545439-8-8P AID: 1112 | 04/04/2017

U R
The width R , of the well-like curve in the versus R plot, is the measure of the
extent of bond stretch in a molecule. It can also be called the spatial extent of the
wavefunction.
Vibration in bond results in a change in R , as we change factors like force constant,
vibration frequency and dipole moment.

Increase in v :
Since, frequency v is directly proportional to energy, thus as v increases, vibrational
energy increases, thus the distance of stretch R also increases.

Therefore, as v increases R also increases.

Increase in :
We know that vibrational energy E and reduced mass are related as follows,
1
E

Thus as increases E decreases, hence R also decreases.

Therefore, as increases R decreases.

Increase in Re :
Since,
R R Re

Where R is the bond length and Re is the equilibrium bond length.

As Re increases, R also increases by the same amount, thus cancelling out the individual
increments. Thus, R remains the same.

Therefore, when Re increases R does not change.

Increase in e xe :
Well depth De and anharmonicity e xe is related as follows,
1
e xe
De
Thus, as e xe increases De decreases and well flattens. Thus, R increases.

Therefore, when e xe increases R also increases.

Increase in k:
For a harmonic oscillator, Energy E is,
kx 2
E
2
Also,
k 1
Eh
2
From above two relations we get,
kx 2 k 1
h
2 2
1/2
2h 1
x
k 2
Thus,
1/2
1
x
k
Where k is the force constant and x is the distance of upper turning point.
Hence, as k increases x decreases and comes closer to Re , decreasing width R .

Therefore, when k increases R decreases.

These results have been tabulated below:

Increase Change in R
v

Re 0
e xe
k

Where means increase, decrease and 0 no change.