Abstract
The vibrational relaxation rate through rotation of diatomic molecules in condensed media is calculated for both the low-barrier and the high-barrier cases using the repulsive potential model. The lack of temperature dependence below a threshold temperature is noted and the inverse isotope effect is found. The vibrational relaxation rate in the low-barrier case when the ground state is approximated by vibration and higher states by rotation is calculated in order to examine the validity of the use of the free-rotation approximation in the ground state. The ratio of the vibrational relaxation rate through rotation to the total vibrational relaxation rate is obtained in order to see the relative contribution of the molecular rotation and lattice vibration to the vibrational relaxation.
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