Variational transition state theory as a tool to determine kinetic selectivity in reactions involving a valley-ridge inflection point

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Abstract

Variational transition state theory has been used to calculate the kinetic isotope effects affecting product ratios in the reaction between 1O2 and d6-tetramethylethylene. The minimum energy path on the potential energy surface for this process reaches a valley-ridge inflection point and then bifurcates leading to the two final products. Using canonical Variational transition state theory, two distinct dynamical bottlenecks were located corresponding to the H- and the D-abstraction, respectively. The calculated KIE at 263 K turns out to be 1.126. Analogously, a H/T KIE of 1.17 at the same temperature has been found for the reaction of 1O2 with the tritiated derivative of tetramethylethylene.
Original languageEnglish
Pages (from-to)13089-13094
JournalJournal of the American Chemical Society
Volume126
Issue number40
DOIs
Publication statusPublished - 13 Oct 2004

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