Collisional Effects upon Rotational Correlations of Symmetric Top Molecules

Abstract

Time‐dependent conditional phase‐space distribution functions are derived for classical ensembles of rigid molecules undergoing collision‐interrupted free rotation. The J‐diffusion and the M‐diffusion models proposed by Gordon, [J. Chem. Phys. 44, 1830 (1966)] are explored in detail. The expressions for the conditional distribution functions are evaluated for these models in terms of multiple time integrals. It is then shown that Fourier transform techniques can be used to express the integrals as convolutions which are analogous to Fixman and Rider's expressions [J. Chem. Phys. 51, 2425 (1969)]. A number of numerical results are presented.