Ab initio group contribution method for activation energies of hydrogen abstraction reactions.
The group contribution method for activation energies is applied to hydrogen abstraction reactions. To this end an ab initio database was constructed, which consisted of activation energies calculated with the ab initio CBS-QB3 method for a limited set of well-chosen homologous reactions. CBS-QB3 is shown to predict reaction rate coefficients within a factor of 2-4 and Arrhenius activation energies within 3-5 kJ mol(-1) of experimental data. Activation energies in the set of homologous reactions vary over 156 kJ mol(-1) with the structure of the abstracting radical and over 94 kJ mol(-1) with the structure of the abstracted hydrocarbon. The parameters required for the group contribution method, the so-called standard activation group additivity values, were determined from this database. To test the accuracy of the group contribution method, a large set of 88 additional activation energies were calculated from first principles and compared with the predictions from the group contribution method. It was found that the group contribution method yields accurate activation energies for hydrogen-transfer reactions between hydrogen molecules, alkylic hydrocarbons, and vinylic hydrocarbons, with the largest deviations being less than 6 kJ mol(-1). For reactions between allylic and propargylic hydrocarbons, the transition state is believed to be stabilized by resonance effects, thus requiring the introduction of an appropriate correction term to obtain a reliable prediction of the activation energy for this subclass of hydrogen abstraction reactions.
Saeys
Mark
M
Laboratorium voor Petrochemische Techniek, Ghent University, Krijgslaan 281(S5), 9000 Gent, Belgium.
Reyniers
Marie-Françoise
MF
Van Speybroeck
Veronique
V
Waroquier
Michel
M
Marin
Guy B
GB