BITS Pilani

Pilani Campus

CHEM F111 : General Chemistry

Lecture 15
13 Feb 2019
AY 2018-19, Sem-II
Vibrational Spectroscopy
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Lecture 14 - Summary
Spectroscopy
• Rotational Spectroscopy
• General conditions for observing rotational spectra –
Energy and Intensity of transitions
• Selection rules
• Line spacings and Level spacings
• Raman spectroscopy – general conditions for
observing Raman spectra
• Pure Rotational Raman – Selection Rules

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Population at thermal equilibrium
• Hence, population at any level, PJ can be expressed as,
PJ = P0.gJ.e(-EJ /kT)
PJ  ( hBJ ( J 1) /( kT ))
or,  (2 J  1)e
P0
• The distribution passes
through a maximum at a
certain value of J, which can
be obtained at
dPJ/dJ = 0
Population is going govern
intensity of spectral transitions
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Rotational Transitions: MW spectroscopy
Transition dipole moment :  final initial d
Square of this value determines intensity. If transition
dipole moment is 0 then no transition takes place.

Selection Rules
Gross selection Rule: The molecule must be polar.
For polar molecules oscillating electric dipole is generated
by rotation.
• No Rotational spectrum for CH4 , SF6 , CO2 , H2 , O2 etc.
(Rotationally inactive)
• Rotational spectra observed for HCl, NH3 , CH3Cl etc.

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Rotational Transitions: MW spectroscopy
Selection Rules
Specific selection Rule: ∆J = ±1
This is based on conservation of angular momentum
Therefore for a rigid rotor, we can write
∆E = EJ+1-EJ = 2hB(J+1)
or, nJ = 2B(J+1)

Therefore for a rigid

rotor molecule the
rotational absorptions
are seen in 2B, 4B, 6B etc.

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 Raman Spectroscopy
Case-I Case-II
- +
Case-I: Molecule J’’ J’’ Case-II: Molecule
Energy
gains energy, release energy, E;
E; State changes J’ J’ State changes from
from J to J’. J” to J’.
J J

Stokes’ radiation Anti-Stokes’ radiation

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Raman Spectroscopy - explanation
+ ve -
ve
This separation of
charge centers
- ve + ve causes an induced
electric dipole
moment
Molecule is polarized

Polarization leads to dipole moment in the molecule –

induced dipole moment
field
a is a parameter – the ease with which a molecule can
be distorted - POLARIZABILITY
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Raman Spectroscopy – Selection rule
Gross Selection Rule

q represents the coordinate in terms of the

internal motion
If molecular rotation/vibration causes some change in molecular
polarizability then those rotation/vibration must be Raman Active
Polarizability must be anisotropic.
All diatomic molecules are Raman active.
Spherical rotors such as CH4 , SF6 are inactive.
Conditions imposed on rotation model we have used:
Molecules must be non-rigid and hence polarizable
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Pure rotational Raman Spectroscopy

Specific Selection Rule (For linear molecules)

E = hB[(J+2)(J+3) – J(J+1)] = 2hB(2J + 3) in energy units

= B[(J+2)(J+3) – J(J+1)] = 2B(2J + 3) in frequency units

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Pure rotational Raman Spectroscopy

Stokes lines at 6B, 10B, 14B,… lower than incident and

Anti-Stokes at 6B, 10B, 14B,… higher than incident frequency.
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Application of MW spectroscopy: Mapping
molecular cloud in interstellar medium
Microwave and millimeter wave astronomy: Microwave identification of molecules

Microwave spectrum of the Orion nebula

Taurus molecular cloud observed at

115 GHz. 12CO emission (J = 1 – 0)
***Not part of the Syllabus***
{Source: Astrochemistry from Astronomy to
Astrobiology, by Andrew M. Shaw, Wiley}
Line of sight through three Giant Molecular
Clouds to the Hubble Space Telescope
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Vibrational Spectroscopy

