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 language | English |
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Pages (from-to) | 13089-13094 |
Journal | Journal of the American Chemical Society |
Volume | 126 |
Issue number | 40 |
DOIs | |
Publication status | Published - 13 Oct 2004 |