A computational investigation on the HO2 and isopropyl peroxy radical reaction: Mechanism and kinetics

Abstract

Reaction mechanism and kinetics of the reaction of HO2 and i-C3H7O2 radicals were investigated at CCSD(T)/aug-cc-pVDZ//B3LYP/6-311G(d,p) level of theory. The reaction pathways on both singlet and triplet potential energy surfaces have been explored. The triplet hydrogen abstraction is found to be highly favored over the singlet hydrogen abstraction and addition-elimination pathways, and the latters can be negligible in atmospheric conditions. The multiconformer transition state theory was employed to obtain the rate coefficients. The calculated rate coefficients over the studied temperature were used to fit the data, and the Arrhenius expression was obtained to be k= 1.65×10-15T3002.31exp2265T cm3 molecule−1 s−1.