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Vibrational spectroscopy

Diatomic molecule: A-B

k is the force constant with unit as N m-1
Using the harmonic approximation:

In terms of wave number:

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Vibrational Levels

Depth of the potential

energy well indicates the
strength of the bond (in
terms of force constant, k)

At v=0, Zero Point Energy

is ½ hn
Vibrational energy levels
are equispaced at hn

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Vibrational spectroscopy
Gross Selection Rule:
The electric dipole moment of the molecule must change
during the vibration. This can be expressed as
Where  = dipole moment, q = internal coordinate
in terms of the vibrational motion
Molecule need not have permanent dipole in it
Thus, homonuclear diatomic molecules such as H2 are
vibrationally inactive (as also are rotationally inactive)
Specific selection rule:
v = 
For any vibrational transition, ∆E = Ev+1 –Ev = hcῡ
Generally, most important transition from v = 0 to v = 1.
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 Vibrational spectroscopy
Vibrational transitions occur at frequencies of 1013 to 1014Hz,
thus it is also called as infrared (IR) spectroscopy.
Ex.1 A single oxygen atom is attached to a smooth metal surface. The
atom vibrates at a frequency of 1.80 X 1013 s-1. Calculate its total
energy for n = 0, 1, and 2 quantum no. states.
Ans: E (n=0) = 5.963 X 10-21 J; E (n=1) = 1.789 X 10-20 J; and
E (n=2) = 2.982 X 10-20 J
Ex. 2: Calculate the wavelength of light necessary to excite a
harmonic oscillator from one energy state to the adjacent state in the
previous example. Ans: 16.66 m
Ex. 3: For temperatures of 25 °C and 1000 °C, calculate the ratio of
molecules in the typical excited vibrational energy level to that in the
lowest energy level, assuming that the level is 1000 cm-1 above the
lowest energy level. Work it out by yourself
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Anharmonicity
Harmonic Approximation:
Bond cannot break Anharmonic
Anharmonicity Harmonic

xe is anharmonicity constant
Plot is called a Morse Curve
Other observations:
• Dissociation of bond can be
explained
Overtones
• Additional weak absorption
lines or overtones appear Morse Curve
corresponding to v = 2,3,..

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Vibrational Spectroscopy of
Polyatomic Molecules
Normal Modes:
Description of vibration is most convenient and simple in
terms of normal modes.
Normal mode – Collective, independent, synchronous
motion of group of atoms, that may be excited without
exciting any other mode.
Each normal mode may be approximated as a harmonic
oscillator with a characteristic frequency and an effective
mass.
Any arbitrary displacement may be expressed as a
superposition of the normal modes.
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Number of Normal Modes in a
Polyatomic Molecule
For a molecule with N atoms, the number of coordinates
required to specify the position of all the atoms is 3N.
These 3N displacements can be thought of in terms of
various degrees of freedom,
Translational : 3 (that change the centre of mass)
Rotational : 2 (for linear) and 3 (for nonlinear)
displacements (that change in the bond angle)
Vibrational : 3N – 5 (for linear) and 3N – 6 (for nonlinear)
degrees of freedom

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Vibrational spectroscopy (polyatomic)

(a) The orientation of a linear molecule requires the specification of

two angles (the latitude and longitude of its axis).
(b) The orientation of a non-linear molecule requires the
specification of three angles (the latitude and longitude of its axis
and the angle of twist (the torsion angle) around that axis).
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Vibrational spectroscopy: CO2

The stretching vibrations

of a CO2 molecule

Independent components
contributing to the motion
(Normal modes): symmetric
and asymmetric stretching

