Variable Reaction Coordinate Direct RRKM Theory

摘要

Various aspects of the direct implementation of the variable reaction coordinate formalism for evaluating the kinetics of barrierless reactions are considered. A new discussion of the decoupling of the conserved and transi- tional modes within this formalism is provided with sample results for NCNO suggesting an optimum simple pro- cedure for implementing this decoupling. The effort involved in replacing analytic potentials with direct ab initio determinations in the Monte Carlo-based evaluation of the transitional mode partition functions is illustrated through sample calculations for Cl~- + CH_3Cl, CN + O_2, ~1CN + CO.