Rate constants for vibrational relaxation of HF in vibrational states n=1 to 7 are calculated semiclassically for HF(n)+HF. The variation with n agrees well with experiment. The absolute values are about 55% of the experimental results. Orbiting collisions are important. The relaxation mechanism found disagrees with three well-known more approximate theories. V–T/R transfer is found to be important especially for the higher levels. A renormalization procedure is suggested as a remedy for the well-known numerical inaccuracy of trajectories with very long-lived collision complexes. This renormalization was not important for the present work.
Semiclassical calculations of rate constants for energy transfer in an HF gas from 300 to 3500 K are reported. The potential hypersurface used was an analytic fit to recent SCF calculations plus the experimental dispersion potential. Good agreement with experiments was obtained without further adjustment of the potential parameters.
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