Molecular Dynamics of Unstable Intermediates

Abstract

AbstractRecent progress in experimental techniques has made possible the detailed study of the molecular dynamics of energy‐rich polyatomic species. The development of more sensitive tools enables us to consider such questions as the lifetime distribution, the branching ratio for alternative decay modes and the energy disposal in the dissociation products.These deeper probes into the dynamics have led to a better understanding of the theory of the formation and decay of unstable intermediates. We review a unified point of view which covers both unimolecular and bimolecular collision phenomena.An important recent diagnostic tool is the distribution of energy among the dissociation products. We consider a theory of such distributions which will enable us to correlate and codify the existing data, with particular emphasis on diviations from the RRKM predictions. A measure of the deviation is provided by the introduction of the concept of entropy thereby establishing a link between non‐equilibrium statistical mechanics and the evolution of energy‐rich super‐molecules.