NONSTATISTICAL DYNAMICS IN THERMAL REACTIONS OF POLYATOMICMOLECULES

A brief review is presented of post-RRKM models for unimolecular reaction kinetics. The dynamics of the gas-phase SN2 reaction are discussed, and the important role of phase-space bottlenecks is highlighted. The remainder of the review is devoted to experimental and trajectory simulation results on thermal reactions of organic molecules that exhibit nonstatistical dynamics quite unlike that seen in the SN2 reaction. Specifically, the intermediates generated in these reactions decay much faster thanRRKMtheorywould predict, and often with bimodal or multimodal lifetime distributions. A qualitative model for this behavior based on overlaps of transitional regions in the molecular phase space is discussed.