Ab Initio chemical kinetics

Converged quantal reaction rate constants for the D + H2 system

Steven L. Mielke, Gillian C. Lynch, Donald G. Truhlar, David W. Schwenke

Research output: Contribution to journalArticle

94 Citations (Scopus)

Abstract

We present accurate quantal rate constants for the D + H2 system in the 167-900 K temperature range and rate constants calculated in the separable rotation approximation up to 1500 K. We have calculated rate constants for the three most accurate ab initio potential energy surfaces. The separable-rotation calculations agree to within 2.2% with the present accurate quantal calculations, and the results show substantially better agreement with high-temperature experimental rate constants than do previous quantal calculations. The ab initio rate constants for the LSTH and DMBE surfaces agree well with experiment over a wide temperature range but the newer BKMP surface gives poor agreement at low temperatures. From 200 to 900 K, a factor of 4.5 in temperature, the present totally ab initio reaction rate constants agree with experiment within 13% or better at each temperature, with an average absolute deviation of only 5%.

Original languageEnglish (US)
Pages (from-to)8000-8008
Number of pages9
JournalJournal of Physical Chemistry
Volume98
Issue number33
StatePublished - 1994
Externally publishedYes

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Reaction kinetics
Reaction rates
Rate constants
reaction kinetics
Temperature
Potential energy surfaces
temperature
Experiments
potential energy
deviation
approximation

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Mielke, S. L., Lynch, G. C., Truhlar, D. G., & Schwenke, D. W. (1994). Ab Initio chemical kinetics: Converged quantal reaction rate constants for the D + H2 system. Journal of Physical Chemistry, 98(33), 8000-8008.

Ab Initio chemical kinetics : Converged quantal reaction rate constants for the D + H2 system. / Mielke, Steven L.; Lynch, Gillian C.; Truhlar, Donald G.; Schwenke, David W.

In: Journal of Physical Chemistry, Vol. 98, No. 33, 1994, p. 8000-8008.

Research output: Contribution to journalArticle

Mielke, SL, Lynch, GC, Truhlar, DG & Schwenke, DW 1994, 'Ab Initio chemical kinetics: Converged quantal reaction rate constants for the D + H2 system', Journal of Physical Chemistry, vol. 98, no. 33, pp. 8000-8008.
Mielke, Steven L. ; Lynch, Gillian C. ; Truhlar, Donald G. ; Schwenke, David W. / Ab Initio chemical kinetics : Converged quantal reaction rate constants for the D + H2 system. In: Journal of Physical Chemistry. 1994 ; Vol. 98, No. 33. pp. 8000-8008.
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