Three-Dimensional Morse-Potential Calculation of Vibrational Energy Transfer: Application to Diatomic Molecules

Abstract

A three‐dimensional semiclassical analysis of the vibrational‐energy‐transfer problem is performed for the Morse potential. The resulting equation is compared with the Schwartz—Slawsky—Herzfeld formulation, and with experimental data for a number of diatomic molecules. The particular case of N₂ gives a different Morse repulsive index than that obtained from the second virial coefficient. In contrast to the SSH formulation, a single value of the index suffices over a large range of temperature for N₂, O₂, and CO. Improvement in the theory is found for cases in which ε/kT becomes large.