CLASS BSC

REGITER NO.

SUBJECT CHEM

COLLEGE GOVERNMENT FIRST GRADE COL

CLASSIFICATION OF MOLECULES, ROTATIONAL
SPECTRA OF RIGID DIATOMIC MOLECULES

SESSION 27

AISHWARYA PADOLKAR, BSC 5TH SEMESTER

 CLASSIFICATION OF
MOLECULES
1. INTRODUCTION
Polyatomic molecules have complex rotational spectra. In order to interpret their
spectra, molecules are divided into four classes based on the shape of their moment
of inertia ellipsoids. In the next section, we discuss the various classes of molecules
and their rotational spectra.

2. CLASSIFICATION OF MOLECULES
Molecular shapes are classified by reference to the relative values
of the moments of inertia about three axes at right angles (Fig. 1).

Figure 1. Principal moments of inertia

 Polyatomic molecules are broadly divided into four classes:
(i)  Linear Molecules
(ii)  Spherical Top Molecules
(iii)  Symmetric Top Molecules
(iv)  Asymmetric Top Molecules

∞h

(homonuclear) point groups. In any case, their main axis is aDiatomic molecules belong to this class of
molecules. These molecules either belong to C∞v (heteronuclear) or D C∞ axis along the bond axis (Fig. 2).

2.1 Figure
LINEAR MOLECULES
2. Diatomic molecule
Along this axis, the moment of inertia is zero since no atoms contribute to it (both lie along this axis). Thus, this is the
IA axis since it is the smallest. The other two inertial axes lie perpendicular to this one and to each other and both are
equal in magnitude. Since we are plotting 1/√I to obtain the
moment of inertia ellipsoid, the major axis is along the bond axis and this is of infinite length. The moment of inertia
ellipsoid is a cylinder of infinite length (Fig. 3).
2.2 Spherical Top Molecules
The next category of molecules is the spherical top molecules and this is the most symmetrical of all
categories. All molecules shaped like spheres, such as SF6, CH4 and CCl4, i.e. those which have Oh
and Td (and also Ih) symmetry belong Figure 3. Moment
this category. of inertia
Because ofellipsoid of a linearsymmetry,
their spherical molecule they have

zero dipole moment and they are microwave inactive.

Figure 4. The spherical top methane molecule

3.3 Symmetric Top Molecules
The next category of molecules is the symmetric top molecules, which have two equal principal moments of inertia
and the third is unique. They are further subdivided into two categories:
(i) Prolate symmetric tops
Let us consider the molecule CH3I, obtained by replacing a hydrogen of methane by iodine, reducing the symmetry
from Td to C3v (Fig. 5)
Figure 5. The CH3I molecule

Along the C3 axis, the only atoms that contribute are the light hydrogens, and hence the moment of inertia is smallest along
this axis. Therefore, this must be the ‘a’ axis, since by convention, the smallest component of the moment of inertia is
labelled IA. The other two axes are perpendicular to this axis and to each other and are also equal.
Hence, for this molecule, we may write
Hence, for this molecule, we may write
I <I =I
A B C

and, because of the reciprocal relationship,

A>B=C
Molecules of this type are called Prolate Symmetric Top molecules. Their shape resembles that of a shuttlecock (Fig. 5).
Linear molecules are a special case of prolate symmetric tops, since their IA = 0.The other possibility is that the unique axis
could be the largest (IC) and such molecules are called
oblate symmetric top molecules.(ii) Oblate symmetric top molecules For these molecules,
A B CSuch molecules are flat, saucer shaped and resemble a Frisbee. An example is the planar D3h
I =I <I

molecule BF3 (Fig. 6).

