Journal of Chemical Physics, Vol.101, No.9, 7603-7617, 1994
On the Energy-Dependence of the Steric Effect for Atom-Molecule Reactive Scattering .2. The Reaction Ca(D-1)+ch3F(Jkm=111)-)Caf((2)Pi)+ch3
The observed increase in the steric effect of the reaction Ca(D-1)+CH3F(JKM =111) -->CaF((II)-I-2)+CH3 with increasing energy has been tentatively ascribed to a reorientation of the initially oriented CH3F axis, due to anisotropic long-range forces [M. H. M. Janssen, D. H. Parker, and S. Stolte, J. Phys. Chem. 95, 8142 (1991)]. Here we present ab initio calculations and use these to construct a long-range potential. To this potential we fit an isotropic model potential and two anisotropic model potentials. On the long-range potential and on the model potentials we perform classical trajectory calculations, and we compare the two methods presented in the preceding paper [G. C. Groenenboom and A. J. H. M. Meijer, J. Chem. Phys. 101, 7592 (1994)] for the extraction of the steric effect. We conclude that already the attractive isotropic model presented in this paper can account for the observed energy dependence of the steric effect for this reaction via a "trapping" mechanism. We show that although reorientation is possible, it contributes little to the positive energy dependence of the steric effect.
Keywords:CROSSED-BEAM REACTION;ALKALINE-EARTH ATOMS;METHYL-IODIDE;BASIS-SETS;ORIENTATION;ABINITIO;STATE;COLLISIONS;EXCITATION;ASYMMETRY