Year: 1977
Type: article
Abstract: The standard tunneling path in transition state theory for reactions such as H+H2→H2+H has been the so-called reaction path, namely the path of steepest ascent to the saddle point. This path is now known to give numerical results for the reaction probability which are in disagreement with the exact quantum mechanical ones by an order of magnitude at low tunneling energies. A new tunneling path corresponding to a line of vibrational endpoints is proposed. It is much shorter and is shown to give results in agreement with the quantum ones to within about a factor of two. A semiclassical basis for choosing this new path is given.
Source: The Journal of Chemical Physics
DOI: 10.1063/1.435172
Authors: R. A. Marcus, Michael E. Coltrin
Institution: University of Illinois Urbana-Champaign
Language: English
Subfield: Physical and Theoretical Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: bronze
OpenAlex ID: W2065425385