Theoretical Study on the Kinetic and Mechanism of H+HO2 Reaction

Abstract

Abstract The kinetics and mechanism of reaction of a hydroperoxyl radical (HO2) with a hydrogen atom on both singlet and triplet surfaces were studied by employing DFT, CCSD, and G3 methods along with the Aug-cc-pVTZ basis set. MC-SCF and CCD methods were used to explore potential energy surfaces. Major end products from different channels were H2O+O, H2+O2, and OH. Formation of chemically activated hydrogen peroxide HOOH was the most exothermic path in this system that dissociates to the ground state OH(2Π) radicals. Another energized transient species was water oxide H2OO, which has local minimum on the singlet potential-energy surface. The energized water oxide rapidly isomerized to hydrogen peroxide HOOH or dissociated to H2O + O(1D). Transition state theory and RRKM theory were used to calculate the rate constants for different channels.