Improved potential energy surfaces for the reaction O(/sup 3/P)+H/sub 2/. -->. OH+H
We present global /sup 3/A' and /sup 3/A'' potential energy surfaces for the reaction O(/sup 3/P)+H/sub 2/..-->..OH+H and its isotopic analogs. The new surfaces are based in part on the surface of Lee et al. (J. Chem. Phys. 76, 3563 (1982)) for collinear O--H--H, which is modified to give accurate properties for reactants and products. The potentials for noncollinear O--H--H geometries are based on bending energies of Bowman et al. (J. Chem. Phys. 81, 1739 (1984)) as fit previously and called surface set M2 by two of the authors (B. C. Garrett and D. G. Truhlar, Int. J. Quantum Chem. 29, 1463 (1986)), and the potentials for H--O--H geometries are based on a new interpolation scheme. The new surfaces treat the approach of an O to either end of H/sub 2/ equivalently. We used improved canonical variational transition state theory calculations with the least-action ground-state tunneling approximation (ICVT/LAG) to recalibrate the classical barrier height to 13.0 kcal/mol. The ICVT/LAG rate constants calculated using the new surfaces are in excellent agreement with experimental values over the temperature range 298--2400 K. Rate constants and kinetic isotope effects for reactions involving D/sub 2/ and HD also are presented and analyzed. Here again, the theoretical results are in very good agreement with experiments.
- Research Organization:
- Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
- OSTI ID:
- 5307177
- Journal Information:
- J. Chem. Phys.; (United States), Vol. 88:11
- Country of Publication:
- United States
- Language:
- English
Similar Records
Reaction kinetics of muonium with the halogen gases (F sub 2 , Cl sub 2 , and Br sub 2 )
Improved parametrization of diatomics-in-molecules potential energy surface for Na(3p /sup 2/P)+H/sub 2/. -->. Na(3s /sup 2/S)+H/sub 2/. [p]
Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
DEUTERIUM
ISOTOPE EFFECTS
HYDROGEN
CHEMICAL REACTION KINETICS
HYDROXYL RADICALS
CHEMICAL REACTION YIELD
COMBUSTION PRODUCTS
OXYGEN
HIGH TEMPERATURE
VERY HIGH TEMPERATURE
ELEMENTS
HYDROGEN ISOTOPES
ISOTOPES
KINETICS
LIGHT NUCLEI
NONMETALS
NUCLEI
ODD-ODD NUCLEI
RADICALS
REACTION KINETICS
STABLE ISOTOPES
YIELDS
400201* - Chemical & Physicochemical Properties
400800 - Combustion
Pyrolysis
& High-Temperature Chemistry