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

摘要

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 dotH [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.