Quantum flux studies of the mechanism of Ca(4s5p 1P)→Ca(4s5p 3P) collisions

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Abstract
We apply a new method [M. H. Alexander, J. Chem. Phys. 9 4, 8931 (1991)] for the study of the mechanism of inelastic collisions, to the analysis of spin‐changing collisions of Ca atoms in the 4s5p Rydberg state. The method involves the determination of the current density associated with, separately, the incoming and outgoing scattering wave functions in a locally adiabatic basis. This yields a picture of how the incoming flux, initially associated with a given internal state, redistributes itself as a function of the interparticle separation both as the particles approach, and, subsequently, as the particles recede. By proper selection of the initial state, we explore the dependence on orbital orientation of the probability for the spin‐changing Ca(4s5p 1P)→Ca(4s5p 3P) process. Further, we show how the distribution of population among the fine‐structure levels of the 3P state depends on final‐state interactions in the exit channel.

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