Title

An Application of Conventional Transition State `Theory To Compute High--Pressure Limit Thermal Rate Coefficients for the Reaction: H(D) + O2  H(D)O2*  OH(D) + O

Document Type

Article

Publication Date

10-1994

Publication Source

Journal of Physical Chemistry

Volume

98

Issue

42

Inclusive pages

10794–10801

DOI

10.1021/j100093a020

Peer Reviewed

yes

Abstract

Several ab initio studies have focused on the minimum energy path region of the hydroperoxyl potential energy surface (PES) (J. Chem. Phys. 1988, 88, 6273) and the saddle point region for H-atom exchange via a T-shaped HO2 complex (J. Chem. Phys. 1989, 91, 2373). Further, the results of additional calculations (J. Chem. Phys. 1991, 94, 7068) have been reported which, when combined with the earlier studies, provide a global description (but not an analytic representation) of the PES for this reaction. In this work, information at the stationary points of the ab initio PES is used within the framework of conventional transition state theory (TST) applied to both unimolecular and bimolecular processes in the high-pressure limit to compute estimates of the thermal rate coefficients for the forward and reverse reactions. Because these reactions proceed via a bound complex, a simple probability model is utilized to interpret the calculated statistical rate coefficients and to compare the present calculations with both the most recent experimental measurements and the results of quasiclassical trajectory calculations completed on the (analytic) DMBE IV PES (J. Chem. Phys. 1992, 96, 5137).

Disciplines

Chemistry

 
 

Link to Original Published Item

http://pubs.acs.org/doi/pdf/10.1021/j100093a020