Microwave

spectroscopy
What’s the microwave spectroscopy?
A sensitive technique for chemical analysis and the
determination of molecular structure
(Bond lengths, bond angles, and dipole moments) and also
relative atomic masses. It is based on the principle that
microwave radiation
Some uses of microwave spectroscopy
Microwave spectroscopy has been used in monitoring and control
of industrial processes. It is an ideal process analyzer as it is:
1. non-invasive: the measurement can be made outside of the
reaction chamber, eliminates the need for sampling or physical
removal of sample.
2. non-destructive.
3. can be used for solids, liquids, gases and suspensions .
4. can be used for dark coloured samples.
5. analyses large sample volumes, as microwaves diffuse out from
the transmitter though the entire sample becomes lower
Microwave spectroscopy has been used in monitoring
and control of industrial processes, such as;
1. materials with low dielectric constants, such as plastics, glass,
ceramics and composite materials.
2. determination of moisture in various tobacco types.
3. Monitoring of a batch esterification reaction as in the
esterification of butanol by acetic acid.
4. Monitoring of the drying process in industry as it is one that is
hard to monitor. For example, huge cakes of wet material when
dried in big vessels.
5. Astrophysical applications, radio astronomy: probe of the
molecular universe (molecular clouds) using Telescope
Fourier transform microwave (FTMW) spectroscopy
can provide accurate and detailed information about the structure and
the dynamics of van der Waals complexes.
The complexes are produced in a pulsed supersonic jet expansion of a
gas mixture into a vacuum chamber. The temperature of the sample in
the jet expansion is on the order of a few Kelvin, and the complexes are
stabilized in this nearly collision-free environment
The analysis of the resulting spectra results in the determination of
rotational constants which are related to the principal moments of
inertia of the complex. From these constants, the molecular geometry of
the complex can be determined
Summary of information from microwave spectroscopy
It is mainly used to get information about gas molecules, such as
1. Accurate bond lengths and angles.
2. Electric dipole moments.
3. Centrifugal distortion constants.
It can also be used to study relaxation times, dielectric
constants, dipole moments in liquids and solutions, and potential
energy barriers to rotation.
In some cases, we can get information about the
mechanism of chemical reactions, such as the
decomposition:
15
NH414NO3  15N14NO
 
The requirements to get a microwave spectrum are:
Substance must have electric dipole moment (or
magnetic dipole moment)
Its vapour pressure > 10-3 mmHg. 
Characteristics of microwave spectroscopy, compared
with other techniques are:
1. It has a high resolving power.
2. It analyses the WHOLE molecule (not like nmr, or ir spectra, which
fingerprint selected parts).
3. It detects isotopic species, and conformational isomers.
4. Only a few ng of gas are required.
5. It is a non-destructive technique.
6. It can be used remotely, such as for interstellar analyses.
7. The spectra of large molecules are very complex. Absolute absorbance is
difficult to measure. NBS has list of microwave spectra for qualitative
analysis.
Basic concepts
Rotational energies of molecules are quantized
(i.e. only have definite energies)

where
E is energy in J
E = h h Planck’s constant, Js
   rotational frequency, Hz.

The range of rotational frequencies is about 8x1010 - 4x1011 Hz, which

corresponds to wavelengths,  ~ 0.75 - 3.75 mm. These wavelengths fall in
the microwave region of the electromagnetic spectrum. 
By absorption of microwave radiation, transitions can occur
between rotational or inversion energy levels of molecules.
N.B. Molecule must have permanent dipole moment (D.M.) if it has
a rotational spectrum.
To an observer, there is a change in dipole moment along z when the molecule
rotates. The oscillating electric field of microwave radiation, incident upon
the molecule, can therefore make this rotation occur (i.e. the radiation is
absorbed).  
Some definitions about rotation.
For simplicity, we consider a diatomic molecule
throughout.
 
Q P

Where
I is moment of inertia
r is distance of atom I from rotation axis (m)
I =  miri2 M is mass in kg.

