A transition state theory-based statistical distribution of unimolecular decay rates with application to unimolecular decomposition of formaldehyde

Abstract

A statistical distribution of state-specific unimolecular decay rates is derived (within the framework of random matrix theory) that is determined completely by the transition state properties of the potential energy surface. It includes the standard χ-square distributions as a special case. Model calculations are presented to show the extent to which it can differ from the χ-square distribution, and specific application is made to the state-specific unimolecular decay rate data for D2CO→D2+CO.