Unit 2 Molecular Spectroscopy

Part A

1. What is an electromagnetic spectrum?.

Ans Electromagnetic spectrum is the arrangement of various types of electromagnetic radiations in

increasing order of their wavelengths or decreasing order of their frequencies.

2. Draw an electromagnetic spectrum with variable energy

Ans
EMR y–rays X–rays UV Visible Infrared Microwaves Radio waves

Energy (eV) 10^6 10^4 10^2 1 10^-2 10^-4 10^-9

3. What is rotational energy?

Ans It is due to the spinning of molecules about the axis passing through the centre of gravity. The
molecules can undergo rotational level transitions by absorbing microwave radiation.

4. Define basic principle of microwave spectroscopy

Ans Microwave Spectroscopy is concerned with transitions between rotational energy levels
in molecules (having electric dipole moment) by absorbing microwave radiation, which
has the same frequency as the quantized rotational energy level difference.

5. Write down the selection rule for rotational spectroscopy

Ans The selection rule represents the change in quantum numbers for allowed transitions. Only those
molecules which possess a permanent dipole moment give rotational spectra. For pure rotational
transitions, the allowed transition is ∆𝐽 = ±1.

6. Define degrees of freedom

Ans The number of degrees of freedom is equal to the sum of coordinates necessary to locate all the
atoms of a molecule in space. Each atom has three degrees of freedom corresponding to the three
Cartesian coordinates (X, Y, Z) which is necessary to describe its position on relative to other atoms
in a molecule.

7. Which of the following diatomic molecules have a rotational microwave

spectrum: IF, O2, KCl, Cl2.

Ans IF, KCl are microwave active as there will be a change in the dipole moment of the
molecules.

8. Identify the molecules that will exhibit a pure rotational absorption microwave
spectrum: N2O, NO2, CClF3, NF3, SF6, CH4, CO2.

Ans N2O, NO2, CClF3, NF3, SF6, are microwave active as there will be a change in the dipole
moment of the molecules during rotational transitions.
9. What are the various types of electronic transitions?

Ans There are four types of electronic transitions involved ultraviolet and visible spectroscopy. They
are:σ –σ* ; n–σ* ; π–π* and n–π*

10. What is the necessary condition for a molecule to absorb infrared radiation?

Ans 1. There should be a change in the dipole moment of the molecules upon IR absorption.

2. The frequency of the incoming radiation should match with the frequency of the energy level
difference between the vibrational states. Vibrational transition occurs when ∆𝜗 = ±1.

11. Calculate vibrational degrees of freedom for CO2.

Ans

Molecule Type Number of Atoms Vibrational Degree of Freedom Number of Modes of Vibrations

CO2 Linear 3 3N – 5 3(3) – 5 = 4

12. Calculate fundamental bands for the linear molecules.

Ans Linear : 3N – 5 (Vibrational Degree of Freedom)

13. How many fundamental bands are observed in the IR spectrum of benzene?

Ans 30 fundamental bands are observed in the IR spectrum of benzene.

Part B

1 Explain in detail about the classification of molecules based on moment of inertia.

Ans Based on the moment of inertia, the molecular shapes are classified into: linear
molecules, symmetric top molecules, spherical top molecules and asymmetric top molecules.

i. Linear Molecules

These are the molecules in which all the atoms are arranged in a straight line. Linear rotors
have one moment of inertia equal to zero [IA = 0 and IB = IC].

Examples: HCl, CO2, OCS, HCN, C2H2 etc.

Linear molecules can be rotated in 3-directions: (i) About the bond axis (ii) End-over end
rotation in the plane of the paper, and (iii) End-over-end rotation at right angles to the plane.

ii. Symmetric Top Molecules

Symmetrical tops are molecules with two rotational axes that have the same moment of
inertia and one unique rotational axis with a different moment of Inertia.
Symmetrical tops can be divided into two categories based on the relationship between the
inertia of the unique axis and the inertia of the two axes with equivalent inertia.
iii. Spherical Top Molecules:

Spherical top molecule is a special case of a symmetric tops with equal moment of inertia
about all the three axes, IA = IB = IC. Because of their spherical symmetry, they have zero
dipole moment and they are microwave inactive.

Examples: Methane (CH4); Phosphorus tetramer (P4); Carbon tetrachloride (CCl4)

iv Asymmetric top molecules

Asymmetric top molecules are a type of polyatomic molecules having all principal axes of the
moment of inertia are different from each other (IA ≠ IB ≠ IC).