Here, too, the unique axis is C3, but this is perpendicular to the plane of the molecule. It passes through the centre of mass
at the boron atom. All three fluorine atoms contribute to the moment of inertia along this axis, and hence it is the highest IC.
The other two moment of inertia axes also pass through boron. One lies along a B-F bond, and the other is perpendicular
to it (see Fig. 6).
Let us evaluate the three moments of inertia. Along the C3 axis is IC.. If mF is the mass of a fluorine atom and mB
that of boron (Fig. 7), we may write
I =0×m +3m r2 C B FBF
I =0×m +mr2 +2m(r sin30)2=mr2 +1mr 2=3mr 2 A BFBFFBF FBF2FBF2FBF. (1)
For IA, we have considered the perpendicular distance of the two fluorine atoms from
the ‘a’ axis and we observe that IA = 1⁄2 IC. Similarly, for IB, we writeIB =0×mB +0×mF +2mF (rBF sin60) =2mFrBF ⎜⎜ 2
⎟
⎟ = m r
2 F BF
(2)

⎛ ⎞2
22 3 32 ⎝⎠

Comparison with equation (1) tells us that IA =IB =1⁄2IC

Another oblate top molecule is the also planar molecule, benzene (D6h).
All molecules that have a single Cn rotation axis with n ≥ 3 are symmetric top molecules.
One of the exceptions is allene (D2d), which has an S4 axis, though its highest order
proper rotation axis is only C2 (Fig. 8).
If the molecule has its highest order rotation axis as C2 or there is no proper rotation
axis, the molecule is an asymmetric top molecule. This is the least
symmetric class of molecules, for which
I ≠I ≠I
A B C

Their spectra are the most difficult to interpret. The vast majority of molecules, e.g.
H2O, C2H2F2, etc. falls in this category.
---
Example 1
Determine the point group symmetry of the following molecules in their electronic ground states: H 2O, C2H2, C2H4,
cis and trans-CHFCHF, CCl4, BF3, XeF4, CH3F, and C6H6.Determine for each molecule whether it is a symmetric top,
a linear rotor, a spherical top, or an asymmetric top.
Fortunately, their spectra resemble either that of prolate symmetric tops or oblate symmetric tops, depending on the geometry.
Several formulae have been used to evaluate their degree of symmetry, and one that is frequently used is Ray’s asymmetry
parameter, κ, defined as
κ = 2B − A − C (3) A−C

Consider first a prolate symmetric top, for which A > B = C. Substituting for B in equation (3), we obtain
κ = 2C − A − C = −1 A−C

Similarly, for an oblate top, A = B > C. Again substituting for B, we obtain κ = 2A− A−C =1
A−C
Thus, an asymmetric top molecule, which has a negative κ value close to -1 is called near prolate and one with a positive
value
close to +1 is called near oblate. A value close to zero signifies the largest degree of asymmetry.
---
Example 2
Consider the molecule thioformaldehyde, H2CS. The rotational constants are A = 291291.641 MHz, B = 17699.628 MHz
and C = 16651.83 MHz. This molecule is a near symmetric top. Which one (oblate or prolate)?Solution
κ = 2B− A−C = 2×17699.628−291291.641−16651.83=−0.99237 A − C 291291.641 − 16651.82

Since this value is close to -1, the molecule is near prolate.

 3. SUMMARY
In order to interpret rotational spectra, molecules are classified, according to the shapes of their moment of inertia ellipsoids
into four categories.
Linear molecules have a moment of inertia ellipsoid that resembles an infinite cylinder. • Polyatomic linear molecules with N atom
have N-1 bond lengths to be determined, but only one moment of inertia can be
extracted from the spectra. The answer is isotopic substitution that gives more equations. Up to four isotopic substitutions
can be done. More often, this need not be done, since many isotopic species are present in natural
abundance.• Spherical top molecules are the most symmetrical but lack a dipole moment, and are thus
microwave inactive.• Symmetric top molecules have one proper rotation axis Cn with n ≥ 3. They have two
moments of inertia equal to each other. They are further subdivided into prolate tops or
oblate tops, depending on whether the unique axis is the smallest or the largest.• Prolate tops molecules are shaped like shuttlecock
and oblate tops like Frisbees.• The most asymmetrical class is of the asymmetric top molecules. All their principal
components of moment of inertia are different. Their spectra resemble either those of prolate or those of oblate top molecules.
Rotational
Spectra
Incident electromagnetic waves can excite the rotational levels of molecules provided they have an electric dipole moment.
The electromagnetic field exerts a torque on the molecule. The spectra for rotational transitions of molecules is typically I
n the microwave region of the electromagnetic spectrum. The rotational energies for rigid molecules can be found with the aid
of the Shrodinger equation.
The diatomic molecule can serve as an example of how the determined moments of inertia can be used to calculate bond
lengths.

