Improved potential energy surface for F+H/sub 2/. -->. HF+H and H+H'F. -->. HF+H'

Journal Article · Tue Jan 01 04:00:00 EST 1985 · J. Chem. Phys.; (United States)

OSTI ID:5993935

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

We present an improved analytic potential energy surface for the F+H/sub 2/..-->..FH+H and H+FH'..-->..HF+H' reactions. The final surface is obtained in two stages. First we create a surface, called No. 4, which is based in the F--H--H barrier region on a previous partly empirical and partly theoretical fit and is based on the F--HxxxH exit channel and H--F--H barrier regions on new large-basis-set configuration interaction calculations. The final surface, called No. 5 incorporates more empirical information for collinear geometries in both the F--H--H and FHxxxH regions but remains a good representation of the ab initio calculations for bending potentials and in the strong-interaction regions. Variational-transition-state theory rate constants and WKB adiabatic barrier heights indicate that the final surface is more accurate than previous surfaces for thermal rate constants and overall reaction thresholds for F+H/sub 2/..-->..HF+H, F+D/sub 2/..-->..DF+D, and F+HD..-->..HF+D and for product-state thresholds for HF (n' = 3) and DF(n' = 4), where n' is the final vibrational quantum number.

• Research Organization: Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
• OSTI ID: 5993935
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 82:1; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTION KINETICS
CONFIGURATION INTERACTION
ELEMENTS
ENERGY
FLUORINE
HALOGENS
HYDROGEN
KINETICS
NONMETALS
POTENTIAL ENERGY
REACTION KINETICS