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PHYS 705: Classical Mechanics

Small Oscillations: Example
A Linear Triatomic Molecule
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A Linear Triatomic Molecule

k k

m M m

b b
x1 x2 x3 x

Experimentally, one might be interested in the radiation resulted from the

intrinsic oscillation modes from these triatomic molecule.

The potential energy for the two springs is,

k k
 2 1   3 2 
2 2
V x  x  b  x  x  b
2 2
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A Linear Triatomic Molecule

k k

m M m

b b
x1 x2 x3 x

Now, we will introduce generalized coordinates relative to their

equilibrium positions, x01 , x02 , x03 :

 j  x j  x0 j j  1, 2,3

Note: x02  x01  x03  x02  b

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A Linear Triatomic Molecule

Expanding the potential energy about its equilibrium position, we have:

k k x2  x1  b  x2  x1   x02  x01 
V   2  1   3   2 
2 2

2 2  x2  x02  x1  x01
  2  1
Multiplying the squares out, we have:

V
2

k 2
1  21 2   22    22  2 23  32 
k
2
V  12  1 2   21  2 22   23  3 2  32  1
k
V  V jk  j k
2 2
In matrix form, this quadratic  k k 0 
 
form has this form: V   k 2k k 
 0 k k 

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A Linear Triatomic Molecule

  2V 
Direct method to evaluate V jk using V jk  
 q q 
 j k 0
k k
Recall, we have V   x2  x1  b    x3  x2  b 
2 2

2 2
By taking the partial derivatives directly and evaluating at x j  x0 j,

V k  2V
V11 :   2  x2  x1  b   and  k
q1 2 q1q1
V k
  2  x2  x1  b     2  x3  x2  b  
k
V12 :
q2 2 2
 k k 0 
V2
 
and
q1q2
 k  V   k 2k k 
 0 k k 

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A Linear Triatomic Molecule

The kinetic energy for the three mass is given by:

T
2

m 2

x1  
x3 
2

M 2
2
x2

Substituting our generalized coordinates  j  x j  x0 j or  j  x j,

1
T  12  32   22
m M
T  T jk  j k
2 2 2

In matrix form, this quadratic m 0 0

 
form has this form: T0 M 0
0 0 m 

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A Linear Triatomic Molecule

Combining these two quadratic forms into the characteristic equation,

k   2m k 0
V   T  V   2T  k 2k   2 M k 0
0 k k   2m
Explicitly evaluating this determinant, we have the following equation,

 k   m   2k   M   2k  k   m   0
2 2 2 2 2

 k   m   k   m  2k   M   2k   0
2 2 2 2

 k   m   2k
2 2
 2k 2  k 2 M  2k 2 m   4 mM   0

 2  k   2 m   k  M  2m    2 Mm   0
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A Linear Triatomic Molecule

And, this has three distinct solutions (eigenfrequencies):

k k  2m 
1  0 2  3  1  
m m M 

Note:

The 1  0 solution means that the corresponding normal coordinate  j will

have the following trivial ODE:
(uniform
1   0   1  0 or 1  0
translational motion)

 The entire molecule will simply move uniformly to the right or left; no
oscillations (not quite interesting motion by itself)
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A Linear Triatomic Molecule

Now, we find the eigenvectors for each solved eigenvalues using:

 V   T a
2
r r 0

 k  r2 m k 0   a1r 
  
  k 2 k   2
r M  k   a2 r   0
 0
 k k  r2 m   a3r 

Normal Mode #1: r  1

 a11k  a21k  0

1  0   a11k  a21 2k  a31k  0
  a21k  a31k  0

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A Linear Triatomic Molecule

Normal Mode #1: r  1

 a11k  a21k  0

  a11k  a21 2k  a31k  0
  a21k  a31k  0


Solving 1st and 3rd equations, we have a21  a31 and a11  a21

Putting them together, we have a11  a21  a31

(Note that the solution a11  a21  a31 also satisfies the 2nd equation.)

