ST.

THOMAS COLLEGE, BHILAI

Free Vibration of Linear Triatomic Molecule

Guided By: TOPIC FROM Presented By:
PAPER-2 PRIYA SAI
AMIT TAMRAKAR SIR CLASSICAL MECHANICS M.Sc. PHYSICS (SEM 1st)

Date – 28/01/2021
 CONTENTS
• Free vibration and linear triatomic molecule

• Longitudinal oscillations of a linear triatomic molecule

• Discuss the eigen vectors

• Modes of vibration of linear triatomic molecule

• Generalised and normal coordinates

FREE VIBRATION: A free vibration is where there is no externally applied vibration forcing. Free
vibrations involve no transfer of energy between the vibrating object and its surroundings,
whereas forced vibrations occur when there's an external driving force and thus transfer of
energy between the vibrating object and its surroundings.

LINEAR TRIATOMIC MOLECULE: Triatomic molecules are molecules that contain three atoms. The
atoms in triatomic molecules can all be the same, as in I3-, all be different, as in HCN, or can be a mix like
CO2. Examples include H2O, which is a bent and has a bond angle of 109o, and a linear triatomic
molecule such as CO2.
Linear triatomic molecules owe their geometry to their sp or sp3d hybridised central
atoms. Well known linear triatomic molecules include carbon dioxide (CO2) and hydrogen cyanide (HCN).
Let us consider a linear triatomic molecule of the type AB2 ( e.g., CO 2)
in which A atom is in the middle and B atoms are at the ends. B

The mass A atom is M and that of each B atom is m.

A k
The interatomic forces between A and B atom is approximated by
B k
elastic force of spring force constant k.

The motion of the three atoms are constrained along the line joining
them.

There are three coordinates marking the positions of three atoms on

the line.

If x1, x2, x3 are the positions of the three atoms at any instant from
some arbitrary origin then,
 m M k m
Equilibrium Configuration

B A B X02 - x01 = x0
x01

x02 X03 – x02 = x0

x03

M
Configuration at any Instant t

q1 q2 q3
x1 qi = xi – x0i
x2
x3

Fig : Longitudinal oscillations of a linear triatomic molecule

 .
Kinetic Energy T = ½ m [ x12 + x32 ] + ½ M x22

Potential Energy V = ½ k ( x2 – x1 – x0 )2 + ½ k ( x3 – x2 – x0 )2

where x0 is the distance between any A and B atoms in the equilibrium configuration.

Let us define the generalized coordinates as

q1 = x1 – x01, q2 = x2 – x02 , q3 = x3 – x03 ,

Where x02 – x01 = x03 – x01 = x0

.
Then, T = ½ m [ q 12 + q 32 ] + ½ M q 22
˙
V = ½ k (q2 – q1)2 + ½ k (q3 – q2)2
 Thus the T and V matrices are :
m 0 0 k -k 0
T= 0 M 0 and K = -k 2k -k ……………..(1)
0 0 m 0 -k k

The secular equation is k – mω2 -k 0

V – ω2 I = = 0
-k 2k – Mω2 -k …………….(2)

0 -k k – mω2

where ω2 ( k – mω2 ) [k (M + 2m) – ω2 Mm] = 0

The solutions of this equation are: ω1 = 0, ω2 = √ k/m , ω3 = √ k ( 1 + 2m/M) …………….(3)

m
The first eigen value ω1 corresponds to the non-oscillatory motion and refers to translatory motion of the molecule
as a whole rigidly.

To determine eigen vectors we use the equation :

K – mωk2 -k 0 a1k
(V – ωk2 T) ak = 0 0r = 0
-k 2k – Mωk 2 -k a2k

0 -k k – mωk2 a3k

Let us now discuss the eigen vectors for the three modes of vibrations
• For ω1 = 0,
k -k 0 a 11

-k 2k -k a 21 = 0
0 -k k a 31

Or a11 – a12 = 0, -a11 + 2a21 –a31 = 0, -a21 + a31 = 0

Or a 11 = a21 = a31 = a (say)

Thus for ω1 = 0, the eigen vector is given by

a

a1 = a ………………(4)

a
• For ω2 = √k/m ,
0 -k 0 a12

-k 2k- M k/m -k a21 = 0

0 -k 0 a31

0r a 22 = 0 , -a12 -a32 =0

Therefore, a 22 = 0, a12 = - a32 = b (say).

