Variational transition state theory calculations for an atom--radical reaction with no saddle point: O+OH

Journal Article · Thu Dec 15 04:00:00 EST 1983 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.445787· OSTI ID:5596914

Rai, S N; Truhlar, D G

We have extended the general polyatomic canonical variational theory formalism of Isaacson and one of the authors to improved canonical and microcanonical variational theory. We have calculated the rate constants for the reaction in the title over the temperature range 200--2500 K using all three variational theories and the Melius--Blint ab initio potential energy surface. The results are compared to canonical variational calculations based on the reaction-path interpolation scheme of Quack and Troe, to the trajectory calculations of Miller, and to experiment. We find that the microcanonical variational transition states have a strong energy dependence and the generalized free energy of activation curves have two maxima. Quantization effects appear to be important at the lower temperatures, and recrossing effects may be important at higher temperatures.

• Research Organization: Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
• OSTI ID: 5596914
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 79:12; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400600 -- Radiation Chemistry
CHEMICAL REACTION KINETICS
ELEMENTS
HIGH TEMPERATURE
HYDROXYL RADICALS
KINETICS
MEDIUM TEMPERATURE
NONMETALS
OXYGEN
RADICALS
REACTION KINETICS
VARIATIONAL METHODS
VERY HIGH TEMPERATURE