Dynamics Calculations Based on ab initio Potential Energy Surfaces

摘要

This paper provides a review of current work in the area of gas phase chemical dynamics. The use of accurate ab initio potential energy surface information in dynamical calculations is emphasized along with comparison of the results of the calculations with experiment. Reviewed in the area of chemical reactions: 1) the ab initio prediction of high barriers with applications to the H + DF yield HF + D and H + DC1 yield HC1 + D reactions; 2) electronic entrance-channel barriers and vibrational exit channel barriers in the F + H2 reaction; and 3) the polyatomic recombination reaction CH3 + H yield CH4. Some aspects of inelastic molecular collisions are also discussed. In many cases some aspects of the dynamical results can be related to rather specific features of the potential energy surfaces. This is important because it allows one to concentrate on the convergence of these specific surface features rather than on convergence of the whole potential energy surface. (Reprints)