Rotational excitation of linear molecules by collisions with atoms: Comparison of classical and quantum methods

Abstract

Exact quantum results for the rotational excitation of rigid linear molecules by collisions with atoms are compared with classical trajectory results. The systems studied are CO–He, CS–H2, OCS–H2, HCl–He, and HCl–Ar at collision energies up to 500 cm−1. Total cross sections and state to state rate constants are compared. The classical results are found to be in good agreement with the quantum results on the average. Differences arising from the existence of purely quantum effects are clearly evident, but consistent and predictable. Two methods of extracting state selective information from moments of the classical distribution are examined and found to be less reliable than the usual histogram method. In conjunction with previous comparisons of classical and quantum results these calculations provide a useful measure of the limitations and reliability of classical trajectories.