Transition path sampling study of classical rate-promoting vibrations

Dimitri Antoniou, Mohammad Ramin Abolfath, Steven D Schwartz

Research output: Contribution to journalArticle

18 Citations (Scopus)

Abstract

The use of transition path sampling to study the classical rate-promoting vibrations was discussed. A complicated dynamical behavior that cannot be captured by transition state theory was found. It was observed that slow promoting vibrations lead to reactive trajectories that overshoot the saddle point, but on the other hand the short period of fast oscillations allows the reactants to stay only briefly in a low-barrier regime. It was shown that there is a competition between these effects, which results to an intermediate value for the frequency of the rate-promoting vibration that is optimal for enhancing the rate.

Original languageEnglish (US)
Pages (from-to)6442-6447
Number of pages6
JournalThe Journal of Chemical Physics
Volume121
Issue number13
DOIs
StatePublished - Oct 1 2004
Externally publishedYes

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sampling
Trajectories
Sampling
vibration
saddle points
guy wires
trajectories
oscillations

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Transition path sampling study of classical rate-promoting vibrations. / Antoniou, Dimitri; Abolfath, Mohammad Ramin; Schwartz, Steven D.

In: The Journal of Chemical Physics, Vol. 121, No. 13, 01.10.2004, p. 6442-6447.

Research output: Contribution to journalArticle

Antoniou, Dimitri ; Abolfath, Mohammad Ramin ; Schwartz, Steven D. / Transition path sampling study of classical rate-promoting vibrations. In: The Journal of Chemical Physics. 2004 ; Vol. 121, No. 13. pp. 6442-6447.
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