Molecular Spectroscopy

Online Workshop on Lectures and Virtual Practical Demonstrations, 6-19 July 2020
Papia Chowdhury
Department of Physics and Materials Science & Engineering
Jaypee Institute of Information Technology Noida, U.P.,
India
• It is defined as the study of the interaction of electromagnetic
radiation and matter.
• Due to interaction the incident of absorption or emission of
electromagnetic radiation by the molecules happens.
• Output of the interaction provides data like frequency or wavelength
of radiation and the intensity of radiation emitted or absorbed by the
molecule.
• In this way we can determine the size, shape, flexibility, electronic
arrangement of the molecule means molecule structure studies.
 Different kind of spectroscopy
• Microwave Spectroscopy.
• Infrared Spectroscopy.
• Raman Spectroscopy
• Electronic Spectroscopy
• Spin Resonance ( NMR and ESR Spectroscopy)
• X-ray Crystallography
• Mass Spectroscopy
• Electron Microscopy
APPLICATIONS

Depending upon the frequency range they are classified. Each class
has its unique set of application in Physics, Chemistry, Biology,
Electronics, Biotechnology and other fields.
The main characteristics of Electromagnetic Radiation:


 Wavelength, frequency and energy of
radiation
• Electronic radiation may be considered as a simple
harmonic wave propagated from a source and
travelling in straight lines.
• Electromagnetic radiation associates electric and
magnetic fields where both fields are perpendicular
to each other and to the direction of propagation.
 Absorption / Emission of Photons
and Conservation of Energy

Eg - Ee =ΔE= h Ee - Eg = h
 Absorption vs. Emission
Absorption vs. Emission
Understanding emission and absorption
Absorption
spectrum of
Sun

Emission
spectra of
various
elements
Energy levels of a molecule
 Microwave region in
electromagnetic spectrum

• Change in orientation
• Wave number = 1-100 cm-1
• Wavelength = 1 cm – 100 m
• Frequency = 3 x1010 – 3 x 1012 Hz
• Energy = 10 -103 Joules/mole
DIRECTION OF ORIENTATION

Direction of dipole
• The molecules which shows microwave spectra must carry
permanent electric dipole moment.

• Carries a permanent net positive charge and other a net

negative charge.
• The rotation of this type of molecule with center of gravity
remain fixed.
• All molecules having permanent moment are microwave active.
HCl, HBr etc.
Infrared/Vibrational
Spectroscopy
 Vibrational (Infrared) spectrum
• If the relative displacement of a molecular vibration
about their mean position gives rise a dipole change
along the direction of displacement during the
vibration, molecule shows vibrational spectrum.

•In order to be infrared active , there must be a dipole

change during the vibration and this change may take
place either along the line of symmetry axis or
perpendicular to it
•Vibrational spectra will be observable only in
heteronuclear molecules since homonuclear molecules
have no dipole moment

•If the atom is removed a distance from its equilibrium

position, it experiences a restoring force that is
proportional to its displacement from the equilibrium
position. The molecule then behaves like a spring.
• The spring which behaves in this manner is said to
obey Hooke’s law:
f x
 f   kx
•x is the measure of the displacement from the
equilibrium position, f is the force which the spring
imposes on atom. k is a proportionality constant called
the force constant, it gives the restoring force from
equilibrium position.
• Negative sign is due to as x increases in one direction
the force increases in opposite direction.
• Hook’s law implies that the energy of the particle
increases as the particle moves in either direction.
• Let work that must be done to displace the particle a
distance dx is fapplied dx, and this work is stored as
potential energy U. Thus
dU = fapplied dx
• Force f that the spring exerts on the particle and it acts
against the applied force as f = - fapplied
dU  ( f )dx This is an important
Relation between force
And potential energy.
dU
 f
dx
 f  kx
dU
 kx  dU  kxdx
dx
1 2
 U  kx
2
If after stretching length of the string is r and equilibrium
Length is re then
1
f  k (r  re ) and U  k (r  re ) 2

2
If we want to describe the motion of the particle then we may
use Newton’s law as f = ma as
d 2x
 kx  m 2   kx  m
x
dt
 this equation has the solution of the form
x  A cos(2t   )
The correctness of this solution can be verified by substituting
This and its second derivative back into the differential equ.
When this is done one obtain an equality if
 4  m   k
2 2

1 k
  Hz
2 m
1 k 1
 cm
2c m
This shows that a particle with mass m held by a spring with
Force constant k will vibrate with frequency .
SHM and Uniform Circular Motion
Springs and Waves behave
very similar to objects that
move in circles.

