Nuclear-motion corrections to Born-Oppenheimer barrier heights for chemical reactions

Bruce C. Garrett, Donald G Truhlar

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40 Scopus citations

Abstract

We use diatomics-in-molecules theory to estimate the nuclear-motion contributions to atom-diatom potential energy surfaces for reactive systems, with special emphasis on the saddle point region. We examine the reactions of H, O, F, and Cl with H2 and H with Cl2. Nuclear-motion corrections at the saddle point are in the range 0.007-0.07 kcal/mol for cases with one or two hydrogens and classical barrier heights in the range 0.7-3 kcal/mol and are about 0.2 kcal/mol for cases with two hydrogens and classical barrier heights in the range 8-12 kcal/mol. For F+H2 with parameters such that the predicted nuclear-motion correction is 0.03 kcal/mol at the saddle point, the correction is as large as 0.2 kcal/mol elsewhere on the surface. Isotopic substitution of D for H changes the classical barrier height by 0.003-0.1 kcal/mol for the cases studied.

Original languageEnglish (US)
Pages (from-to)4543-4547
Number of pages5
JournalThe Journal of chemical physics
Volume82
Issue number10
DOIs
StatePublished - Jan 1 1985

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