Examples: HCHO; H2O; CH3OH

2. Explain rotational spectra of diatomic molecules with energy level spectrum.

Ans The rotational energy in terms of wave number can be calculated for various J values by
using the expression (11).

For J = 0; 𝛾̅(𝑖𝑛 𝑐𝑚−1 ) = 0

For J = 1; 𝛾̅(𝑖𝑛 𝑐𝑚−1 ) = 2𝐵
For J = 2; 𝛾̅(𝑖𝑛 𝑐𝑚−1 ) = 6𝐵
For J = 3; 𝛾̅(𝑖𝑛 𝑐𝑚−1 ) = 12𝐵

The selection rule represents the change in quantum numbers for allowed transitions.

For pure rotational transitions, the allowed transition is ∆𝐽 = ±1.

3. Explain rotational spectra of polyatomic molecules.

Ans To determine the two bond lengths in the linear triatomic, we neede to determine the
moment of inertia IA’ of an isotope of the triatomic. From two values of IA and IA ’ , we can
determine the two bond lengths.

The rotational spectra of asymmetric molecules for whom IA ≠ IB ≠ IC can be quite

complicated. For symmetric tops, two moments of inertia are equal ie.,

IA = IB ≠ IC ; IC ≠ 0

In CH3Cl for example, the main symmetry axis is the C – Cl axis. We need two quantum
numbers to describe the rotational motion with respect to IA and IC respectively. Let J
represent the total angular momentum of the molecule and K the angular momentum with
respect to the C – Cl axis of the symmetric top. J takes on integer values and K cannot be
greater than J (recall that ml ≤ ‫ ׀‬l ‫ ׀‬for orbital angular momentum). The (2J + 1) “degeneracy”
is expressed through the 2J + 1 values that K can take.
K = J, J – 1, ….. 0, - (J – 1), - J
The rotational energies of a symmetric top are given by

2 1 , / ( 1) ( ) , − EJ K hc = BJ J + + A − B K cm
The moments of inertia are related to B and A as

B = h/(8π^2Ic.C) and A = h/(8π^2IA.C)

As the energy depends on K2 , energies for states with + K and – K are doubly degenerate.
Thus there will be J + 1 levels and (2J + 1) states for each values of J.

The selection rules for the symmetric top are,

, ΔJ = ± 1 and ΔK = 0

It can be easily shown that

(EJ +1, K – EJ,,K)/hc = 2 BJ (J +1)

This implies that the spectrum is independent of the value of K. The physical meaning is as
follows. K refers to the rotation about the symmetry axis such as the C - Cl axis. A rotation
about this axis does not change the dipole moment. We mentioned in the section on the
rotational spectra of diatomics that the molecular dipole moment has to change during the
rotational motion to induce the transition.

Rotation along the axis A and B changes the dipole moment and thus induces the transition.
By using rotational or microwave spectroscopy, very accurate values of bond lengths can be
obtained. For example, in HCN, the C-H length is 0.106317 ± 0.000005 nm and the CN bond
length is 0.115535 ± 0.000006 nm. The principle of the microwave oven involves heating the
molecules of water through high speed rotations induced by microwaves. The glass
container containing water however remains cold since it does not contain rotating dipoles.

4. Calculate J (1 to 3) values of CO molecule.

Ans For the rotational quantum number J = 1, the change in rotational transition is given by:

∆𝜸̅(𝟏→𝟐) = 2𝐵(𝐽 + 1) = 2𝐵(1 + 1) = 𝟒𝑩

For the rotational quantum number J = 2, the change in rotational transition is given by:

∆𝜸̅(𝟐→𝟑) = 2𝐵(𝐽 + 1) = 2𝐵(2 + 1) = 𝟔𝑩

For the rotational quantum number J = 3, the change in rotational transition is given by:

∆𝜸̅(3→4) = 2𝐵(𝐽 + 1) = 2𝐵(3 + 1) = 8𝑩

5. Explain the types of vibrations and its diagrammatic representation.

Ans 1. Stretching Vibration

If two bonded atoms continuously oscillate between the bonds by changing their distance
without altering the bond angles, it is known as stretching vibration.

Example (i): Diatomic molecules like H–H or H–Cl vibrates in one way by moving towards or
away from each other when they interact with suitable IR radiations.

Example (ii): However, triatomic molecules such as CO2 possess two different stretching
modes namely symmetrical stretch and unsymmetrical stretch. In the symmetrical stretch,
each O moves towards C or away from C simultaneously.

