Exact quantum quasiclassical, and semiclassical reaction probabilities for the collinear F+D_2 → FD+D reaction

Abstract

Exact quantum, quasiclassical, and semiclassical reaction probabilities and rate constants for the collinear reaction F+D_2 → FD+D are presented. In all calculations, a high degree of population inversion is predicted with P^R_(03) and P^R(04) being the dominant reaction probabilities. In analogy with the F+H_2 reaction (preceding paper), the exact quantum 0→3 and 0→4 probabilities show markedly different energy dependence with PR03 having a much smaller effective threshold energy (E_T=0.014 eV) than P^R_(04) (0.055 eV). The corresponding quasiclassical forward probabilities P^R_(03) and P^R_(04) are in poor agreement with the exact quantum ones, while their quasiclassical reverse and semiclassical counterparts provide much better approximations to the exact results. Similar comparisons are also made in the analysis of the corresponding EQ, QCF, QCR, and USC rate constants. An information theoretic analysis of the EQ and QCF reaction probabilities indicates nonlinear surprisal behavior as well as a significant isotope dependence. Additional quantum results at higher energies are presented and discussed in terms of threshold behavior and resonances. Exact quantum reaction probabilities for the related F+HD → FH+D and F+DH → FD+H reactions are given and an attempt to explain the observed isotope effects is made.

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