The illustration at left shows some

perspective about the nature of 
rotational transitions. The diagram
shows a portion of the potential
diagram for a stable electronic state of a
diatomic molecule.That electronic state
will have several vibrationalstates
associated
with it, so that vibrational spectra can be
observed. Most commonly,
rotational transitions which are associated
with the ground vibrational state
are observed.
Rotational
Energies
The classical energy of a freely rotating molecule can be expressed as  rotational kinetic energy
where x, y, and z are the principal axes of rotation and Ix represents the moment of inertia about the x-axis, etc. In terms
of the angular momenta about the principal axes, the expression becomes
The formation of the Hamiltonian for a freely rotating molecule is accomplished by simply replacing the angular
momenta
with the corresponding quantum mechanical operators.
Diatomic
Molecules
For a diatomic molecule the rotational energy is obtained from the Schrodinger equation 
with the Hamiltonian expressed in terms of the angular momentum operator.
where J is the rotational angular momentum quantum number and I is the 
moment of inertia.
Rotational transitions
Determining the rotational constant B
enables you to calculate the bond length R. The allowed transitions for the diatomic molecule are
regularly spaced at interval 2B. The measurement and identification of one spectral line allows one to calculate the
moment
of inertia and then the bond length.
Examples
HCl
CN
CH
Table of diatomic molecule parameters
Rotational Transitions,
Diatomic
For a rigid rotor diatomic molecule, the selection rules for rotational transitions are ΔJ = +/-1,
ΔMJ = 0 .

The rotational spectrum of a diatomic molecule

consists of a series of equally spaced absorption
lines, typically in the   of the
microwave region

  . The energies of
electromagnetic spectrum

the spectral lines are 2(J+1)B for the transitions

J -> J+1.
For real molecules like the   , the
example of HCl

successive transitions are a bit lower than

predicted because centrifugal distortion
lengthens
the molecule, increasing its moment of inertia.
Moment of Inertia,
Diatomic
The   about the   is , Where μ is called reduced
moment of inertia center of mass

mass
REFERENCE
1. YoutuTube Videos
2. Google Search
3. Chemistry Base Papers
4. Physical Chemistry by Puri and Sharma
THANK YOU
 Rotational Spectra (Microwave Spectroscopy)

Types of molecules

Linear Symmetric top Spheric Assymmetric tops

molecu (It has axes of symmetry) al Top I = I =I
le H- F H B C A
Cl I =I =I H H
O-C-S
B C A O
O-C-O C (I is not negligible) C C
I =I
A H H =C
B H H H
C H H
(I is I
negligible
=A and =0) H H H
A Vinyl Chloride
Most of the
IA = IB = IC molecules fall in this
catogory
(No interest)
Pr Oblat
ol e
I B= I < I C
at C A
e l
CF B—
Cl
H C
H H
l

1.3 ROTATIONAL SPECTRA OF RIGID DIATOMIC MOLECULE (RIGID

ROTATOR MODEL)
A rigid diatomic molecule means that the distance between the atoms (bond length) does not
change during rotation. No vibrational movement is taking place during rotation.
Let us consider a diatomic molecule A—B in which the atoms A and B having masses m 1 and m2
are joined together by a rigid bond of length r0 = r1 + r2 (figure 1). The molecule A—B rotates about a
point C, the centre of gravity: this is defined by the moment, or balancing, equation.
m1r1 = m2r2 ...(1.1)
m1 m2

r0

A B

r r
2
Fig. (1.1) : A rigid diatomic molecule A-B having atomic masses, m1 and
1

m2, joined together by a rigid bond of length r0 =r1 + r2 and rotates about a
point C.

