Published February 1, 1975 | Version v1
Journal article

Semiclassical collision theory. Application of multidimensional uniform approximations to the atom-rigid-rotor system

  • 1. Department of Chemistry, University of Illinois, Urbana, Illinois 61801

Description

The multidimensional Bessel and Airy uniform approximations developed earlier in this series for the semiclassical S matrix are applied to the atom rigid−rotor system. The need is shown for (a) using a geoemetrical criterion for determining whether a stationary phase point (s.p.pt) is a maximum, minimum, or saddle point; (b) choosing a proper quadrilateral configuration of the s.p. pts. with the phases as nearly equal as possible; and (c) choosing a unit cell to favor near−separation of variables. (a) and (b) apply both to the Airy and to the Bessel uniform approximations, and (c) to the Bessel. The use of a contour plot both to understand and to facilitate the search in new cases is noted. The case of real and complex−valued stationary phase points is also considered, and the Bessel uniform−in−pairs approximation is applied. Comparison is made with exact quantum results. As in the one−dimensional case, the Bessel is an improvment over the Airy for ''k = 0'' transitions, while for other transitions they give similar results. Comparison in accuracy with the results of the integral method is also given. As a whole, the agreement can be considered to be reasonable. The improvement of the present over various more approximate results is shown.

Additional details

Identifiers

Publishing Information

Journal Title
The Journal of Chemical Physics
Journal Volume
62
Journal Issue
3
Series
J. Chem. Phys.
Journal Page Range
913-926
ISSN
0021-9606

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