where

is the isotopic mass

and

are not primed since it is

presumed that they are not affected by isotopic substitution.
In accurate work isotopic bond lengths differ, due to differences in zero point energy


J J+1 B(cm
-1
)
0 1 2 0.4055 0.2027
1 2 0.8109 0.4054 0.2027
2 3 1.2163 0.4054 0.2027 Calculate
3 4 1.6217 0.4054 0.2027 I
B

4 5 2.0271 0.4055 0.2027
Rotational Spectra 13

Chemistry Department University of Lagos
Symmetric tops:
A symmetric top is a molecule in which two
moments of inertia are the same. They are divided
into two classes,
- Oblate symmetric tops (saucer or disc
shaped) with I
A
= I
B
< I
C
e.g benzene
(C
6
H
6
), cyclobutadiene (C
4
H
4
), ammonia
(NH
3
)
- Prolate symmetric tops (rugby football, or
cigar shaped) with I
A
< I
B
= I
C
e.g.
chloromethane (CH
3
Cl), propyne (CH
3
CCH)
The spectra look rather different, and are instantly recognizable. Like in the case of the linear
molecules, the structure of symmetric tops (bond lengths and bond angles) can be deduced from
their spectra.
The rotational motion of a symmetric top molecule can be described by two independent
rotational quantum numbers (since two axes have equal moments of inertia, the rotational motion
about these axes requires only one rotational quantum number for complete description). Instead
of defining the two rotational quantum numbers for two independent axes, we associate one of
the quantum number (J) with the total angular momentum of the molecule and the other quantum
number (K) with the angular momentum of the axis which has different moment of inertia (i.e.
axis C for oblate symmetric top and axis A for prolate symmetric tops). The rotational energy
F(J,K) of such a molecule, based on rigid rotor assumptions can be expressed in terms of the two
previously defined rotational quantum numbers as follows,

and
where

and

for a prolate symmetric top molecule or

for an
oblate molecule.
Selection rule for these molecules provide the guidelines for possible transitions. Accordingly,
J=1 and K=0.
This is so because K is associated with the axis about which the molecule is symmetric and
hence has no net dipole moment in that direction. Thus there is no interaction of this mode with
the light particles (photon).
Rotational Spectra 14

Chemistry Department University of Lagos
This gives the transition
wavenumbers of,

which is the same as in the
case of a linear molecule.
In case of non-rigid rotors, the
first order centrifugal distortion
correction is given by,

The suffixes on the centrifugal distortion constant D indicate the rotational mode involved and
are not a function of the rotational quantum number. The location of the transition lines on a
spectrum is given by,

1. Spherical tops:
A spherical top molecule, can be considered as a special case of symmetric tops with equal
moment of inertia about all three axes (I
A
= I
B
= I
C
).
Examples of spherical tops: phosphorus tetramer (P
4
), carbon tetrachloride (CCl
4
), nitrogen
tetrahydride (NH
4
), ammonium ion (NH
4
+
), sulfur hexafluoride (SF
6
)

Unlike other molecules, spherical top molecules have no net dipole moment, and hence they do
not exhibit a pure rotational spectrum.
However, consider the methane molecule. Rotation about any of the C
3
axes (i.e. any of the four
axes in methane containing a CH bond) results in a centrifugal distortion in which the other
three hydrogen atoms are thrown outwards slightly from the axis. This converts the molecule
into a symmetric rotor and gives it a small dipole moment resulting in a very weak rotational
spectrum.
Rotational Spectra 15

Chemistry Department University of Lagos

Part of the far-infrared
rotational spectrum of silane
(SiH4) is shown. It was
obtained under the following
conditions using a Michelson
interferometer: absorbing path
of 10.6 m and a pressure of 4.03
atm (4.086105 Pa), these
conditions indicating how very
weak the spectrum is. The
dipole moment has been
estimated from the intensities of the transitions to be 8.361076 D (2.7610735 C m).
The rotation term values for a spherical rotor are given by

This is an identical expression to that for a diatomic or linear polyatomic molecule and, as the
rotational selection rule is the same, namely, J = 1,the transition wavenumbers or frequencies
are given by

and adjacent transitions are separated by 2B.
All regular tetrahedral molecules, which belong to the T
d
point group, may show such a
rotational spectrum. However, those spherical rotors that are regular octahedral molecules and
that belong to the O
h
point group do not show any such spectrum. The reason for this is that
when, for sample, SF
6
rotates about aC
4
axis (any of the FSF axes) no dipole moment is
produced when the other four fluorine atoms are thrown outwards.
2. Asymmetric tops:
a molecule is termed an asymmetric top if all three moments of inertia are different. Most of the
larger molecules are asymmetric tops, even when they have a high degree of symmetry.
Generally for such molecules a simple interpretation of the spectrum is not normally possible.
Sometimes asymmetric tops have spectra that are similar to those of a linear molecule or a
symmetric top, in which case the molecular structure must also be similar to that of a linear
molecule or a symmetric top. For the most general case, however, all that can be done is to fit the
spectra to three different moments of inertia. If the molecular formula is known, then educated
guesses can be made of the possible structure, and from this guessed structure, the moments of
inertia can be calculated. If the calculated moments of inertia agree well with the measured
Rotational Spectra 16