The radius of the circle is

symbolic of the
displacement, x, of a spring
or the amplitude, A, of a
wave.

xspring  Awave  rcircle

 H’ H’’
Cl
e5

Cl

H’’
e1
H’
 Vibration of Diatomic Molecule
• Consider a diatomic molecule where two atoms are
bounded by bond.
• TWO ATOMS OR PARTICLES BE ALLOWED TO
MOVE ONLY ALONG LINE OF THE SYSTEM.
• Let x1 and x2 represent displacement of the particles
of mass m1 and m2 from initial position in which the
perticles were separated by their equilibrium distance,
if Hook’s law is assumed for the spring the kinetic and
potential energy
1

T  m1 x1  m2 x2
2
2 2

U  k  x2  x1 
1 2

2
 Vibration of Diatomic Molecule
•Compression and extension of a bond may be likened to the
behaviour of a spring. Assuming that the bond, like the spring,
obeys Hook,s law. We may then write
f = - k ( r- req.). Here f is a restoring force and r the inter
nuclear distance. In this case the energy curve is parabolic and
has the form
U = ½ k ( r - req.)2
•This is identical in form to that for single vibrating particle.
• This model of vibrating diatomic molecule-so called simple
harmonic oscillator model- while only an approximation, forms
an excellent starting point for the discussion of vibrational
spectra.
• The zero of the parabolic curve is at r=re and energy in
excess of this arises because of extension or
compression of the bond.
• During vibration heavy atom stays still and lighter
atom generally moves. But only distance between two
atoms is important in vibration.
• During extension or compression vibrational frequency
will not change because intrinsic vibrational frequency
dependent on mass of the system and force constant
and independent of amount of distortion.
• All these behaviour are same as the simple harmonic
oscillator.
Schrodinger’s equation for the harmonic oscillator is
d  2m 
2
1 2
 2  E  kx   0
dx 2
  2 
1
1  2
2m
if y km  x x
  
2E m 2E
and   
 k 
d
 
2
 2
   y 2
 0
dx ……..(1)
The solution to this equation that are acceptable here are limited by

 2



dy  1

The mathematical property of (1) is such that a condition must fulfil

 = 2v+1 v = 0, 1, 2, 3, ….
The energy level of a harmonic oscillator is given by

 1
E v   v   h
 2
Schrodinger’s equation for the harmonic oscillator is
d 2 2m  1 2 
 2  E  kx   0
dx 2
  2 

Ev = ( v + ½ ) h osc joules ( v = 0, 1, 2, …..),

where v is the vibrational quantum number.
 The simple Harmonic Oscillator
In spectroscopic units
ev = ( v + ½ ) osc cm-1 ………………………(3)
The lowest energy obtained by putting v = 0 is
e0 = ½ osc cm-1
Implication from this result is that diatomic molecule( indeed
any molecule) can never have zero vibrational energy; the
atoms can never be completely at rest relative to each other.
The quantity ½ osc cm-1 is known as the zero point energy.
Selection Rule: Δ v = ± 1
Vibrational energy changes will only give rise to an
observable spectrum if the vibration can interact with
radiation.
 The simple Harmonic Oscillator
Applying the selection rule we have immediately:
e v+1v = ( v+1 + ½ ) osc - ( v + ½ ) osc = osc cm-1
for emission and
e v  v+1 =  osc cm-1 for absorption, whatever the initial value
of v.
• Such a simple result is obvious as vibrational levels are
equally spaced, Transitions between any two neighbouring
states will give rise to same energy change.
• spectrosco pic =e =  osc cm-1 The vibrating molecule will
absorb energy only from radiation with which it can
coherently interact and this must be radiation of its own
oscillation frequency.
 H’ H’’
Cl
e5