Angular momentum = I, where the

 = 2 angular frequency (radian s-1),
Classification of molecules according to I values
1. Linear molecules 2. Symmetric tops
IA = 0; IB = IC
I A  0; IB
 
= IC 
 3. Spherical tops 4. Asymmetric tops
 
IA = IB = IC IA  IB  IC

This is type of molecule has no rotational

spectrum.
Can you classify the following molecules into
these types:
I get HCN linear; CH3I, H2CO, C6H6 symmetric
top; CH2=CHCHO, C4H4N2 asymmetric top; SF6,
CH4 spherical top.
Rotation spectra of diatomic molecules
 
Consider molecule with nuclear masses m1 and m2

Assume a rigid (not elastic) bond

  r0 = r1 + r2

For rotation about center of gravity, C :

  m1r1 = m2r2 ( = m2 (r0 - r1) )
(C is centre of mass)
/ \
m2r0 m1r0
r1  r2 
m1  m2 m1  m2
Moment of inertia about C:
IC = m1r12 + m2r22 = m2r2r1 + m1r1r2
= r1r2 (m1 + m2)
 
m1m2 2 2
  I  r0  μr0
m1  m2
1 1 1
 = reduced mass,  
μ m1 m2
More detailed derivation:
2 2
IC  m1r1  m2r2
 m2r2   m1r1 
 m1r1    m2r2  
 m 1   m 2 

 r1r2 m1  m2 
 m1r0   m2r0 
     m1  m2 
 m1  m2   m1  m2 
m1m2 2
 r0
m1  m2
 From the Schrödinger equation:

Rotational energy of level J,

h2
EJ  J(J+1) Joules Where
8π 2I h is planks constant
I is the moment of inertia
J is the rotational quantum number
J= 0, 1 , 2 , 3 ,….
Note that:
J = 0 is the lowest level, and the molecule is not rotating in this level.
Dividing above equation by hc
Not that
E = h = hc/ = hc ν
ν = 1/
ν ν = E/hc

is rotational constant B

So, J(J+1) cm-1 = BJ(J+1) cm-1

Appearance of microwave spectrum
 

J =0  BJ(J+1) = B X 0 (0+1) = 0B cm-1

J =1  BJ(J+1) = B X 1 (1+1) = 2B cm-1
J =2  BJ(J+1) = B X 2 (2+1) = 6B cm-1
J =5  BJ(J+1) = B X 5 (5+1) = 30B cm-1
J =6  BJ(J+1) = B X 6 (6+1) = 42B cm-1

Note that:
the selection rule is J = 1
where + applies to absorption and - applies to
emission. This diagram shows the rotational
energy levels of a diatomic molecule
Difference of wave number
J = 3  J = 4 : ∆ = 2B(3+1) = 8B cm-1
= B(J+1)(J+2) - BJ(J+1) J = 4  J = 5 : ∆ = 2B(4+1) = 10B cm-1
= 2B(J+1) cm-1
J = 5  J = 6 : ∆ = 2B(5+1) = 12B cm-1
J=0 J=1:
J = 6  J = 7 : ∆ = 2B(6+1) = 14B cm-1
∆ = B(J+1)(J+2) - BJ(J+1)
= B(0+1)(0+2) – B0(0+1) = 2B - 0 = 2B cm-1
OR = 2B(J+1) = 2B(0+1) = 2B cm-1

J=1 J=2:
∆ = 2B(J+1) = 2B(1+1) = 4B cm-1 Note that
The spectra appear at an equal distance
J=2 J=3:
∆ = 2B(J+1) = 2B(2+1) = 6B cm-1
This is part of the rotational (far infrared) spectrum of CO. You can see
that the separation, 2B, is roughly 4 cm-1. Assign the lines.

12
C16O (major species)
13
C16O and 12C18O lines
 Intensity of rotational spectral lines

NJ/No = 2J+1 e-E/kT

Where:
F(J) is energy of levels as a function of J.
2J+1 = degeneracy of J level.
e-E/kT = Boltzmann temperature factor.
NJ//No = population of level J compared with level O.
= transition wavenumber

Rotational Energy Levels of CO

Note that
NJ/No increase with j increase then NJ/No decrease
Application
 
The measurement of a microwave spectrum enables us to determine bond
lengths and angles accurately for gaseous molecules.
 
Example for CO:
(J=0  J=1) for 12
C16O is at 3.84235 cm-1.
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 1010 cm s-1
Find r(CO)
  h 2.7992774 10  46

I 2  kgm2
8π Bc B
= r2
B = 1.921175 cm-1 ;  = 1.1386378 x 10-26 kg

 r I
= 1.131 x 10-10 m
μ
 0.1131 nm
Answer: C-O bond length is 0.1131 nm.
Intensities of rotation spectral lines
 
Now we understand the locations (positions) of lines in the
microwave spectrum, we can see which lines are strongest.
 
