An improved potential energy surface for the H2Cl system and its use for calculations of rate coefficients and kinetic isotope effects

Thomas C. Allison, Gillian C. Lynch, Donald G. Truhlar, Mark S. Gordon

Research output: Contribution to journalArticle

112 Citations (Scopus)

Abstract

We present a new potential energy surface (called G3) for the chemical reaction Cl + H2 → HCl + H. The new surface is based on a previous potential surface called GQQ, and it incorporates an improved bending potential that is fit to the results of ab initio electronic structure calculations. Calculations based on variational transition state theory with semiclassical transmission coefficients corresponding to an optimized multidimensional tunneling treatment (VTST/OMT, in particular improved canonical variational theory with least-action ground-state transmission coefficients) are carried out for nine different isotopomeric versions of the abstraction reaction and six different isotopomeric versions of the exchange reaction involving the H, D, and T isotopes of hydrogen, and the new surface is tested by comparing these calculations to available experimental data. The theoretical data are also used to investigate the equilibrium constant and the branching ratio for the reverse reaction, and calculations of these quantities are compared to the available experimental and theoretical data.

Original languageEnglish (US)
Pages (from-to)13575-13587
Number of pages13
JournalJournal of Physical Chemistry
Volume100
Issue number32
StatePublished - Aug 8 1996
Externally publishedYes

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Potential energy surfaces
Isotopes
isotope effect
potential energy
Kinetics
kinetics
coefficients
Hydrogen
Equilibrium constants
Surface potential
Electron transitions
Ground state
Electronic structure
Chemical reactions
chemical reactions
isotopes
electronic structure
ground state
hydrogen

ASJC Scopus subject areas

  • Engineering(all)
  • Physical and Theoretical Chemistry

Cite this

An improved potential energy surface for the H2Cl system and its use for calculations of rate coefficients and kinetic isotope effects. / Allison, Thomas C.; Lynch, Gillian C.; Truhlar, Donald G.; Gordon, Mark S.

In: Journal of Physical Chemistry, Vol. 100, No. 32, 08.08.1996, p. 13575-13587.

Research output: Contribution to journalArticle

Allison, Thomas C. ; Lynch, Gillian C. ; Truhlar, Donald G. ; Gordon, Mark S. / An improved potential energy surface for the H2Cl system and its use for calculations of rate coefficients and kinetic isotope effects. In: Journal of Physical Chemistry. 1996 ; Vol. 100, No. 32. pp. 13575-13587.
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