Microwave Spectroscopy

• When the molecule rotates – change in dipole moment should be obtained

• Molecules can be microwave active or inactive
• Homonuclear molecules – H2 – do not show change in dipole moment
• Heteronuclear molecules like HCl – change in dipole moment
• Incase of Linear molecules :
• Any molecule will have moment of inertia..it will possess in three dimensions
a) Along the bond axis – IA
b) End over end rotation – in the plane – IB
c) End over end rotation – perpendicular to plane – Ic
Incase of Linear molecules
IA = 0 , I B = IC
• Symmetric top molecule :

• Prolate : IB = IC  IA , IA  0
• IB = I C > I A

• Moment of inertia about C-F axis is not negligible as it involves rotation of 3

comparatively massive H atoms off this axis. Such a molecule spinning about this
axis can be imagined as a top.
• Oblate – BCl3 - planar and symmetrical

• IA = I C < I A
• IA = 2 IB = 2IC
• 3) Spherical top : methane
• IA = IB = Ic - as all 3 moments of inertia are identical
• No change in dipole moment. – microwave inactive
• I = 8/3 mA R2

4) Asymmetric tops : These molecules, to which majority of substances belong,

have all 3 moments of inertia different :
• IA  IB  I C

• Simple examples are water, vinyl chloride

• allowedEnergy levels
• Allowed transitions between rotational levels
 Intensity of spectral lines
• Boltzmann distribution
• Degeneracy of energy level
Effect of Isotopic substitution
• Effect of isotopic substitution
on energy levels and hence
rotational spectrum of
carbon monoxide.
 No rigid rotator
• Rotational spectrum of HF
• If bond is elastic, molecule may have vibrational energy – bond may stretch and
compress with a certain fundamental frequency
• If motion is simple harmonic, force constant is

• Weaker the bond, more readily it will distort under centrifugal forces.
• Second consequence of elasticity is that r and B vary during a vibration.
• Many hundreds of vibrations occur during a rotation. Consider bond of
equilibrium length 0.1nm vibrating between the limits 0.09 and 0.11nm.

• Real vibrations may not be simple harmonic

• 3 different sets of values of B and r :
• At equilibrium separation re , between the nuclei, rotational constant is Be
• In vibrational ground state, average internuclear separation is r0 associated with a
rotational constant B0
• If molecule has excess vibrational energy, rv and Bv where v is the vibrational
quantum number.
• Hf and other diatomic hydrides – small moment of inertia and a large B value
• Spacings between rotational energy levels becomes large and fall into IR region after only a few
transitions.

SPECTRUM OF A NON-RIGID ROTATOR

• Schrodinger eqn may be set up and rotational energy levels are :

• Centrifugal distortion constant D is given by :

• The below applies to simple harmonic force field only

• If the force field is anharmonic,

• H, K are constants. From defining eqns of B and D ,

where  is vibrational frequency of bond.

• Vibrational frequencies are of order of 103 cm-1 , while B is found to be of order of
10 cm-1.
• D is found to be of order of 10-3 cm-1 . For small J, correction term DJ2 (J+1)2 is
almost negligible. While for J values of 10 or more, it may become appreciable.
• Change in rotational energy levels when passing from a rigid to a non-rigid
diatomic molecule. Lowering of rotational levels has occurred.
• Selection rule : J = 1
• An analytical expression for the transitions

• The value of D gives useful information :

1) Allows us to determine the J values in an observed spectrum
2) Knowledge of D enables us to determine vibrational frequency of a diatomic
molecule

From the data for HF, we have

The force constant is :

This indicates that H-F has a relatively strong bond.

 POLYATOMIC MOLECULES
• Linear molecules such as OCS or chloro acetylene where all atoms lie on a striaght
line.
• Since IB=IC; IA=0 as for diatomic molecules, energy levels are:

•
• The spectrum will show 2B separation modified by distortion constant.
1) Since moment of inertia for end-over-end rotation of a polyatomic linear
molecule is greater than that of a diatomic molecule, B value will be much
smaller . Spectral lines are more closely spaced. B values are about 10cm-1 for
diatomic molecules.
2) Molecule must possess a dipole moment if its to exhibit a rotational
spectrum.OCS will be microwave active while OCO will not.Isotopic substitution
does not lead to a dipole moment.
3) A non-cyclic polyatomic molecule containing N atoms will have N-1 individual
bond lengths to be determined.
4) In OCS- triatomic : CO distance rco , CS distance rCS
5) There is only one moment of inertia for end-over-end rotation of OCS.
• Its impossible to deduce two unknowns
• Difficulty can be overcome by isotopically substituted molecule
• Microwave specrtum of carbon oxysulphide
• Carbon oxysulphide
 Symmetric Top molecule
• Choosing methyl fluoride : IB = IC  IA
• IA 0
• 2 directions of rotation in which molecule might absorb or emit energy – about
the main symmetry axis (C-F bond) and that perpendicular to this axis.
• We need two quantum numbers to describe degree of rotation, one for IA, and
one for IB or IC
• J – total angular momentum
• K for angular momentum about top axis – about C-F bond
• Values allowed to K and J : both must be integral or zero
• Total angular momentum can be as large i.e J can be 0,1,2….,∞
• K can be negative ..-1 or -2 etc – clockwise or anticlockwise rotation
• K – 2J+1 values

• Rigid symmetric top :

• Energy depends on K2 . For all K > 0, rotational energy levels are doubly
degenerate.
• Rigid molecule

• When centrifugal stretching is taken into account, energy levels become :

where DJ, DJk and DK are small correction terms for non-rigidity.
• Spectrum is :
 Stark Effect
• Exptally – requires placing of an electric field –either perpendicular or parallel to
direction of radiation beam across the sample.
• A molecule exhibiting a rotational spectrum must have an electric dipole moment
and its rotational energy levels will be perturbed by application of an exterior
field since interaction will occur.
• Absorption lines will be shifted by an amount depending on extent of interaction
and on both E, and dipole moment.
• Measurement is on very dilute gas samples
2) Application of stark effect – assignment of observed spectral lines to particular J
values.
3) 3rd application : signal to noise ratio – random fluctuations in backround
radiation may be removed by modulating beam by means of stark effect.