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).

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 by I a =∑miri2,

I a = moment 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

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+r 2 so r2 = r-r1 Put the value of r2 in above equation
id

The value of r1and r2 put the eq I = m1r 12+m2r 22

I= m1( 2 / 1+ 2) 2+m2( 1 / 1+ 2) 2

I=[ 1 22 / ( 1+ 2) 2+ 2 12 /( 1+ ] r2
2) 2

I=[ 1 22+ 2 12 /( 1+ 2) 2 ] r2
I=[ 1 2( 1+ 2 ) /( 1+ 2) 2 ] r2
I=[ 1 2 /( 1+ 2)] r2

I= 2

ℎ = 1 2/ 1+ 2

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, Iωwhere 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/(8π2B c)
= 6.626 x 10 -34/(8 x 3.14152 x 1.92118 x 3 x 1010)
= 1.45579 x 10-46kg 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 10-27kg. ℎ = 1 2

/ 1+ 2. 1/ ( N is A.V. no 6.023x1027kg or 6.023x1023gm)

Put the value in this equation calculated the reduce mass

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 10-27m2
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 =
8π2I

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)- B(J2+J)
= 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).
Effect of Isotopes Diatomic (Rigid Rotator) Molecule
 Addition/mixing of isotope in each MW inactive (zero-dipole moment) molecule
also will not give any rotational spectra. Because, isotope changes the mass only.
 Replacement of one atom by its isotope alters the nuclear mass, but the dipole
moment and bond length are intact.
 Mass change alters the moment of inertia: I → I ′ = µ ′ r2 . Let us take
I/ I ′ = µ/ µ ′ = ρ2 where µ is reduce mass of substances.
 Corresponding energy-change becomes ν ′ = 2B ′ (J + 1).
 So, alteration in energy-change becomes ∆ν = ν − ν ′ = 2(J + 1)(B − B ′ ) ⇒
2(J + 1) h/ 8π2I (1 − I/ I ′) ⇒ ∆ν = 2B(J + 1)(1 − ρ2 ).
 When atomic mass increase ∆ν also increases. Transitional energy will be lesser by
∆ν from the initial energy.
 Replacing with corresponding isotope shifts the change in energy due to rotational
transitions (∆ν).

 ∆ν helps to find exact atomic mass of atoms. Ex. Isotope Molecules 12C 16O and 13C
16O.