Semiclassical initial value representation: From Møller to Miller. II

Abstract

As shown by W. H. Miller in a seminal article [J. Chem. Phys. 53, 3578 (1970)], the most convenient and accurate semiclassical (SC) theory of molecular scattering in action-angle coordinates is based on the initial value representation (IVR) and the use of shifted angles, which are different from the natural angles usually used in the quantum and classical treatments. Here, we show for an inelastic molecular collision that the initial and final shifted angles define three-segment classical paths that are exactly those involved in the classical-limit of Tannor–Weeks quantum scattering theory [J. Chem. Phys. 98, 3884 (1993)], provided that the translational wave packets |g+⟩ and |g−⟩ into play in this theory are both taken at |0⟩. Assuming this to be the case, using van Vleck propagators, and applying the stationary phase approximation, Miller’s SCIVR expression of S-matrix elements is found, with an additional cut-off factor canceling the energetically forbidden transition probabilities. This factor, however, is close to unity in most practical cases. Furthermore, these developments show that the Møller operators underlie Miller’s formulation, thus confirming, for molecular collisions, the results recently established in the simpler case of light-induced rotational transitions [L. Bonnet, J. Chem. Phys. 153, 174102 (2020)]. Last but not least, we show, based on the previous results, that for processes involving long-range anisotropic forces, implementing the Skinner–Miller method [Chem. Phys. Lett. 300, 20 (1999)] in shifted coordinates makes its predictions both easier and more accurate than in natural coordinates.