A potential source of atmospheric sulfate from O2ĝ'-induced SO2 oxidation by ozone

Abstract

It was formerly demonstrated that O2SOO forms at collisions rate in the gas phase as a result of SO2 reaction with O2 . Here, we present a theoretical investigation of the chemical fate of O2SOO by reaction with O3 in the gas phase, based on ab initio calculations. Two main mechanisms were found for the title reaction, with fundamentally different products: (i) formation of a van der Waals complex followed by electron transfer and further decomposition to O2 CSO2 CO3 and (ii) formation of a molecular complex from O2 switching by O3, followed by SO2 oxidation to SO3 within the complex. Both reactions are exergonic, but separated by relatively low energy barriers. The products in the former mechanism would likely initiate other SO2 oxidations as shown in previous studies, whereas the latter mechanism closes a path wherein SO2 is oxidized to SO3 . The latter reaction is atmospherically relevant since it forms the SO3 ion, hereby closing the SO2 oxidation path initiated by O2 . The main atmospheric fate of SO3 is nothing but sulfate formation. Exploration of the reactions kinetics indicates that the path of reaction (ii) is highly facilitated by humidity. For this path, we found an overall rate constant of 4:01011 cm3 molecule1 s1 at 298K and 50% relative humidity. The title reaction provides a new mechanism for sulfate formation from ion-induced SO2 oxidation in the gas phase and highlights the importance of including such a mechanism in modeling sulfate-based aerosol formation rates.