Communication: An existence test for dividing surfaces without recrossing

Ryan Gotchy Mullen, Joan Emma Shea, Baron Peters

Research output: Contribution to journalArticle

Abstract

The claim that Grote-Hynes theory (GHT), when it provides accurate rates, is equivalent to multidimensional variational transition state theory (VTST) has been debated for decades with convincing arguments on both sides. For the two theories to be equivalent a perfect dividing surface with no recrossing must exist. We describe an easily implemented test employing deterministic microcanonical (NVE) trajectories which can identify situations where no perfect dividing surface exists and thereby potentially falsify the claim of equivalence. We use this test to reach data-supported conclusions about the relationship between GHT and VTST.

Original languageEnglish (US)
Article number041104
JournalJournal of Chemical Physics
Volume140
Issue number4
DOIs
StatePublished - Jan 1 2014
Externally publishedYes

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ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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