Abstract
Vibration-to-vibration energy transfer probabilities for $HF(v=n)+H_2(v=0){\to}HF(v=n-1)+H_2(v=1)$ and $DF(v=n)+D_2(v=0){\to}DF(v=n-1)+D_2(v=1)$ including both the vibration-to-vibration and translation (V-V, T) and vibration-to-vibration and rotation (V-V, R) energy transfer paths have been calculated semiclassically using a simplified collision model and Morse-type intermolecular interaction potential. The calculated results are in reasonably good agreement with those obtained by experimental studies. They also show that the transition processes for $HF(v=1-3)+H_2(v=0){\to}HF(v=0-2)+H_2(v=1)$ and $DF(v=1,\;4)+D_2(v=0){\to}DF(v=0,\;3)+D_2(v=1)$ are strongly dependent on the V-V, T path at low temperature but occur predominantly via the V-V, R path with rising temperature. The vibration-to-vibration energy transfer for $HF(v=4)+H_2(v=0){\to}HF(v=3)+H_2(v=1)$ and $DF(v=2-3)+D_2(v=0){\to}DF(v=1-2)+D_2(v=1)$ occur predominantly via V-V, R path and V-V, T path through whole temperatures, respectively.