Cl

H’’
e1
H’
 The Anharmonic Oscillator
•Real HCl do not obey the laws of simple harmonic
motion. If the bonds between the atom is stretched ,
there comes a point at which it will break- the molecule
dissociates into atoms.
•The purely empirical expression which fits the
anharmonic curve to a approximation was derived by
P.M. Morse, and is called the Morse function:
•V(r) = Deq.[ 1 - exp { a ( req - r)}]2, where a is a constant
for a particular molecule and Deq is the dissociation
energy.
Selection Rules:  v = ± 1, ± 2, ± 3,…….
1. v=0v=1, v = + 1 with considerable intensity.
e = ev=1 - ev=0
= (1 + ½ ) e - (1 + ½ )2 e xe - {½ e -(½)2 e xe }
= e( 1 - 2 xe)cm-1 ……………………(a)
2. v=0v=2, v = + 2 with small intensity.
e = ev=2 - ev=1
= (2 + ½ ) e - (2 + ½ )2 e xe - {½ e -(½)2 e xe }
= 2e( 1 - 3 xe)cm-1
3. v=0v=3, v = + 3 with considerable intensity.
e = e v=3 - e v=0
= (3 + ½ ) e - (3 + ½ )2 e xe - {½ e -(½)2 e xe }
= 3 e( 1 - 4 xe)cm-1 ……………(c)
To a good approximation since xe 0.01, the three spectral
lines lie very close to e,2 e and 3 e. They are known as
fundamental absorption, first overtone and second overtone
respectively.
Example: For HCl molecules we have three peaks at
at 2886 cm-1, at 5668 cm-1,and at 8347 cm-1
 The Vibrations of Polyatomic Molecules.
The spectrum of polyatomic molecules is quite complex.
• Fundamental Vibrations and their Symmetry:
• For a molecule containing N atoms, 3N
coordinate values are required to define it
completely. If 3N coordinates are fixed then the
bond distances and bond angles of the
molecule are also fixed then Molecule is said
possessing 3 N degree of freedom.
• Degrees of freedom is a general term used in
explaining dependence on specific parameters and
implying the possibility of counting the number of
those parameters.
• If the molecule is free to move in three dimensional space
without change of shape such that the molecule has only
translational change. so the degrees of freedom will be 3N-3.

•As there are 3 translations and rotations which do not form

internal vibrations so we have
•For Non-linear: 3N - 6 fundamental vibrations.
•For Linear : 3N - 5 fundamental vibratons as rotation
about the bond axis is restricted.

Since an N atomic molecule has N-1 bonds between its atoms,

N-1 of the vibrations are bond stretching, the other 2N-
5(nonlinear) or 2N-4(linear) are bending motions.
 Examples: For diatomic molecule, N=2, 3x2 -5 =1,
only one fundamental vibration.

•For water, N=3, 3x3-6 = 3 allowed fundamental vibrational

modes.

•These vibrational modes are also referred to as the normal

modes of vibration of the molecule.

• By utilizing the symmetry elements in the molecules each

motion may be leveled symmetric or antisymmetric.
Bending Symmetric stretching Asymmetric stretching
 S(OH) AS(OH)

# IR active modes

frequency (cm-1) Intensity Mode

1800.00 265.83 

3810.00 10.00 S(OH)

3945.00 70.84 AS(OH)

The spectrum of liquid water recorded with a 2 m m thick normal liquid cell with ZnSe
windows in transmission mode (red spectrum) and original ATR spectrum (blue
spectrum) both normalized to the OH stretching intensity.
Reflection-Absorption Infrared Spectrum of
NPB

1468

1314
1586

1284 789
1391 782
819 760 702 518 424

1492
775
1593
1393 1292 799
824 753 697
1275 513 426

1500 1000 500

Wavenumbers (cm-1)
Reflection-Absorption Infrared Spectrum of
AlQ3

N O

O Al N

N O

1473
752 1386
1116 1338 1580 1605

800 1000 1200 1400 1600

Wavenumbers (cm-1)
 The diatomic vibrating Rotator
• In liquid molecules are very close together, so
interaction during rotation produce the change
in bond length and so the vibrational spectra.

• Energy needed for rotational spectra is so small

that at room temperature the molecule get
sufficient amount of energy to rotate.

• In gas phase the distance between the

molecules is quite large so to see vibrational
spectra excitation energy is needed.
 The diatomic vibrating Rotator
Born-Oppenheimer approximation: A diatomic molecule
can execute rotations and vibrations quite
independently. The combined rotational vibrational
energy is simply the sum of the separate energies:
Etotal = Erot. + Evib. (joules)
etotal = erot. + evib. (cm-1)
Taking the separate expression for erot. and evib. From
previous discussions, we have
eJ,v = eJ + ev
=BJ(J+1) - DJ2(J+1) 2 + ….+( v + ½ ) e -
(v + ½ )2 e xe cm-1
• If we ignore the effect of centrifugal distortion
and anharmonicity then the energy levels of a
diatomic molecule is
 1  2
 J J  1
k
Ev , J   v  
 2  2I

Selection Rule: The selection rules for the combined

motions are the same as those for each separately
v = ± 1 J = ± 1,

The v=0 to v=1 transition fall into two categories, the P

branch in which J = - 1(that is J TO J-1) and the R branch
In which J = + 1 (J TO J+1)
 E1, J 1  E0, J 
  J  1J  J  J  1
1 k
P  
h 2  4I

