The rates of unimolecular reactions in gases

Abstract

The molecule of a dissociating gas is treated as a dynamical system with n normal modes of vibration with incommensurable frequencies. The assumption that the molecule dissociates when one coordinate attains a critical high value leads to a unimolecular velocity constant expressed as an integral; analytical expressions are derived for bounds to its value. Calculations in a simple case indicate that the velocity constant is approximately of the formThis is in general agreement with experiment if the constant W is identified with the corresponding empirical energy constant.