Dynamics of X+CH 4 (X=H, O, Cl) reactions

How reliable is transition state theory for fine-tuning potential energy surfaces?

A. J C Varandas, P. J S B Caridade, John Zhang, Q. Cui, K. L. Han

Research output: Contribution to journalArticle

Abstract

Trajectory calculations run on global potential energy surfaces have shown that the topology of the entrance channel has strong implications on the dynamics of the title reactions. This may explain why huge differences are observed between the rate constants calculated from global dynamical methods and those obtained from local methods that employ the same potential energy surfaces but ignore such topological details. Local dynamics approaches such as transition state-based theories should then be used with caution for fine-tuning potential energy surfaces, especially for fast reactions with polyatomic species since the key statistical assumptions of the theory may not be valid for all degrees of freedom.

Original languageEnglish (US)
Article number064312
JournalJournal of Chemical Physics
Volume125
Issue number6
DOIs
StatePublished - 2006

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Potential energy surfaces
Tuning
potential energy
tuning
methylidyne
entrances
Rate constants
topology
degrees of freedom
Trajectories
Topology
trajectories

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Dynamics of X+CH 4 (X=H, O, Cl) reactions : How reliable is transition state theory for fine-tuning potential energy surfaces? / Varandas, A. J C; Caridade, P. J S B; Zhang, John; Cui, Q.; Han, K. L.

In: Journal of Chemical Physics, Vol. 125, No. 6, 064312, 2006.

Research output: Contribution to journalArticle

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