OH-initiated tropospheric photooxidation of allyl acetate: a theoretical study

Abstract

The mechanisms of OH-initiated oxidation of allyl acetate in the presence of O2/NO have been investigated by performing density functional theory calculations. Two patterns (OH-addition and H-abstraction) of the initial reaction and the subsequent reactions of the primarily produced intermediates (IM1, IM2, and IM4) have been proposed. The OH-addition reactions are more favorable than the H-abstraction reactions, but H-abstraction from the CH2 group cannot be ignored. The major degradation products have been identified. The rate coefficients and the branching ratios of the primary reactions are obtained over the temperature of 200–500 K and the pressure range of 0.001–1000 atm. The total rate coefficient is 3.17 × 10−11 cm3 molecule−1 s−1 at 298 K and 1 atm. With respect to the typical concentration of OH radical (2.0 × 106 molecule cm−3), the atmospheric lifetime of AAC is estimated to be 4.40 h.