Nonstatistical Dynamics in Unlikely Places: [1,5] Hydrogen Migration in Chemically Activated Cyclopentadiene

Lawrence M. Goldman, David R. Glowacki, Barry K. Carpenter

Research output: Contribution to journalArticle (Academic Journal)peer-review

37 Citations (Scopus)

Abstract

A molecular dynamics simulation reveals the occurrence of nonstatistical dynamical effects in the ring-opening and subsequent [1,5] H migration of bicyclo[2.1.0]pent-2-ene. The symptoms of the effects do not show up in the overall kinetics or product branching ratios of the reaction, which are well explained by a master-equation analysis, but in an oscillatory preference for migration of the two methylene hydrogens. It is predicted that these oscillations could have an observable effect on final product ratios in isotopically labeled analogues, and that the effect might be greater in certain solvents than in the gas phase.

Original languageEnglish
Pages (from-to)5312-5318
Number of pages7
JournalJournal of the American Chemical Society
Volume133
Issue number14
DOIs
Publication statusPublished - 13 Apr 2011

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