Dynamics-driven reaction pathway in an intramolecular rearrangement

Salai Cheettu Ammal, Hiroshi Yamataka, Misako Aida, Michel Dupuis

Research output: Contribution to journalArticlepeer-review

130 Citations (Scopus)


A critical role is traditionally assigned to transition states (TSs) and minimum energy pathways, or intrinsic reaction coordinates (IRCs), in interpreting organic reactivity. Such an interpretation, however, ignores vibrational and kinetic energy effects of finite temperature. Recently it has been shown that reactions do not necessarily follow the intermediates along the IRC. We report here molecular dynamics (MD) simulations that show that dynamics effects may alter chemical reactions even more. In the heterolysis rearrangement of protonated pinacolyl alcohol Me3C-CHMe-OH2+ (Me, methyl), the MD pathway involves a stepwise route with C-O bond cleavage followed by methyl group migration, whereas the IRC pathway suggests a concerted mechanism. Dynamics effects may lead to new interpretations of organic reactivity.

Original languageEnglish
Pages (from-to)1555-1557
Number of pages3
Issue number5612
Publication statusPublished - Mar 7 2003

ASJC Scopus subject areas

  • General

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