 0  J
2I
E1, J 1  E0, J 
  J  1( J  2)  J  J  1
1 k
R  
h 2  4I

  0  ( J  1)
2I

There will be no line at  = 0 because transition for J=0

Are forbidden in diatomic molecules.
 The diatomic vibrating Rotator

An analytical expression for the spectrum may be

obtained by applying the selection rules to the
energy levels. Considering only the v=0v=1
transition we have in general
eJ,v = eJ’, v=1 - eJ”, v=0
=BJ’(J’+1) - DJ’2(J’+1) 2 +1 ½ e -2 ¼ e xe
- {BJ”(J”+1) - DJ”2(J”+1) 2 + ½ e - ¼ e xe }cm-
1
= o + B(J’ - J”)(J’ + J” +1) cm-1 Considering D
negligible.
Applications
IR Detector
Body temperature detection by Infrared modes
IR imaging by temperature variation
 Pollution detection by IR modes

Bomd or bomb material detection

Chemical detection
Microwave Oven
 Recent Publications
1. M. Rana, A. Jain, V. Rani, P. Chowdhury; Glutathione capped core/shell CdSeS/ZnS quantum dots as a medicalimaging
tool for cancer cells; Inorganic Chemistry Communications (2020), 112, 107723 .[Index in scopus, Impact factor:
1.794].
2. M. Rana, P. Chowdhury; Studies on Size Dependent Structures and Optical Properties of CdSeS Clusters; Journal of
Cluster Science (2020), https://doi.org/10.1007/s10876-019-01719-0.[Index in scopus, Impact factor: 2.15]
3. Pooja, M, Rana.M, P. Chowdhury; Optical and Structural Investigation of CdTe Quantum Dots in Freezed Solid Phase
Between PVA Polymer Matrix; AIP Conference Proceedings,(2020), (in press) .[Index in scopus, Impact factor: 0.40].
4. M. Rana, P. Chowdhury, L-glutathione capped CdSeS/ZnS quantum dot sensor for the detection of environmentally
hazardous metal ions; J of Luminescence, (2019), Vol 206. 105-112 [Index in scopus, Impact factor: 2.367].
5. Pooja, M, Rana.M, P. Chowdhury; Influence of size and shape of optical and electronic properties of CdTe quantum dots
in aqueous; AIP Conference Proceedings,(2019), 2136, 040006 (2019); https://doi.org/10.1063/1.5120920; .[Index in
scopus, Impact factor: 0.40].
6. M. Rana, Pooja, P. Chowdhury; Investigation on Nonlinear Optical Responses of Different Pyrrole Derivatives: AIP
Conference Proceedings,(2019), A Computational Study; 2136, 040005 (2019); https://doi.org/10.1063/1.5120919;
.[Index in scopus, Impact factor: 0.40].
7. Rana M., Chowdhury P., “Perturbation of hydrogen bonding in hydrated pyrrole-2-carboxaldehyde complexes”, Journal
of Molecular Modelling, vol. 23, pp. 216-227, 2017. (Thomson Reuters I. F. = 1.425, h-index = 54, h5-index = 34,
Published by Springer, Indexed in SCI and SCOPUS).
8. Rana M., Chowdhury P., “Effects of hydrogen bonding between pyrrole-2-carboxaldehyde and nearest polar and
nonpolar environment”, Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, vol. 185, pp. 198–206,
2017. (Thomson Reuters I. F. = 2.536, h-index = 89, h5-index = 53, Published by Elsevier, Indexed in SCI and
SCOPUS).
9. Rana M., Singla N., Pathak A., Dhanya R., Narayana C., Chowdhury P., “Vibrational-electronic properties of intra/inter
molecular . hydrogen bonded heterocyclic dimer: An experimental and theoretical study of pyrrole-2-
63
carboxaldehyde”, Vibrational Spectroscopy, vol. 89, pp. 16-25, 2017. (Thomson Reuters I. F. = 1.74, h-index = 62, h5-
index = 23, Published by Elsevier, Indexed in SCI and SCOPUS).
10. Rana M., Singla N., Chatterjee A., Shukla A., Chowdhury P. “Investigation of nonlinear optical (NLO) properties by
charge transfer contributions of amine functionalized tetraphenylethylene" Optical Materials, vol. 62, pp. 80-89, 2016.
(Thomson Reuters I. F. = 2.238, h-index = 84, h5-index = 35, Published by Elsevier, Indexed in SCI and SCOPUS).