Rate constants from the reaction path Hamiltonian. II. Nonseparable semiclassical transition state theory

Baron Peters; Alexis T. Bell; Arup Chakraborty

doi:10.1063/1.1778162

Rate constants from the reaction path Hamiltonian. II. Nonseparable semiclassical transition state theory

Baron Peters, Alexis T. Bell, Arup Chakraborty

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Abstract

The parabolic barrier semiclassical transition state theory (SCTST), truncated parabolic barrier SCTST and fully anharmonic SCTST were studied to motivate reaction path Hamiltonian (RPH)-SCTST. It was found that the SCTST is qualitatively correct in the low and high temperature limits. The new correction captures the effects of curvature and barrier anharmonicity with just three frequency calculations. The results show that the effect of barrier anharmonicity can result in calculated rates that are much smaller than rates predicted by truncated harmonic SCTST.

Original language	English
Pages (from-to)	4461-4466
Number of pages	6
Journal	Journal of Chemical Physics
Volume	121
Issue number	10
DOIs	https://doi.org/10.1063/1.1778162
State	Published - 8 Sep 2004
Externally published	Yes

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Rate constants from the reaction path Hamiltonian. II. Nonseparable semiclassical transition state theory

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