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Published October 15, 1984 | public
Journal Article Open

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

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.

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.

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August 22, 2023
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October 16, 2023