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Test of variational transition state theory against accurate quantal results for a reaction with very large reaction-path curvature and a low barrier

Truhlar, Donald G. and Garrett, Bruce C. and Hipes, Paul G. and Kuppermann, Aron (1984) Test of variational transition state theory against accurate quantal results for a reaction with very large reaction-path curvature and a low barrier. Journal of Chemical Physics, 81 (8). pp. 3542-3545. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:TRUjcp84

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Abstract

We present three sets of calculations for the thermal rate constants of the collinear reaction I+HI-->IH+I: accurate quantum mechanics, conventional transition state theory (TST), and variational transition state theory (VTST). This reaction differs from previous test cases in that it has very large reaction-path curvature but hardly any tunneling. TST overestimates the accurate results by factors of 2×10^10, 2×10^4, 57, and 19 at 40, 100, 300, and 1000 K, respectively. At these same four temperatures the ratios of the VTST results to the accurate quantal ones are 0.3, 0.8, 1.1, and 1.4, respectively. We conclude that the variational transition states are meaningful, even though they are computed from a reaction-path Hamiltonian with large curvature, which is the most questionable case.


Item Type:Article
Additional Information:Copyright © 1984 American Institute of Physics. Received 27 April 1984; accepted 1 June 1984. The work at the University of Minnesota was supported in part by the U.S. Department of Energy, Office of Basic Energy Sciences, by contract No. DE-AC02-79ER-10425. The work at Chemical Dynamics Corporation was supported in part by the U.S. Army Research Office by contract No. DAAG29-81-C-0015. The work at the California Institute of Technology was supported in part by the U.S. Air Force Office of Scientific Research by contract NO. AFOSR-82-0341.
Subject Keywords:CHEMICAL REACTION KINETICS, IODINE, HYDRIODIC ACID, VARIATIONAL METHODS, QUANTUM MECHANICS
Record Number:CaltechAUTHORS:TRUjcp84
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:TRUjcp84
Alternative URL:http://dx.doi.org/10.1063/1.448082
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:10494
Collection:CaltechAUTHORS
Deposited By: Archive Administrator
Deposited On:09 May 2008
Last Modified:26 Dec 2012 10:01

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