Semiclassical initial value theory of rotationally inelastic scattering: Some remarks on the phase index in the interaction picture

TL;DR

This paper improves the semiclassical initial value theory for rotationally inelastic scattering by modifying the phase index, extending its applicability and achieving results close to exact quantum calculations.

Contribution

It introduces a new phase index in the interaction picture, enhancing the accuracy and applicability of the semiclassical theory for rotationally inelastic scattering.

Findings

Extended the semiclassical theory's applicability.

Achieved close agreement with quantum scattering results.

Applicable to both planar and three-dimensional models.

Abstract

This paper deals with the treatment of quantum interferences in the semiclassical initial value theory of rotationally inelastic scattering in the interaction picture [C. W. McCurdy and W. H. Miller, J. Chem. Phys. 67, 463 (1977)]. It is shown that substituting the original phase index by a new one extends the range of applicability of the theory. The resulting predictions are in close agreement with exact quantum scattering results for a model of atom-rigid diatom collision involving strong interferences. The developments are performed within the framework of the planar rotor model, but they are readily applicable to the three-dimensional case.