Kinetics, Mechanistics,and Energy Transfer by the Quasiclassical Trajectory Analysis of Potential Energy Functions.

摘要

A generalized formulation of a multiple integral equation for the calculation of rate is developed. Depending upon the number and kind of variables not integrated there obtains from the general equation an expression of rate in terms of rate constants, cross-sections, differential cross sections, doubly differential cross sections, reaction probability as a function of impact parameters, etc. Half of the variables here mentioned are those that determine the initial position and motion status of two molecules approaching a collision with one another and of their component atoms. The other half of the variables are those determining the position and motion status of the two to three molecules and their component atoms that result from the collision. A formal evaluation of this multiple integral equation is developed in terms of the completely detailed transform probability. This formal evaluation yields working equations for the computation of the above listed specific rate expressions in terms of the partially integrated transform probability. The use of tabulated (e.g. ab initio) potential energy surfaces is developed along three lines. Lastly, a method is outlined for the extension of the classical trajectory method for evaluation of the transform probabilities P(JI) to multi-potential energy function.