The role of vibrational–rotational coupling in V–V and V–R,T energy transfer

The effect of neglecting vibrational–rotational coupling in energy transfer calculations is studied for collisions of HF (v=1–7) with HF (v=0). An analog of a "classical path" method is considered in which rigid-rotor trajectories are used to determine a time-dependent forcing term on the vibrational motion of each molecule. The results are compared with our quasiclassical calculations in which no such approximation was used. At higher vibrational states the rigid-rotor forced-oscillator model is found to predict substantially smaller V–R,T rate constants than those found in the exact study.