Semiclassical transition state theory for nonseparable systems: Application to the collinear H+H$sub 2$ reaction

Journal Article · Mon Sep 15 04:00:00 EDT 1975 · J. Chem. Phys., v. 63, no. 6, pp. 2710-2716

DOI:https://doi.org/10.1063/1.431620· OSTI ID:4198865

Chapman, S; Garrett, B C; Miller, W H

Two different kinds of semiclassical approximations are used to evaluate a previously obtained quantum mechanical transition state theory rate expression. No assumptions, however, such as separability of the Hamiltonian, vibrationally adiabatic motion along a reaction coordinate, etc., are incorporated. Application is made to the collinear H+H$sub 2$ reaction, and agreement with accurate quantum scattering calculations is found to be reasonably good. The results indicate that transition state theory: provided no assumptions of separability are included: is probably as accurate quantum mechanically as it has been found to be classically for describing the threshold of chemical reactions with an activation barrier.

• Research Organization: Department of Chemistry and Inorganic Materials Research Division, Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
• Sponsoring Organization: USDOE
• NSA Number: NSA-33-003974
• OSTI ID: 4198865
• Journal Information: J. Chem. Phys., v. 63, no. 6, pp. 2710-2716, Journal Name: J. Chem. Phys., v. 63, no. 6, pp. 2710-2716; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

*HYDROGEN-- CHEMICAL REACTION KINETICS
640302* --Physics Research--Atomic
Molecular & Chemical Physics--Atomic & Molecular Properties
ACTIVATION ENERGY
ARRHENIUS EQUATION
N60200* --Physics (Atomic & Molecular)--Atomic & Molecular Properties
SEMICLASSICAL APPROXIMATION