The moment of inertia about C is defined by

 Rotational Spectra (Microwave Spectroscopy)

I = m r121+ m r22 Q ⎡m
⎣ r1 1= 2m2 ⎦r
2
⎤
= m2 r 2 r 1 +
m1r1r2
2 1 1 ....
= r r (m +2 (1.2)
from eqn (1)
m )r = m r = m (r – r )
1 1 2 2 2 0 1

m1r1 = m2r0 – m2r1

o m1r1 + m2r1 =
r m2r0
o 1 1 2
r r (m +2m
0 ) = m

r
m2 m1
⇒ r1 r Similarl r
2 r ...
= m10 + = m10+
y (1.3)
m2 m2
Putting the value of r1 & r2 from (3) in (2)

m2 0 m m1 + m m 1m2
I r
10
( 2
r0 2 = μ0 ...
= = m1 + r2 (1.4)
)r
1 2 1
( m +m )( m2 + m
) m2

where μ is the reduced mass of the system i.e.

m1 m
μ
2 ...
m1+
(1.5)
= m2
Equation (1.4) defines the moment of inertia conveniently in terms of the atomic masses and the
bond length.
By the use of the Schrödinger equation it may be shown that the rotational energy levels allowed
to the rigid diatomic molecule are given by the expression

h J ( J + 1) Joules when J = 0, 1, 2 ......

EJ 2 ...
= 8π 2
(1.6)
I
In this expression h is Planck’s constant, are I is the moment of inertia, either IB or IC, since
both are equal. The quantity J, which can take integral values from zero upwards, is called the
rotational quantum number and each level is (2J + 1) fold degenerate.
Often it is convenient to analyse the rotational energy spectrum in wave number units.

Therefore we may write.

 Rotational Spectra (Microwave Spectroscopy)

EJ h
J(J + 1 ⎡E =1
−
εJ = 2 1
=
hc 8π cm ⎣⎢⎤ λ⎦
Ic hc ⎥

J = 0, 1, ) ...
= BJ ( J + 2.... (1.7)
where B is the rotational constant and is given by
1)cm−1
h h
B cm21 =
−
2

8π2 Ic 8π I
Joule
=
Denoting the lower state by J´´ and the upper state by J´
ΔεJ = εJ′ – ε J′′

= BJ′ ( J′ + 1) − BJ′ ( J′ + 1)

⎡ ′ ′ ′ ′ ⎤
B ⎣ J ( J + 1) − J (J + 1) ⎦

use of the selection rule or J′ − J′ = 1 gives the frequency of the absorption

line as
( ΔJ = ±1 )

v = Δε = B⎣⎡( J′ +⎦ 1)( J′ + 2) − J′ (
J

⎤ ...
+(1J)′ + 1)2
JB (1.8)

J ⎯⎯→J + 1

ε = B ( J + 1) (J
+ 2)
J +1
ε = B J ( J + 1)
J

Δε = B ( J + 1) ( J+2

) −1 where J = 0, 1, 2....
Δε = 2B ( J + 1−) Jcm

The rotational constant B is assumed to be the same in both lower and upper rotational states
and double prime is dropped from equn (8)
The allowed energy levels of a rigid diatomic rotor are illustrated in Fig. 1.2(a). Thus a
step-wise raising of the rotational transitions result in an absorption spectrum consisting of spectral
lines with a separation of 2 B, that is at 2B, 4B, 6B, .... (Fig. 1.2(b)). The lowering of stepwise energy
results in identical emission spectrum.

