Monte Carlo Classical Trajectory Calculation of the Rates of F-Atom Vibrational Relaxation of HF and DF

Abstract

Rates of F‐atom vibrational relaxation of HF and DF have been calculated for the temperature range 600–2000°K using Monte Carlo classical trajectory methods. The processes $\mathrm{F+(D)HF}\mathrm{(v)\to }\mathrm{F+(D)HF}\text{(v−1)}$ , where v=1, 3, and 5 and $\mathrm{F+HF}\text{(0)→}\mathrm{F+HF}\text{(1)}$ were investigated. Agreement with available experimental data is excellent. The calculations show that vibrational de‐excitation is due to vibration‐rotation transfer and that excitation is due to translation‐vibration transfer. Multiple‐quantum transfers are found to occur in de‐excitation of higher vibrational levels. A semiempirical valence‐bond potential‐energy surface was used. No adjustments were made to the surface to cause agreement between calculated and experimental energy‐transfer results.