Numerical calculations on vibrational relaxation in chlorine are presented. A Lennard-Jones potential is used, and the results are compared with the results of the Schwartz-Slawsky-Herzfeld (SSH) theory, which uses a shifted exponential potential. Approximate wavefunctions of the Airy function form are shown to be sufficiently accurate for the calculation of the transition matrix elements. The SSH analysis of the effect of attractive forces is shown to be valid. There is a significant difference between the results for the exponential and for the Lennard-Jones potentials, with the exponential giving better agreement with experiment.
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Hartmann et al. (1967) studied this question.
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