Quantum and semiclassical study of the intramultiplet transitions in collisions of Cl(2P) and O(3P) with He, Ar and Xe

Abstract

Quantum and semiclassical (SC) close coupling and coupled states approaches, as well as the analytical two-level model of Nikitin, are implemented for studying Cl(2pj) and O(3pj) intramultiplet mixing dynamics in collisions with the rare gas atoms He, Ar and Xe. The validity of different approximations and the effects of electrostatic (ES) and Coriolis couplings are investigated in the calculations of room-temperature rate constants. SC methods are used to analyze the mechanism for the non-adiabatic dynamics. In particular, it is shown that the j = 0→1 transition in oxygen atoms, forbidden to first order, proceeds through post-collision relaxation induced by a complicated interplay between ES and Coriolis interactions.