6
 Rotational Spectra (Microwave Spectroscopy)
Fig. (a) allowed energy levels of a rigid diatomic rotor showing electric dipole allowed
transitions and (b) the resulting absorption spectrum.
J 6 42 B
12B

5 30 B 0 1 2 4
10 B 5J
3
4 20 B
8B
3 12 B
6B
2 6B
4B
1 2B
2B
A
0 0 b 2B 4B 6B 8B 10 B 12
ms s B
o
Fig. 1.2 (a) Fig. 1.2(b) r
p
Fig. 1.2(a) allowed energy levels of a right diatomic
t rotor showing electric dipole
allowed transitions and 1.2(b) the resulting absorption
i spectrum.
1.4 THE SELECTION RULES o
n

i
The selection rule for a transition between any two rotational
n states is quantum chemically given
by t
ij ∫i j e
μ = ψ μΨ dτ n
s
i
Ψ t μ
where ψi and j are the wave functions for the rotational
y
states i and j and is the permanent
dipole moment of the molecule. The dipole moment being a vector quantity can be expressed
→ by→its
three components along the Cartesian coordinates axes, μ = μ + μ + μ →
x y z

μ2 =y μ2 + μz2 + μ2
and
x . The transition moment integral can be split in terms of the components
of the dipole moment,

⎡⎣ μijx ⎦⎤ ∫ i μ x μ
j
dτ
=
⎡⎣μijy⎦⎤ ∫ i μ y jμ
dτ
=
⎡μz ⎤
⎣ ij ⎦
∫ μi z jμ
dτ
If atleast
= any one of the integrals is non zero, then the transition is allowed and forbidden
otherwise. The intensity of an allowed rotational transition depends on the square of the
 Rotational Spectra (Microwave Spectroscopy)
transition dipole moment. Consequently, the intensity of the rotational line depends on the square of the
permanent dipole moment of the molecule.
Schrödinger equation shows that for a diatomic rigid rotor (in the absence of an external electric
or magnetic field) only transitions in which J changes by one unit, that is, ΔJ = ±1 are allowed and all
other transactions are forbidden. Thus the selection rule for rotational spectra is ΔJ = ±1 ( plus sign for
absorption and minus sign for emission) and second, the molecule must have a permanent dipole
moment (only hetronucelar diatomic molecules will exhibit the rotational spectrum since homonuclear
diatomic molecules do not possess permanent dipole moment)
1.5 NON RIGID ROTOR
It is observed that in the pure rotational spectra of a diatomic molecule when the bond in it is
considered as a rigid, the spacing between successive lines is same, i.e. 2 B cm –1. However, the
assumption that the bond is rigid is only an approximation. Actual bond is not a rigid bond and the bond
length is not constant. It increases with rotations and is elastic. In a rapidly rotating molecule, there is
always a tendency of the bond to stretch due to centrifugal effects. Hence, the moment of inertia
increases with the rotational energy. This causes rotational levels to be same what closer as the J value
increases.
For example, consider the spectrum of hydrogen fluoride

(
B cm−1 r
) (nm)
J=0→J=1
20.56 0.09
29
J=1→J=2 20.48 0.09
31
J=2→J=3 20.43 0.09
32
J=4→J=5 20.31 0.09
35
It is evident that the separation between successive lines (and hence the apparent B value)
.
decreases steadily with increasing J.
. .
The reason for this decrease.may be seen if we. calculate .internuclear distance from the B values.
In simple harmonic motion a molecular bond is compressed and extended an equal amount on each
. . .
side of the equilibrium distance and the average value of the distance is therefore unchanged, the
.
average value for a bond of equilibrium length 0.1 .nm vibrating
. between the limits 0.09 and 0.11 nm,
we have
J = 10 → J = 18.91 0.09
11
69