A phase-space method for arbitrary bimolecular gas-phase reactions: Theoretical description

摘要

A theoretical model for the. calculation of rate constants for arbitrary bimolecular gas-phase reactions was developed. The method is based on the phase-space statistical method developed by Light and co-workers [1 - 6]. In the present article this method is extended to arbitrary molecular systems. The new method requires knowledge of the molecular properties in the reaction and products channels of the chemical system. The properties are the vibrational frequencies, moments of inertia,,and potential energy for the interacting species in their ground state equilibrium configuration. Furthermore, we have to calculate either the energy barrier or the long-range potential for the chemical system (if the reaction channel does not have an energy barrier). The usefulness of the method is that it can be applied to all bimolecular reactions, trimolecular reactions, and even reactions of higher orders. Therefore, it can be applied to cases where rate constants of complex chemical reactions are required, but reliable laboratory measurements or other means to estimate rate parameters are not yet possible. Even if spectroscopic data are not available for the reactants and products, it is possible to use electronic structure theory to calculate the required data. (C) 2001 John Wiley & Sons, Inc. [References: 33]