Abstract

A semiclassical approximation to the S matrix of the infinite-order-sudden approximation is introduced. This is employed to yield for the energy-transfer effective cross section a purely classical approximation, analogous to the Mason-Monchick approximation [J. Chem. Phys. 36, 1622 (1962)] for traditional collision integrals. Constraints on energy and on angular momentum transfer are included. Numerical evaluation of this new approximation can readily be performed alongside that for traditional collision integrals. The new result is tested against full classical trajectory calculations for six potential energy surfaces for the collision systems H-N(2), He-N(2), He-CO, and Ar-CO(2). Differences of no more than 15% from the classical trajectory calculations have been obtained.

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