ECE/EE/AEIE Spectroscopy BS-CH101

Rotational spectroscopy
Atoms in a diatomic molecule are held together by a chemical bond and undergo rotation and vibration
through absorption of electromagnetic radiation in IR range. However, these rotational and vibrational
energies are much smaller than bond breaking energy. Rotational energy usually lies within 10 
100 ⁄ while vibrational energy usually lies within 10 ⁄ . Spectroscopy in microwave region
is concerned with the study of rotating molecules. For rigid rotor system, molecules are rotating without any
vibration. The following figure illustrates the rigid rotor system

Figure 1 Rotation of a diatomic molecule.

C.G. is operating at the point C. Bond length     

At equilibrium, we have     

The moment of inertia is given by

                     

       . ,     

       .  ,        .  ,    
  
  
 ,     . ! ,              " 
     

  1 1 1
" .  ,  
   "  

" is called reduced mass.

Rotation of a diatomic molecule is equivalent to rotation of mass " at a distance from the origin #.
$%
Rotational kinetic energy is given by & , where,   '  (  )(

It has been established that

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  Square of the magnitude of angular momentum    1ℏ

Thus rotational energy, +$ is given by

ℏ ℎ
+$    1     1  0  1
2 8/ 
Energy difference between two successive energy levels,  and   1 is given by

ℎ ℎ!
∆+  2  1  20  1. , ∆+  ℎ2   ℎ!2̅
8/   3
ℎ 0 0
! , 2̅    52  16  52  16  07 52  16, 8ℎ , 07 
8/ !
 ℎ! ℎ!

ℎ ℏ
0 
8/   2

Selection rules
1. Selection rule states that quantum number changes only by 1 or 1. Thus for an allowed rotational
transition, we have ∆  ±1 and ∆:$  0. All other transitions are spectroscopically forbidden.
Probability of forbidden transitions is zero and probability of all allowed transitions is almost the same.
2. Selection rule also states that molecule, having permanenet dipole moment only will show rotational
spectra. So molecules, such as #, # etc. show rotational spectra but  , # will not show rotational
spectra.

Characteristics
1. Klystron valve is the monochromatic source, which emits radiation over only a very narrow frequency
range.
2. Electromagnetic radiation interacts with a molecule, changing to rotational state and the rotation gives
rise to a spectrum.
3. Rotational transition occurs in the microwave region of the electromagnetic spectrum within 200 !;.

+$<  +$  ∆+  207   1 = +$  +$;  ∆+  207 

4. Energy difference between two successive levels is given by


5. 0 ∝ & . So the value of 0 decreases as  increases. So the value of ∆+ decreases. Thus large moleules
have closely spaced rotational energy levels.
6. Rotational energy levels are degenerate and the number of degeneracy is given by 2  1. For   0,
there is only one degenerate level. For   1, there are three degenerate levels.
7. Energy difference betwwen   0 level and   1 level is low. Rotational population of   1 level is
more than that of   0 level as the degeneracy of   1 is 3 compared to   0, where degeneracy is 1.

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Figure 2 Rotational energy levels of a rigid diatomic molecule and the allowed transitions.

Applications
1. Bond lengths of a diatomic molecule can be calculated using correcponding value of rotational constant.
2. Calculation of relative positions of rotational enetgy levels.
3. Degeneracy of rotational energy states can be calculated.
4. Isotopic mass and isotopic abundance of an element can be calculated accurately by studying
microwave spectroscopy.
5. Microwave spectroscopy can be used to monitor and control of different industrial processes.
6. It can be used to study the reaction kinetics, e.g., esterification reaction.
7. Microwave spectroscopy is useful to monitor the drying process in industries.

Vibrational spectroscopy
Vibrational spectroscopy is a fast and non-destructive analytical method. Generally wave number instead of
wavelength is used in IR spectroscopy since vibrational excitations occur at characteristics frequencies.
When a chemical sample is exposed in IR electromagnetic radiations at a particular frequency, atoms in the
molecule vibrate at that frequency, resulting in stretching of bond lengths and angles like a spring. During
bond stretching or compressing an opposing spring force is automaticaly induced in the sample. The spring
force is given by Hooke’s law ?  @, where,  is the spring constant and @ is the distance between
atomic nuclei.

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Figure 3 Vibrational stretching and compressing of a diatomic molecule.

Figure 4 Stretching and bending processes of a triatomic molecule.

Each bond type can be excited at a characteristic frequency. When bond is excited to vibrate, it absorbs
energy at a particular frequency, where a peak is observed. Stronger the bond, higher energy is required to
vibrate. Vibrational excitation leads to stretching, compressing and bending of bonds.

