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

doi:10.1063/1.455914

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 journal › Article › peer-review

85 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 language	English (US)
Pages (from-to)	3110-3120
Number of pages	11
Journal	The Journal of chemical physics
Volume	90
Issue number	6
DOIs	https://doi.org/10.1063/1.455914
State	Published - 1989
Externally published	Yes

ASJC Scopus subject areas

General Physics and Astronomy
Physical and Theoretical Chemistry

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10.1063/1.455914

Cite this

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title = "Global potential-energy surfaces for H2Cl",

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.",

author = "Schwenke, {David W.} and Tucker, {Susan C.} and Rozeanne Steckler and Brown, {Franklin B.} and Lynch, {Gillian C.} and Truhlar, {Donald G.} and Garrett, {Bruce C.}",

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T1 - Global potential-energy surfaces for H2Cl

AU - Schwenke, David W.

AU - Tucker, Susan C.

AU - Steckler, Rozeanne

AU - Brown, Franklin B.

AU - Lynch, Gillian C.

AU - Truhlar, Donald G.

AU - Garrett, Bruce C.

PY - 1989

Y1 - 1989

N2 - 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.

AB - 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.

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Global potential-energy surfaces for H₂Cl

Abstract

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