Thus, for ω 2 = √ k/m , b

a2 = 0 ……………….(5)

-b
• For ω3 = √k/m ( 1+2m/M )
- 2mk/M -k 0 a13

-k - k M/m -k a23 = 0

0 -k - 2mk/M a33

Which yields 2m/M a 13 + a23 = 0 , a13 + M/m a23 + a33 + 0 , a23 + 2m /M a33 = 0

Therefore, a 13 = a33 = g (say) and a23 = - (2m/M ) g

thus for ω3 = √ k/m ( 1+2m/M ) , g

a3 = -2m/M g ................(6)

g
 a11 a12 a13 a b g
Now, the A matrix is
A= a21 a22 a23 = a 0 -2m/M g ………………(7)

a31 a32 a33 a -b g

We impose the condition

ATA=I

a a a m 0 0 a b g 1 0 0
i.e., b 0 -b 0 M 0 a 0 -2m/M g = 0 1 0
g -2m/Mg g 0 0 m a -b g 0 0 1
 a2 ( 2m + M ) 0 0 1 0 0
Or 0 2b 2 m 0 = 0 1 0
0 0 2g2 m (1 + 2m/M) 0 0 1

Thus a = 1/ √2m + M , b = 1/ √2m , g = 1 / √ 2m ( 1+ 2m/ M)

Hence the eigen vectors are

1 1 1
a1 = 1/√ 2m+M 1 , a2 = 1/ √2m 0 , a3 = 1/ √2m ( 1+ 2m/M) -2m/M ……….(8)
1 -1 1
Thus in case (1), a11 = a21 = a31 means that
the displacements of three atoms are the same
in the same direction, this is what expected B A B
from translatory motion.

In case (2), a22 = 0, and a12 = - a32 implies

that in this mode, the middle atom does not
vibrate and the end atoms (B) oscillate with
equal amplitudes but in opposite direction. B A B

In case (3),
a13 = a33 = g and a23 = -(2m/M)g
Shows that end atoms oscillate in phase with
equal amplitudes, while the central atom
vibrates in opposite phase with different
amplitude.
B A B
(a) Mode 1, all the three atoms are displaced equally in the same direction,
(b) Mode 2, A atom does not vibrate and B atoms oscillate with equal
amplitudes but in opposite directions,
(c) Mode 3, B atoms vibrate in phase with equal amplitudes and the middle
atom A vibrates in opposite phase with different amplitude.

Fig : longitudinal normal modes of the triatomic molecule.

 The generalized co-ordinates q1, q2 and q3 are related to the normal coordinates Q1, Q2 and Q3 by using the relation
3
qi = ∑ aik Qk where i = 1, 2, 3.
k= 1

therefore q1 a b g Q1
q2 = b 0 -2m/Mg Q2 …………….(9)
q3 g -b g Q3

Further the normal coordinate Q1 oscillates with frequency ω1 = 0, Q2 with ω2 = √ k/m and Q3 with ω 3 = √ k/m (1+2m/M) .
So that
Q1 = f1 cos (ω1 t + Φ1) , Q2 = f2 cos (ω2t + Φ2) , Q3 = f3 cos (ω3 t + Φ3) ……………(10)
Thus,
q1 = a f1 cos (w 1t+ f1) + b f2 cos(w 2t + f2 ) + g f3 cos (w 3t + f3)
or
x 1 = A cos ( w 1t + f1) + B cos (w 2 t + f2) + C cos ( w 3t + f 3) + x01
But ω1 = 0 , therefore
x1 = A’ + B cos (ω2t + Φ2 ) + C cos (ω3 t + Φ 3 ) + x01 ………………..(11 a )

x2 = A’ - 2m/M C cos (ω3 t + Φ3 ) + x02 ………………..(11 b)

x3 = A’ - B cos (ω2 t + Φ2) + C cos (ω3 t + Φ3 ) + x03 ………………..( 11 c)

Where A’ represents a constant corresponding to rigid translation and x0i is the equilibrium position of the atom.

Thus we observe from equations (11) that any general longitudinal vibration of a molecule, if it doesn’t
involve a rigid translation, is some linear combination of the normal modes ω2 and ω3 . The amplitudes of
the normal modes and their phases relative to each other may be determined by the initial conditions.
• Images– google images

• Websites -- Wikipedia.com ,

phylibretexts.com

https://www.maplaboratory.net/infrared-spectroscopy-ftir1.html

• Books -- Classical Mechanics by J.C. Upadhyaya,

Classical Mechanics by Goldstein Poole & Safko