Vibrational transitions usually occurs in IR range of electromagnetic spectrum. Classification of IR region is

shown below.

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The vibrational frequency range is 400 !;  4000 !;. Each functional group has a characteristic IR
frequency and hence structure of a molecule can be identified using IR spectra. Most of the functional
groups show bending vibrations within the frequency range 500 !;  1500 !;. This particular
frequency range is called Fingerprint region.

Potential energy curves and energy levels

Figure 5 Potential energy curves.

Potential energy curve looks like a parabola and the expression of C is given by
1
C@  @  = @  D  DE
2
At D  DE , he curve shows a minimum, where, C′@  0 and  is the force constant of the bond. Steeper
the parabolic curve, stiffer the bond is and higher the value of  is.

Considering harmonic oscillator, potential energy, C@, can be expanded using Taylor series as follows
1
C@  C0  C G 0. @  C′′0. @   ⋯ ⋯ ⋯ ⋯
2

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C0  0 according to the expression of C@ and C G 0  0 at the minimum. Neglecting the higher degree
of @, we can write
1 1
C@  C GG 0. @  . ! ,   C GG 0
2 2
If C@ changes sharply,  is large. If C@ is changes slowly,  is small.

Figure 6 Change in I value with steepness of the curve.

In a harmonic oscillator, vibrational energy levels are shown in the following figure.

Figure 7 Vibrational energy levels in a molecule considering harmonic oscillator.

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Selection rules
1. The molecule under investigation may not have permanent dipole moment but must gain temporary dipole
moment during vibrational bending and stretching processes. Thus in general heteronuclear diatomic

molecules, like #, have no permanent dipole moment but they are IR active as they gain positive dipole
molecules are IR active but homonuclear diatomic molecules are IR inactive. Some heteronuclear diatomic

moment during vibrational mode.

2. Transitions with ∆J  ±1 are all allowed allowed transitions. When ∆J  1, energy is absorbed and
when ∆J  1, energy is emitted. Other transitions, with ∆J  ±2, ±3 ….etc. are forbidden transitions.
3. J  0 to J  1 transition is normally called the fundamental vibration, while those with larger ∆J are
called overtones.
4. ∆J  0 transition is allowed between the lower and upper electronic states with energy + and + are
involved, i.e. + , J G  1 → + , J GG  1, where, J′ and J′′ indicate the lower and upper quantum
states.
Characteristics
1. Permitted vibrational energy levels are given by
1   
+M  J   ℏ', 8ℎ , '  N = J  0,1,2 … … , "
2 "   
So, +M depends on reduced mass ", not on the total mass.
+M is expressed in  and the Term Value OM  is given by

+M ℏ' 1 ' 1 1
OM  !;  J    J    'E J  
ℎ! ℎ! 2 2/! 2 2

'E is called harmonic vibrational constant with unit !;. 2P  'E !


2. The energy at J  0 level is called zero point energy, which is given by +P   ℏ'
3. Population ratio of the energy levels J  JQ and J  JR is given by
R R ST ;T W⁄X Z
 U V Y
Q Q
4. Heteronuclear diatomic molecules are IR active and execute vibrational transitions. Homonulear
diatomic molecules are IR inactive and do not execute vibrational transitions.
5. Vibrational frequency is given by
+M<  +M ℏ' [⁄"
2̅   
ℎ! ℎ! 2/!
6. The value of 2̅ lies in IR region. Force constant value, , can be calculated from vibrational spectrum
data. Vibrational spectroscopy is observed within frequency range 400  4000 !; .
7. According to the selection rule, ∆J  ±1 and the transition is called fundamental transition. The other
transitions, ∆J  ±2, ±3.. etc. are called forbidden transitions with weak intensity. These transitions are
known as overtones.

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Applications
1. Calculation of relative positions of vibrational enetgy levels.
2. Identification of characteristics IR frequencies of diffeent functional groups and hence molecular
structure can be elucidated.
3. IR studies are widely used in pharmaceutical analysis.
4. IR study is useful to identify an unknown substance. It is used to establish whether a given sample of
an organic substance is identical with another or not. So if two compounds have identical IR spectra
then both of them must be samples of the same substances.
IR spectra of two enantiomers of a compound are identical. So IR spectroscopy fails to distinguish
between enantiomers.
5. IR spectroscopy is useful to study the reaction kinetics.
6. IR spectroscopy is also effective to determine impurities. IR spectrum of the test sample to be
determined is compared with the standard compound. If any additional peaks are observed in the IR
spectrum, then it is due to impurities present in the compound.
7. IR spectroscopic method is used in quantitative analysis of a particular substance. The quantity of the
substance can be determined either in pure form or as a mixture of two or more compounds.

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