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Annu Rev Phys Chem. 2005;56:57-89.

Nonstatistical dynamics in thermal reactions of polyatomic molecules.

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  • 1Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853-1301, USA.


A brief review is presented of post-RRKM models for unimolecular reaction kinetics. The dynamics of the gas-phase S(N)2 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 S(N)2 reaction. Specifically, the intermediates generated in these reactions decay much faster than RRKM theory would 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.

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