Global potential-energy surfaces for H2Cl

David W. Schwenke, Susan C. Tucker, Rozeanne Steckler, Franklin B. Brown, Gillian C. Lynch, Donald G. Truhlar, Bruce C. Garrett

Research output: Contribution to journalArticle

82 Scopus citations

Abstract

We present two new analytic potential-energy surfaces suitable for studying the competition between the abstraction reaction H + DCl→HD + Cl and the exchange reaction H + DCl→HCl + D. In the abstraction channel the surfaces are only slightly different from the Stern-Persky-Klein GSW surface, but the exchange barrier on both surfaces is raised by inclusion of a three-center term fitted to ab initio extended-basis-set multireference configuration interaction calculations with scaled external correlation. The two surfaces differ significantly only for the steepness of H-Cl-H bend potential. The exchange and abstraction saddle points are characterized by harmonic analysis for H 2Cl, HDCl, and D2Cl, and we also compute vibrationally adiabatic barrier heights including anharmonicity. We also report thermal rate constants and activation energies for both reactions mentioned above.

Original languageEnglish (US)
Pages (from-to)3110-3120
Number of pages11
JournalThe Journal of Chemical Physics
Volume90
Issue number6
DOIs
StatePublished - Jan 1 1989

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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