Semiclassical collision theory. Application of multidimensional uniform approximations to the atom–rigid-rotor system
- 1 February 1975
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 62 (3) , 913-926
- https://doi.org/10.1063/1.430543
Abstract
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.Keywords
This publication has 15 references indexed in Scilit:
- Semiclassical collision theory. Multidimensional integral methodThe Journal of Chemical Physics, 1974
- Semiclassical transition probabilities by an asymptotic evaluation of the S matrix for elastic and inelastic collisions. Bessel uniform approximationThe Journal of Chemical Physics, 1973
- S matrix elements for excited rotational state transitionsThe Journal of Chemical Physics, 1973
- Asymptotic evaluation of multidimensional integrals for the S matrix in the semiclassical theory of inelastic and reactive molecular collisionsMolecular Physics, 1973
- Multidimensional canonical integrals for the asymptotic evaluation of the S-matrix in semiclassical collision theoryFaraday Discussions of the Chemical Society, 1973
- Theory of Semiclassical Transition Probabilities (S Matrix) for Inelastic and Reactive Collisions. Uniformization with Elastic Collision TrajectoriesThe Journal of Chemical Physics, 1972
- Theory of Semiclassical Transition Probabilities for Inelastic and Reactive Collisions. II Asymptotic Evaluation of the S MatrixThe Journal of Chemical Physics, 1971
- Classical S Matrix for Linear Reactive Collisions of H+Cl2The Journal of Chemical Physics, 1971
- Extension of the WKB method to wave functions and transition probability amplitudès (S-matrix) for inelastic or reactive collisionsChemical Physics Letters, 1970
- A validation of the method of amplitude density functions in computing the S-matrix for a scattering problemChemical Physics Letters, 1967