 1
1  0 is:  
So, the eigenvector for a1  a11  1
 1
 
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A Linear Triatomic Molecule

Normal Mode #1: r  1

The eigenvector needs to be normalized with respect to T:

m 0 0  1
  
a 1Ta1  1 a112 1 1 1  0 M 0  1  1
0 0 m  1

1
This gives: a 2
 M  2m   1 a11 
11
M  2m

1
Finally, we have the normalized 1  
a1   1
eignvector for 1  0 : M  2m  
1
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A Linear Triatomic Molecule

Normal Mode #2: r  2

 k 
 k  m0 k 0 
m
   a12 
2 
k  k 2k 
kM
k  a   0
m  m   22 
   a32 
 k
0 k k  m  0 
 m 

  a22 k  0
  a22  0
  M

 12 a k  a22 
k 2    a32 k  0 
  m a12   a32
  a22 k  0
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A Linear Triatomic Molecule

Normal Mode #2: r  2

1
 a22  0  
 a 2  a12  0 
a12   a32  1 
 
Again, we need to normalized with respect to T:

m 0 0  1 
  
a 2 Ta 2  1 a122 1 0 1  0 M 0  0  1
0 0 m   1

1
1  
This gives: a122  2m   1 a2   0
2m  
 1 
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A Linear Triatomic Molecule

Normal Mode #3: r  3

 k  32 m k 0   a13 
k  2m    
3  1     k 2 k   2
3M  k   a23   0
m M   0
 k k  32 m   a33 

First, let try to simply the matrix elements first:

 k  2m    k  2m  
k   m  k   1 
2
3  m 2k   M  2k    1 
2
3  M
m M  m M 
 2m   kM 
 k k1    2k    2k 
 M   m 
2km 
kM

M m
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A Linear Triatomic Molecule

Normal Mode #3: r  3

Putting these values back into the matrix, we have

  2km M k   a13 
0
  
 k  kM m k   a23   0
 0 k  2km M   a33 


 2km 2m
a23 
  a13 M  a23 k  0
a13
M

 kM
  a13 k  a23  a33 k  0 2 m M
m a13  a13  a33  0
 M m
 2km
  a23 k  a33 0
 M a13  a33
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A Linear Triatomic Molecule

Normal Mode #3: r  3

 2m  1 
 23
a  a13  
 M a3  a13  2m M 
 a33  a13  1 
 
Again, we need to normalized with respect to T:

 1 
m 0 0  
 2m    2 m
a 3Ta3  1 a132 1  1  0 M 0    1
 M    M 
0 0 m
1 
 
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A Linear Triatomic Molecule

Normal Mode #3: r  3
 1 
m 0 0  
 2m     2m 
a132 1  1  0 M 0  1
 M    M 
0 0 m 
 1 
 m 
2  2m    2  4m 2 
a13 1  1  2m   a13  2m   1
 M    M 
 m 

This gives:
 1 
1 1  
a13  a3   2 m M
2m 
4m 2 2m 1  2m M   

 1 
M
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A Linear Triatomic Molecule

Then, our general solution is given by:

ir t *  ir t (the complex coefficient Cr

 j  a jr r and  r  Cr e C e
r
will be determined by IC)

a1 a2 a3
1 1 1
1  1  2  3
M  2m 2m 2m 1  2m M 

1 2
2  1  0  3
M  2m 2M  2  M m 

1 1 1
3  1  2  3
M  2m 2m 2m 1  2m M 
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Longitudinal Normal Modes

So, if a single normal mode  r is active, the motion of the three generalized
coordinates   will looks like the following,
j

1 ,2 ,3

1
 1 : 1  0  m 1 , M  1 , m  1
M  2m

 k  m
 2 :  1    2 , 0,   2 
 m 2

 k  2m   nM
 3 :  1  1     3 ,  2  3 ,  3

 m  M  2  2m  M 
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Longitudinal Normal Modes

Animations for the two non-rigid-translational modes:  2 and  3

http://cis.poly.edu/~mleung/CS4744/f03/ch04/L
inMole/LinMole.html
(from Polytechnics Institute of NY Univ: K. Ming Leung)
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Summary
1. Pick generalized coordinates and find T ( q j ) and V ( q j )
2. Expand T and V about equilibrium q0 j
 This gives two real symmetric quadratic forms: T jk ( j ) V jk ( j )

with  j  q j  q0 j
3. Calculate eigenfrequencies r  r2 from characteristic equation
det V jk  r2T jk   0
4. Calculate eigenvectors for each eigenfrequencies using V jk  r2T jk  a jr  0
5. Normalize eigenvectors with respect to T: T jk a jr akr  1
6. General solutions are in terms of the normal modes
 r  t   Cr ei t  Cr*e  i t
r
Cr determined by IC
r

7. Original coordinates are related back through  j  a jr r