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

83 Citations (Scopus)

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
StatePublished - 1989
Externally publishedYes

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Potential energy surfaces
potential energy
Harmonic analysis
harmonic analysis
Rate constants
saddle points
Activation energy
configuration interaction
inclusions
slopes
activation energy

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Schwenke, D. W., Tucker, S. C., Steckler, R., Brown, F. B., Lynch, G. C., Truhlar, D. G., & Garrett, B. C. (1989). Global potential-energy surfaces for H2Cl. The Journal of Chemical Physics, 90(6), 3110-3120.

Global potential-energy surfaces for H2Cl. / Schwenke, David W.; Tucker, Susan C.; Steckler, Rozeanne; Brown, Franklin B.; Lynch, Gillian C.; Truhlar, Donald G.; Garrett, Bruce C.

In: The Journal of Chemical Physics, Vol. 90, No. 6, 1989, p. 3110-3120.

Research output: Contribution to journalArticle

Schwenke, DW, Tucker, SC, Steckler, R, Brown, FB, Lynch, GC, Truhlar, DG & Garrett, BC 1989, 'Global potential-energy surfaces for H2Cl', The Journal of Chemical Physics, vol. 90, no. 6, pp. 3110-3120.
Schwenke DW, Tucker SC, Steckler R, Brown FB, Lynch GC, Truhlar DG et al. Global potential-energy surfaces for H2Cl. The Journal of Chemical Physics. 1989;90(6):3110-3120.
Schwenke, David W. ; Tucker, Susan C. ; Steckler, Rozeanne ; Brown, Franklin B. ; Lynch, Gillian C. ; Truhlar, Donald G. ; Garrett, Bruce C. / Global potential-energy surfaces for H2Cl. In: The Journal of Chemical Physics. 1989 ; Vol. 90, No. 6. pp. 3110-3120.
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