Global dynamics and transition state theories: Comparative study of reaction rate constants for gas-phase chemical reactions

Li Ping Ju, Ke Li Han, John Z.H. Zhang

Research output: Contribution to journalReview articlepeer-review

Abstract

In this review article, we present a systematic comparison of the theoretical rate constants for a range of bimolecular reactions that are calculated by using three different classes of theoretical methods: quantum dynamics (QD), quasi-classical trajectory (QCT), and transition state theory (TST) approaches. The study shows that the difference of rate constants between TST results and those of the global dynamics methods (QD and QCT) are seen to be related to a number of factors including the number of degrees-of-freedom (DOF), the density of states at transition state (TS), etc. For reactions with more DOF and higher density of states at the TS, it is found that the rate constants from TST calculations are systematically higher than those obtained from global dynamics calculations, indicating large recrossing effet for these systems. The physical insight of this phenomenon is elucidated in the present review.

Original languageEnglish (US)
Pages (from-to)305-316
Number of pages12
JournalJournal of Computational Chemistry
Volume30
Issue number2
DOIs
StatePublished - Jan 30 2009

Keywords

  • PES
  • Quantum dynamics
  • Quasi-classical trajectory
  • Rate constant
  • Recrossing
  • Transition state theory

ASJC Scopus subject areas

  • Chemistry(all)
  • Computational Mathematics

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