In the unsymmetrical stretch, one O moves towards C while the other O moves away from C

2. Bending Vibration

If two bonded atoms continuously oscillate between the bonds by changing the bond angles
with respect to the centre atom in and out of the bond axis, it is known as bending vibration.
There are two types of bending vibrations:

IN-PLANE: bending vibrations: All the atoms are on same plane; Examples: Scissoring
and rocking.

OUT-OF-PLANE: bending vibrations: If two atoms are on same plane while the one atom
is on the opposite plane; Examples: Twisting and wagging.

Scissoring: If the two atoms joined to centre atom move towards and
away from each other, it is known as scissoring.

Rocking: If the two atoms joined to centre atom move simultaneously

in the same direction, it is known as rocking.
Twisting: If one of the atoms moves up (coming forward)
and the other moves down (going back) with respect to centre
atom and changing the bond angles, it is known as twisting.

Wagging: If the two atoms move back and forth in the same direction
with respect to the centre atom and changing the bond angles, it is
known as wagging. Such vibrations are generally referred to as
degenerate modes.

6. Calculate the force constant of CO molecule having ῡ = 2143 cm-1

Ans

Substituting the values of 𝜇 and(2𝜋𝑐𝛾̅) 2 in equation (2), we get:

𝑘 = 11.38 × 10^−27𝑘𝑔 × 16.32 × 10^28𝑠 ^−2

𝒌 = 𝟏𝟖𝟓𝟕𝒌𝒈𝒔−2
7. Explain the electronic transitions in organic molecules with suitable examples.

Ans 1. σ –σ* → Transitions

When a molecule absorbs energy in near uv of maximum wavelength of absorption (120-

180 nm), the σ bonding electrons are promoted to σ (sigma star) anti-bonding orbital, and the
phenomenon is known as → transition. For this transition, a very high energy is required.

Examples: Organic compounds containing saturated single bonds (methane, propane,

cyclohexane etc.) follow → transitions.

2. n–σ*→ Transitions

When a molecule absorbs energy in mid-uv of maximum wavelength of absorption (150- 250
nm), the n-nonbonding lone pair electrons are promoted to σ (sigma star) antibonding orbital,
and the phenomenon is known as n→ transition. The energy required for n– transition is
lower than n→ transition.

Examples: Organic compounds containing double bonds with hetero atoms (e.g: C=O; C=S;
N=O) follow n→ transition.

3. π–π*→ Transitions

When a molecule absorbs energy in a uv-visible region of maximum wavelength of

absorption (200-780 nm), the bonding electrons are promoted to (pi star) antibonding
orbital, and the phenomenon is known as → transition. Since orbital and orbital are situated
in the same plane, less amount of energy is required for transition.

Examples: Organic compounds containing double bonds and triple bonds (ethylene,
acetylene) follow → transitions.

4. n–π*→ Transitions

When a molecule absorbs energy in a uv-visible region of maximum wavelength of

absorption (200-780 nm), the n-non bonding electrons are promoted to (pi star) antibonding
orbital, and the phenomenon is known as n→ transition. Since the n-nonbonding orbital is
situated perpendicular to the orbital, the probability of jumping electrons from n→ is less
intense, though this transition requires less energy.

Examples: Organic compounds containing hetero atoms bearing lone pair electrons follow
n→ transitions.
8. Define Beer Lamberts law and derive its mathematical formulae

Ans When a beam of monochromatic light passes through an absorbing solution, the rate of
decrease of intensity of incident light with any thickness (x = 0→l) of the absorbing solution is
proportional to (i) the concentration of solution (c) and (ii) the intensity of incident light (I ).

Mathematically, it is stated as:

−𝑑𝐼 /𝑑𝑥 ∝ 𝑐𝐼

−𝑑𝐼/ 𝑑𝑥 = 𝑘 ′ 𝑐𝐼 . . . (1)

Where, I is the intensity of incident light; x is the thickness of the absorbing solution; c is the
concentration of the solution and k’ is molar absorption coefficient. When the thickness of
solution x = 0, then I = Io and when the thickness of the solution x = l, then I = I.

Where, 𝑙𝑜𝑔 𝐼𝜊 𝐼 is known as absorbance (A) or optical density; l is thickness or path length of
the cell; c is the molar concentration of the solution and ε is the molar absorptivity.

The equation (3) is the mathematical derivation of Beer-Lambert’s law.