Calculation of vibrational deactivation of HF(1 ⩽n ⩽ 7) by DF(0) and of DF(1 ⩽ n ⩽ 7) by HF(0)

Abstract

Rate constants are calculated semiclasically for vibrational deactivation of HF(n) by DF(0) and of DF(n) by HF(0) for n = 1–7 in the temperature range from 300 K to 3000 K. The variation with temperature agrees rather well with experiments for HF(1) and DF(1), although the theoretical rate for HF(1) amounts only to about 50% of the experimental results at low temperature (300 K). The scaling with n agrees very well with experiments for DF(n) at 300 K. Single quantum transitions are found to dominate while multiquantum transitions contribute insignificantly. DF(n) is deactivated by a V—T/R energy transfer at all temperatures. HF(n) is deactivated both by a V—V and a V—T/R energy transfer at low temperature, V—V being about twice as fast as V—T/R at 300 K, while V—T/R dominates increasingly at higher temperatures. Complex collisions are important for both V—V and V—T/R energy transfer.