On the Theory of Chemical-Reaction Cross Sections. I. A Statistical-Dynamical Model

Abstract

A statistical‐dynamical model is formulated for total chemical‐reaction cross sections as a function of the relative velocity and the vibrational and the rotational state of the reactants. It is derived for reactions for which activated‐complex configurations can be defined; reactions with or without steric and activation barriers. A quasiequilibrium is postulated between reacting pairs and activated complexes of the same energy and angular momentum. An integral equation is obtained which is solved for the reaction cross section by introduction of a second postulate: The reaction probability is a function of the excess initial energy along the reaction coordinate (in excess of potential energy barrier, centrifugal potential barrier, and vibrational adiabatic requirements). A possible dynamical origin of the postulates is considered in later papers.

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