Progress on the Modeling of the Collisional Energy Transfer Mechanism in Unimolecular Reactions

摘要

The RRKM theory of uniomlecular reaction rates is a statistical mechanical theory based on an assumption of microcanonical equilibrium in the reactant phase space. The energy transfer in reactant medium collisions was originally described by a canonical strong collision assumption, i. e., an assumption of full thermal equilibration in each collision. In our work we first introduced a microcanonical strong collision assumption which gives the RRKM theory a consistent from.