Exploring the OH-initiated reactions of styrene in the atmosphere and the role of van der Waals complex

Abstract

Reacting with OH provides a major sink for styrene in the atmosphere, with three possible pathways including OH-addition, H-abstraction and addition-dissociation reactions. However, the total rate coefficients of styrene + OH were measured as 1.2–6.2 × 10−11 cm3 molecule−1 s−1 under atmospheric conditions, varying by a maximum factor of 5. On the other hand, only one theoretical work reported this rate coefficient as 19.1 × 10−11 cm3 molecule−1 s−1, which exhibits up to 16 times that measured in laboratory studies. In the present study, the reaction kinetics of styrene + OH was extensively studied with high-level quantum chemical methods combined with RRKM/master equation simulations. In particular, we carried out theoretical treatments for the formation of pre-reaction Van der Waals complexes of styrene + OH, and examined their influence on the reaction kinetics. The total rate coefficient for styrene + OH is calculated to be 1.7 × 10−11 cm3 molecule−1 s−1 at 300 K, 1 atm. The main products are addβ (88.2%), add5 (6.9%), addα (1.9%) and add3 (1.7%). Using our computed rate coefficient and the global atmospheric hydroxyl radical concentration (2 × 106 radicals per cm3), the lifetime of styrene in the atmosphere is estimated at 8.0 h. The degradation of styrene might be negligible for the formation of ozone in the atmosphere based upon the photochemical ozone creation potentials calculation. The computed product yields indicate that addβ via subsequent reactions could significantly produce formaldehyde and benzaldehyde that were observed in previous experimental studies on styrene oxidation, and contribute to the formation of secondary organic aerosols.