Insights into the semiclassical Wigner treatment of bimolecular collisions

TL;DR

This paper rigorously derives the semiclassical Wigner approach for bimolecular collisions from fundamental principles, integrating previous theories and principles to enhance understanding of molecular collision dynamics.

Contribution

It provides a first-principles derivation of the semiclassical Wigner treatment, combining multiple foundational ideas and principles for the first time.

Findings

Derivation from first principles clarifies the theoretical basis.

Integration of Heller's ideas with collision models enhances accuracy.

Provides a rigorous foundation for semiclassical collision analysis.

Abstract

The semiclassical Wigner treatment of bimolecular collisions, proposed by Lee and Scully on a partly intuitive basis [J. Chem. Phys. 73, 2238 (1980)], is derived here from first principles. The derivation combines E. J. Heller's ideas [J. Chem. Phys. 62, 1544 (1975); 65, 1289 (1976); 75, 186 (1981)], the backward picture of molecular collisions [L. Bonnet, J. Chem. Phys. 133, 174108 (2010)] and the microreversibility principle.