The rate constants for the H+H2 reaction and its isotopic analogs at low temperatures: Wigner threshold law behavior

Toshiyuki Takayanagi, Nobuyuki Masaki, Kazutaka Nakamura, Makoto Okamoto, Shin Sato, George C Schatz

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Abstract

Variational transition-state theory rate constants for the H+H2 reaction and its isotopic analogs at very low temperatures have been calculated using the LSTH potential surface. The Wigner threshold law is found to hold quantitatively below 1 K and to within 34% on average at 5 K. The transition-state theory rate constants are found to be consistent with the requirements of the Wigner threshold law provided that a tunneling probability having the correct threshold behavior is used in calculating the transmission coefficient. Using these calculated rate constants, decay rates of H and D atoms in solid H2, D2, and HD were estimated and compared with experiment. The good agreement found suggests that these decays occur through quantum mechanical tunneling exchange reactions.

Original languageEnglish
Pages (from-to)6133-6139
Number of pages7
JournalJournal of Chemical Physics
Volume86
Issue number11
Publication statusPublished - 1987

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ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

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