ROLE OF ANGULAR-MOMENTUM IN STATISTICAL UNIMOLECULAR RATE THEORY

A variety of topics is reviewed with an emphasis on assessment of models and discussion of their underlying physical assumptions, rather than on an overview of applications. Different treatments of angular momentum in the Rice-Ramsperger-Kassel-Marcus theory are surveyed and compared for tight and flexible transition states. The influence of angular momentum on thermal reaction rates is examined within the framework of variational transition state theory. The vibrational/rotational adiabatic theory of unimolecular decomposition is discussed. Various models for product energy distributions are summarized. The nature of non-thermal distributions of reactant angular momentum, arising from particular experimental techniques, is examined. A brief discussion of theoretical studies of vibrational/rotational coupling in the reactant and at the transition state is provided. The review attempts to unify advances in the fields of neutral and ion unimolecular decomposition.