Chemistry Department University of Lagos
moments of inertia, then the structure can be said to have been determined. For this approach to
determining molecular structure, isotopic substitution is invaluable.
Examples of asymmetric tops: anthracene (C
14
H
10
), water (H
2
O), nitrogen dioxide (NO
2
)
The spectrum for these molecules usually involves many lines due to three different rotational
modes and their combinations. The following analysis is valid for the general case and collapses
to the various special cases described above in the appropriate limit.
From the moments of inertia one can define an asymmetry parameter as




which varies from -1 for a prolate symmetric top to 1 for an oblate symmetric top.
One can define a scaled rotational Hamiltonian dependent on J and . The (symmetric) matrix
representation of this Hamiltonian is banded, zero everywhere but the main diagonal and the
second subdiagonal. The Hamiltonian can be formulated in six different settings, dependent on
the mapping of the principal axes to lab axes and handedness. For the most asymmetric, right-
handed representation the diagonal elements are, for ||
H
k,k
() = k
2

and the second off-diagonal elements (independent of ) are
.
Diagonalising H yields a set of 2J + 1 scaled rotational energy levels E
k
(). The rotational energy
levels of the asymmetric rotor for total angular momentum J are then given by

Degeneracy Stark effect
For each J there, are (2J+1) state with the same energy. This is called degeneracy. In the
presence of an external magnetic field this degenarcy is removed. This is the Stark effect. It is
the shifting and splitting of spectral lines of atoms and molecules due to the presence of an
external static electric field. It is the electric analogue of the Zeeman effect where a spectral line
is split into several components due to the presence of a magnetic field. The amount of splitting
and or shifting is called the Stark splitting or Stark shift.
In general one distinguishes first- and second-order Stark effects. The first-order effect is linear
in the applied electric field, while the second-order effect is quadratic in the field.
Rotational Spectra 17

Chemistry Department University of Lagos
The Stark effect is responsible for the pressure broadening (Stark broadening) of spectral lines by
charged particles. When the split/shifted lines appear in absorption, the effect is called the
inverse Stark effect.

Hyperfine interactions:
In addition to the main structure that is observed in microwave spectra due to the rotational
motion of the molecules, a whole host of further interactions are responsible for small details in
the spectra, and the study of these details provides a very deep understanding of molecular
quantum mechanics. The main interactions responsible for small changes in the spectra
(additional splittings and shifts of lines) are due to magnetic and electrostatic interactions in the
molecule. The particular strength of such interactions differs in different molecules, but in
general, the order of these effects (in decreasing significance) is:
1. electron spin - electron spin interaction (this occurs in molecules with two or more
unpaired electrons, and is a magnetic-dipole / magnetic-dipole interaction)
2. electron spin - molecular rotation (the rotation of a molecule corresponds to a magnetic
dipole, which interacts with the magnetic dipole moment of the electron)
3. electron spin - nuclear spin interaction (the interaction between the magnetic dipole
moment of the electron and the magnetic dipole moment of the nuclei (if present)).
4. electric field gradient - nuclear electric quadrupole interaction (the interaction between
the electric field gradient of the electron cloud of the molecule and the electric
quadrupole moments of nuclei (if present)).
5. nuclear spin - nuclear spin interaction (nuclear magnetic moments interacting with one
another).
These interactions give rise to the characteristic energy levels that are probed in "magnetic
resonance" spectroscopy such as NMR and ESR, where they represent the "zero field splittings"
which are always present.
Applications
Microwave spectroscopy is commonly used in physical chemistry to determine the structure of
small molecules (such as ozone, methanol, or water; planarity and non-planarity of molecules;
accurate determination of geometric parameters such as bond lengths and bond angles) with high
precision. This is because it is highly sensitive, it gives high resolution and is non-destructive.
Other common techniques for determining molecular structure, such as X-ray crystallography
don't work very well for some of these molecules (especially the gases) and are not as precise.
Rotational Spectra 18

Chemistry Department University of Lagos
However, microwave spectroscopy is not useful for determining the structures of large molecules
such as proteins.
Modern microwave spectrometers have very high resolution. When hyperfine structure can be
observed the technique can also provide information on the electronic structures of molecules.
provides number and energy difference of rotational isomers
determination of electric properties of the molecules (dipolar and quadrupolar moment)
Microwave spectroscopy is one of the principal means by which the constituents of the universe
are determined from the earth. It is particularly useful for analysis of the chemical composition in
the interstellar medium (ISM). One of the early surprises in interstellar chemistry was the
existence in the ISM of long chain carbon molecules. It was in attempting to research such
molecules in the laboratory that Harry Kroto was led to the laboratory of Rick Smalley and
Robert Curl, where it was possible to vaporize carbon under enormous energy conditions. This
collaborative experiment led to the discovery of C
60
, buckminsterfullerene, which led to the
award of the 1996 Nobel Prize in chemistry to Kroto, Smalley and Curl.
Rotational Spectra 19

Chemistry Department University of Lagos