Reaction rates of H(H2), D(H2), and H(D2) van der Waals molecules and the threshold behavior of the bimolecular gas-phase rate coefficient

Gene C. Hancock, C. Alden Mead, Donald G Truhlar, Antonio J.C. Varandas

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52 Scopus citations

Abstract

We study low-energy quantal phenomena in the rearrangement of three-atom systems composed of H and D. All calculations are carried out on the double many-body expansion potential energy surface for the hydrogen trimer. The unimolecular rearrangements of van der Waals molecules, such as D⋯H 2→HD⋯H, are studied as a model for the exchange transfer reaction in condensed phases, and the gas-phase bimolecular reactions, such as D + H2→HD + H, are studied to probe the limiting low-temperature threshold behavior, which is compared to that predicted by quantum mechanical threshold laws. The reaction rates are studied down to temperatures of 10 -3 K. We also predict the spectroscopic tunneling shift on the lowest energy levels of the H⋯H2 complex.

Original languageEnglish (US)
Pages (from-to)3492-3503
Number of pages12
JournalThe Journal of chemical physics
Volume91
Issue number6
DOIs
StatePublished - Jan 1 1989

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