Global potential-energy surfaces for H/sub 2/Cl

Journal Article · Wed Mar 15 04:00:00 EST 1989 · J. Chem. Phys.; (United States)

OSTI ID:6477882

Schwenke, D W; Tucker, S C; Steckler, R; Brown, F B; Lynch, G C; Truhlar, D G; Garrett, B C

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/sub 2/Cl, HDCl, and D/sub 2/Cl, and we also compute vibrationally adiabatic barrier heights including anharmonicity. We also report thermal rate constants and activation energies for both reactions mentioned above.

• Research Organization: Department of Chemistry and Supercomputer Institute, University of Minnesota, Minneapolis, Minnesota 55455
• OSTI ID: 6477882
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 90:6; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACTIVATION ENERGY
CHEMICAL REACTION KINETICS
CHLORINE
ELEMENTS
ENERGY
FLUIDS
GASES
HALOGENS
HYDROCHLORIC ACID
HYDROGEN
HYDROGEN COMPOUNDS
INORGANIC ACIDS
KINETICS
NONMETALS
REACTION KINETICS