Nonstatistical dynamics in thermal reactions of polyatomic molecules

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 o...

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Bibliographic Details
Published inAnnual review of physical chemistry Vol. 56; no. 1; pp. 57 - 89
Main Author Carpenter, Barry K
Format Journal Article
LanguageEnglish
Published United States Annual Reviews, Inc 01.01.2005
Subjects
Atoms & subatomic particles
Chemical reactions
Chemistry
Heat
Molecules
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Summary: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.
Bibliography:ObjectType-Article-2
SourceType-Scholarly Journals-1
ObjectType-Feature-3
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ObjectType-Review-1
ISSN:0066-426X
1545-1593
DOI:10.1146/annurev.physchem.56.092503.141240