A general small-curvature approximation for transition-state-theory transmission coefficients

Rex T. Skodje, Donald G Truhlar, Bruce C. Garrett

Research output: Contribution to journalArticlepeer-review

308 Scopus citations

Abstract

We derive an expression for the effective mass along the reaction coordinate in a chemically reacting system. This expression is used in two convenient algorithms for including quantum mechanical effects on the reaction coordinate into transition-state theory or generalized transition-state theory. One algorithm is based on a uniform semiclassical approximation; the other is based on a parabolic approximation to the effective potential. Examples are presented to show that the theory accurately accounts for reaction-path-curvature effects on the tunneling contributions to the reactions H + H2, D + D2, and D + H2. Although the derivation, and hence expected reliability, of the new methods is most valid for systems with small reaction-path curvature, the methods are generally applicable and should provide useful accuracy even for medium-curvature and some large-curvature systems.

Original languageEnglish (US)
Pages (from-to)3019-3023
Number of pages5
JournalJournal of Physical Chemistry
Volume85
Issue number21
DOIs
StatePublished - Jan 1 1981

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