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Vibrational spectroscopy – CO2
• For CO2 Normal modes are 3N-5 = (3 x 3)-5 = 4;
• 2 stretching modes; (Stretching modes are equal to no of
bonded connections; remaining are bending modes); In
CO2 these are also called as parallel modes (dipole
moment change is parallel to inter-nuclear axis);
• In stretching mode bond length changes
• In bending mode bond angle changes (lower frequency
compared to stretching) and for CO2 there are two
bending modes (perpendicular modes; degenerate;
combined)
• Collective vibrations of whole molecule occur at around
1500 cm-1. Finger print region. Bending modes difficult to
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CO2: Normal modes of vibrations
The Gross Selection rule needs to be valid each
mode to be IR active

Symmetric stretch – IR inactive

Why??
Bend – IR active

Bend – IR active

Asymmetric stretch – IR active

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Vibrational spectroscopy (polyatomic) H2O

For H2O Normal modes are 3N-6 = (3 x 3) -6 = 3;

2 stretching and one bending;

Symmetric stretch Asymmetric stretch Bend

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Vibration-Rotation Spectroscopy
Vibrational transitions accompanied by rotational
transitions – band observed in spectra
In the harmonic oscillator and rigid rotator approximation,
energy is Ev,J = (v + ½)hn + hBJ(J+1)
Corresponding to v =  (absorption), one can have
J = , nJ = n  2BJ (J = 1,2,…) (P branch)
J = +, nJ = n + 2B(J+1) (J = 0,1,2,…) (R branch)
J = 0, nJ = n (only in molecules with non-zero
electronic angular momentum about axis) (Q branch)

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Vibration-rotation Spectrum

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Diatomic vibrating rotor (CO)
No Q branch

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IR Spectroscopy - Applications
• Powerful tool in identifying organic molecules
• Modes essentially describe the motions of the individual
functional groups.
• IR spectrum is generally represented as an absorption
spectrum in Transmittance mode
Gas Phase Infrared Spectrum of Formaldehyde, H2C=O

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IR frequency calculation
Absorption frequency:

Or, ῡ = /c in cm-1

Few examples of some typical bonds
C-H: k ~ 494 Nm-1; (n~ 3000 cm-1)
N-H: k ~ 642 Nm-1; (n~ 3400 cm )
-1

O-H: k ~ 726 Nm-1; (n~ 3600 cm-1)

C=C: k ~ 972 Nm-1; (n~ 1650 cm-1)

C≡C: k ~ 1650 Nm-1; (n~ 2150 cm-1)

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IR frequencies of functional groups
The IR frequencies reflect the effect of different factors on
the nature of the bonds

Here the effect is

mainly due to bond
strength

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Interpreting IR spectra – Typical ranges
O C=O at 1725 cm-1 O C=O at 1710 cm -1

R C also look for aldehyde R C also look for OH

(H-bonded) and
H CH 2850 and 2750 cm-1 O H C-O ~1200 cm-1

O C=O at 1690 cm-1 O C=O at 1735 cm-1

R C R C also look for two
N H also look for two O R' C-O at 1200 and
NH peaks at
H 3400 cm-1 1000 cm-1

Ketones have C=O at 1715 cm-1 and no NH, OH, C-O or -CHO

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IR frequency data

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IR frequency data

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Interpreting IR spectra
C-H stretching frequencies:
<3000 cm-1 for sp3; >3000 cm-1 for sp2; ~3300 cm-1 for sp;
Methylene and methyl C-H stretching: ~2850 cm-1 (sym); ~2950
cm-1 (asym)

Hexane

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Interpreting IR spectra
O-H stretching: ~3600 cm-1 for alcohols;
broadens and lowers to 3300 cm-1 due to H-bonding in
alcohols, acids, etc.

OH
O-H CH2
H-bond C-O

C-H

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The O-H stretching region

• O-H 3600 cm-1 (alcohol, free)

• O-H 3300 cm-1 (alcohols & acids, H-bonding)
broadens

shifts

FREE H-BONDED

3600 3300

•O-H stretching frequency decreases as well as broadens due to

hydrogen bonding.
How to distinguish between intramolecular and intermolecular
H-bonding?
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