J  BJ(J+1)
 
J=0  0
Intensity depends upon initial state population
Greater initial state population gives stronger spectral
lines. This population depends upon temperature, T.
NJ  EJ   hcν 
 exp    exp  
N0  kT   kT 
k = Boltzmann’s constant, 1.380658 x 10-23 J K-1
(k = R/N) hc
 1.52034 cmK
k
 
NJ  1.52034ν 
 e  
No  T 
We conclude that the population is smaller for higher J states.
Intensity also depends on degeneracy of initial state.
(degeneracy = existence of 2 or more energy states having exactly the
same energy)
Each level J is (2J+1) degenerate
 population is greater for higher J states.
To summarize: Total relative population at energy
EJ  (2J+1) exp (-EJ / kT) & maximum population
occurs at nearest integral J value to : 1 kT
 
J 
2 2hcB
Look at the values of NJ/N0 in the figure, slide #24
Here is some more detail that you might like to skip

At maximum population value,

Plot of population of rotational energy
slope = 0: Putting x = hc/kT
levels versus value of J.
 d
slope  2J  1e  xBJ(J 1)
 0
dJ
0  (2J  1) xBe  xBJ(J 1)
 (2J  1)  2e  xBJ(J 1)

0e  xBJ(J 1)
 xB(2J  1) 2
 2

SO,  xB(2J  1) 2  2  0
1 1
J   
2 2xB
1 kT
J   
2 2hcB
Effect of isotopes
From 12
C16O  13
C16O
mass increases, B decreases ( 1/I ), so energy levels lower.
Comparison of rotational energy levels of 12
CO and 13
CO
 
Can determine:
(i) isotopic masses accurately, to within 0.02% of other methods for atoms
in gaseous molecules;
(ii) isotopic abundances from the absorption relative intensities.
Example:
for 12
CO J=0  J=1 at 3.84235 cm-1
for 13
CO 3.67337 cm-1
Given : 12C = 12.0000 ; O = 15.9994 amu
What is isotopic mass of C ?
13

B(12CO) = 1.921175 cm-1

B(13CO) = 1.836685 cm-1
Now 1 1
B 
I μ
μ(13 CO) 1.921175
 12   1.04600
μ( CO) 1.836685
(13 C)  15.9994 12  15.9994
 1.046  13 
( C)  15.9994 12  15.9994
 (13C) = 13.0006 amu
Refinements to theory for diatomic molecules
Rotation spectrum of hydrogen fluoride in the far IR region 
Note that: r increases with J because the bond is not rigid
but elastic.
H-F atoms are pushed apart at higher rotational speed by
centrifugal force.
 
2 2 2
For an elastic bond : k  4π ν c μ
where k is the bond force constant (Nm-1). Smaller k, less
rigid bond.
Note also that r and B vary during a vibration.
We can refine the theory by adding a correction term, containing the
centrifugal distortion constant, D, which corrects for the fact that the
bond is not rigid. Assuming harmonic forces:
EJ = BJ(J+1) - DJ2(J+1)2 cm-1
3
h3 1 4B
D 4 2 2
cm 
32π I r kc ν vib
2

where is bond stretch wavenumber.

 i) can find J values of lines in a spectrum - fitting 3 lines gives 3
unknowns: J, B, D.
ii) We can estimate ν vib from the small correction term, D.
Polyatomic molecules
 
Things get much more complicated, but the general principles
are the same.
 
e.g. OCS HCCCl Ic = IB; IA = 0
 
* I greater than for diatomic molecule,  B smaller; lines more
closely spaced.
 
* Remember that the molecule must have D.M. for microwave
spectrum.
Microwave spectrum of carbon oxy-sulphide

N atoms  N-1 bond lengths, so for OCS must determine

rCO, rCS : that is, two bondlengths are unknown - not just 1 as
in a diatomic molecule
 need 2 values for IB - the second can come from an isotopically substituted
molecule, which has same bondlength (almost), but different mass.
 
e.g. 16OC34S, 18OC34S ….

OCS

centre of gravity
moro + mCrC = mSrS

I = moro2 + mCrC2 + mSrS2

 

In accurate work isotopic bond lengths differ, due to differences in zero

point energy.