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 Microwave Spectroscopy
▪ Rotational energies of molecules are quantized. Ex. Energy E = hν.
(ν: rotational frequency)
▪ The range of rotational frequencies: 8 × 1010 − 4 × 1011 Hz (or)
wavelength range: 0.75 − 3.75 mm ⇒ MWs
▪ Interaction of EM radiation of proper frequency (MWs) with
rotating molecule results in rotational energy transitions.
▪ i.e. By absorption of MW radiation, transitions can occur between
rotational energy levels of molecules.
▪ The direction of dipole moment changes continuously. This
fluctuating dipole interact with electric field of applied EM
radiation gives rotational spectrum. (Molecule must have
permanent dipole moment).
▪ Molecules with zero dipole moment show no rotational spectrum. Ex.:
Homonuclear diatomic molecules H2, N2, O2, etc.
▪ Heteronuclear molecules CO2, CS2, etc. Spherical top molecules.
▪ Addition/mixing of isotopes also becomes MW inactive (only it changes the
mass).
▪ To a static observer, it appears like a change in dipole moment along a
direction/axis (say z) when the molecule rotates. (Due to these rotations
radiation is absorbed).

Dr. Manish Srivastava, Department of Chemistry

Advantages of Microwave Spectroscopy

▪ It has a high resolving power.

▪ It analyses the WHOLE molecule (not like NMR, or IR spectra, which
fingerprint selected parts).
▪ It also detects isotopic species, and conformational isomers. Requirements
are very less.
▪ It is a non-destructive technique. Mainly, it can be used remotely, such as
for interstellar analyses.
▪ Disadvantage: Similar to others, the spectra of large molecules are very
complex.
 Principal moment of inertia

▪ It is defined as the algebraic sum of product of mass and the

square of distance from the axis.
▪ It is given byI mI ar N=∑miri2 ,
I a = momentiof inertia about axis a
mi = mass of particle i
ri = radius from particle i to the axis of rotation
▪ Each particle provides some resistance to change in angular
motion.
▪ The units are mass. squared length: kg.m2
▪ Moment of inertia is affected by both the mass and how the mass is distributed
relative to the axis of rotation.
▪ Unlike mass which remains constant regardless of the direction of motion, the
moment of inertia of an object changes depending on the axis of rotation.

Classification of rotors

Rigid rotor Non rigid rotor

 Rigid rotors

A diatomic molecule consists of two masses bound together. The distance

between the masses, or the bond length, (l) can be considered fixed
because the level of vibration in the bond is small compared to the bond
length.
The two independent rotations of this molecule are with respect to the
two axes which pass though C and are perpendicular to the “bond
length” r. The rotation with respect to the bond axis is possible only for
“classical” objects with large masses.
For quantum objects, a “rotation” with respect to the molecular axis
does not correspond to any change in the molecule as the new
configuration is indistinguishable from the old one.
The center of mass is defined by equating the moments on both
segments of the molecular axis.
r = r1+r2 so r2 = r-r1 Put the value of r2 in above
equation

The value of r1 and r2 put the eq I = m1r12+m2r22

 𝑚 .𝑟 𝑚𝑟
2
I= m1 (𝑚 +𝑚 )2 +m2 ( 𝑚 +𝑚
1
)2
1 2 1 2

𝑚1 𝑚22 𝑚2 𝑚12 2
I= [ 𝑚 +𝑚 + ] r
1 2 𝑚1+𝑚2

𝑚1 𝑚22+𝑚2 𝑚12
I= [ 𝑚 +𝑚 2 ] r2
1 2

𝑚1𝑚2(𝑚1+𝑚2) 2
I = [ 𝑚 +𝑚 2 ] r
1 2

𝑚𝑚1 2
I = [𝑚 +𝑚 ] r2
1 2

𝑚1 𝑚2
I = 𝜇 𝑟2 𝑊ℎ𝑒𝑟𝑒 𝜇 =
𝑚 1 + 𝑚2
The rotation of a diatomic is equivalent to a
“rotation” of a mass μ at r from the origin C. The
kinetic energy of this rotational motion is K.E. =
L2/2I where L is the angular momentum, Iω where ω
is the angular (rotational) velocity in radians/sec.
Example .1: Calculate the value of I and r of CO. B = 1.92118 cm-1.

Solution: I = h/(8π2 B c)
= 6.626 x 10 -34/(8 x 3.14152 x 1.92118 x 3 x 1010)
= 1.45579 x 10-46 kg m2
Since the value of B is in cm-1, the velocity of light c is taken in cm/s. I = μr2.
The atomic mass of C ≡ 12.0000 amu, O ≡ 15.9994 amu. 1 amu = 1.6604 x 10-27
𝑚1𝑚2 1
kg. 𝑊ℎ𝑒𝑟𝑒 𝜇 = 𝑚 +𝑚 . 𝑁 ( N is A.V. no 6.023x1027 kg or 6.023x1023 gm)
1 2
Put the value in this equation calculated the reduce mass 𝜇
The reduced mass of CO can be calculated to be 1.13836 x 10-27 kg.
Therefore r2 = I/µ = 1.45579 x 10-46/1.13826 x 10-27 m2
Or r = 1.131 Ǻ Result .
 Calculate the energy of rigid rotors

The quantized rotational energy levels for this diatomic

𝐽 𝐽 + 1 ℎ2
𝐸𝑗 =
8𝜋 2 𝐼

The energy differences between two rotational levels is usually expressed in cm-1.
The wave number corresponding to a given ∆E is given by ν = ∆E /h c, cm-1 The
energy levels in cm-1 are therefore,

EJ = B J(J+1)
Where B= h/8∏2Ic
The rotational energy levels of a diatomic molecule are shown in Fig

Fig. Rotational energy levels of a rigid diatomic molecule and the

allowed transitions
The selection rule for diatomic molecules is ∆ J = ± 1
+ sign refers to the absorption and – sign to emission of radiation .
Microwave spectra are usually observed as absorption spectra
If the transition take place J to J+1 the rotational frequency is given by

V J-J+1 = B(J+1) (J+2) - B J(J+1)

= B[(J2+3J+2)- (J2+J)]
= B(2J+2)
= 2B(J+1) cm-1
Thus V0-1 =2B; V1-2 = 4B; V2-3
=6B etc.
The selection rule for a rotational transition is, ∆ J = ± 1 In addition to this
requirement, the molecule has to possess a dipole moment. As a dipolar molecule
rotates, the rotating dipole constitutes the transition dipole operator μ. Molecules
such as HCl and CO will show rotational spectra while H2, Cl2 and CO2 will not.
The rotational spectrum will appear as follows

Fig. Rotational spectrum of a rigid diatomic. Values of B are in cm-1.

Typical values of B in cm-1 are 1.92118 (CO), 10.593 (HCl), 20.956 (HF),
1H2 (60.864), 2H2 (30.442), 1.9987 (N2).