Semiclassical calculations on the energy dependence of the steric effect for the reaction Ca(D-1)+CH3F(jkm=111)->CaF+CH3

In a previous article [A. J. H. M, Meijer, G. C. Groenenboom, and A. van der Avoird, J. Chem. Phys. 101, 7603 (1994)] we investigated the energy dependence of the steric effect of the reaction Ca (D-1)+CH3F (jkm = 111)-->CaF (A (II)-I-2)+CH3 using a quasiclassical trajectory method. It was found that we could not reproduce the experimental results for this reaction [M. H. M. Janssen, D. H. Parker, and S. Stolte, J. Phys. Chem. 95, 8142 (1991)]. In this article, we reinvestigate this reaction using a semiclassical method, in which the rotation of the molecule and the electronic states of the interacting atom and molecule are Created quantum mechanically. For the chemical reaction we use a model which correlates the projection of the electronic orbital angular momentum of the Ca atom on the intermolecular axis with the projection of the electronic orbital angular momentum of the CaF product on the diatomic axis [M. Menzinger, Polon. Phys. Acta A 73, 85 (1988)]. This model is applied to examine the CaF (A (II)-I-2, B (2) Sigma(+), A'(2) Delta) exit channels separately. We conclude that we can reproduce the experimental;results for the steric effect using this model. The improvement with respect to the classical trajectory results is shown to be due primarily to the extended reaction model rather than to the semiclassical description of the dynamics. We find trapping and reorientation in the semiclassical calculations, as in the previous classical trajectory results, but also non-adiabatic effects are present. The latter do not affect the reactive cross sections very much. (C) 1996 American Institute of Physics.