Kinetics of ion–molecule collision complexes in the gas phase. Experiment and theory

Abstract

Essential elements of a transition switching model formulation of statistical rate theory are presented. The model is developed for use on rather complex polyatomic potential surface. Data on the energy dependence of the absolute unimolecular rate constants and branching ratios, thermal biomolecular rate constants and branching ratios including isotopic-substitution studies, and kinetic-energy distributions for the lowest-energy pathways are presented for the C₄H^+˙₈, C₄H^+˙₆ and C₆H^+˙₆ reaction systems. Detailed comparisons are made between experiment and the transition-state switching model. Comments are directed toward tests of the fundamental assumptions of statistical rate theory and toward detailed mechanistic interpretation of the specific systems studied.