Theoretical studies of OH radical reactions

There is still considerable uncertainty associated with the detailed chemical mechanism of the reactions of OH radicals with alkenes such as isoprene (2-methyl-1,3-butadiene) and oxygenated compounds such as hydroxyacetone, and the subtle interactions that control the reactivity of these systems.  Recent studies have suggested that the mechanisms for these reactions may proceed through pre-reactive stable intermediates.

We are using ab initio electronic structure and state-of-the-art ab initio dynamics calculations to determine the potential energy surface for these reactions, including the structures and energetics of the transition states leading to each product.  These results are used in conjunction with reaction rate theories and compared to experimental measurements to help elucidate the oxidation mechanism for these compounds in the atmosphere, and to give fundamental information on the factors controlling the kinetics of radical-molecule reactivity.