Rate constants from the reaction path Hamiltonian. I. Reactive flux simulations for dynamically correct rates

Baron Peters, Alexis T. Bell, Arup Chakraborty

Research output: Contribution to journalArticlepeer-review

Abstract

A method to construct a transverse eigensystem to analyze the rate constants from the reaction path Hamiltonian in systems with many degenerate transverse frequencies was discussed. Reactive flux calculations were facilitated by the attainment of smoothly varying coupling constants by the diabatically constructed reaction path. The reaction flux formalism could be applied to an ab initio reaction path hamiltonian for a system with 54 degrees of freedom. The results show that the variational transition state theory only accounts for half of the rate constant reduction due to recrossing trajectories.

Original languageEnglish (US)
Pages (from-to)4453-4460
Number of pages8
JournalJournal of Chemical Physics
Volume121
Issue number10
DOIs
StatePublished - Sep 8 2004
Externally publishedYes

ASJC Scopus subject areas

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

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