Theoretical kinetics of hydrogen abstraction and hydroperoxyl addition reactions of 3-hexene by hydroperoxyl radicals

The reaction kinetics of alkenes + hydroperoxyl (H<(O) over dot>(2)) system is of importance to low/intermediate temperature chemistry of alkanes. This work is a follow up of our previous study on 3-hexene + <(O) over dot>H [1],. The rate coefficients were determined using the canonical variational transition-state theory. Results revealed that the asymmetric geometry of the H<(O) over dot>(2) radical generated numerous reaction sub-channels. The rate coefficients, with a conservative uncertainty (factor of 5), were obtained to develop the detailed chemical mechanism of 3-hexene. Additionally, potential energy surface, minimum reaction path, adiabatic ground-state energy, and activation free Gibbs energy change (Delta G) calculations were also performed.