Atmospheric Fate of the CH3SOO Radical from the CH3S + O-2 Equilibrium

The atmospheric oxidation mechanisms of reduced sulfur compounds are of great importance in the biogeochemical sulfur cycle. The CH3S radical represents an important intermediate in these oxidation processes. Under atmospheric conditions, CH3S will predominantly react with O-2 to form the peroxy radical CH3SOO. The formed CH3SOO has two competing unimolecular reaction pathways: isomerization to CH3SO2, which further decomposes into CH3 and SO2, or a hydrogen shift followed by HO2 loss, leading to CH2S. Previous theoretical calculations have suggested that CH2S formation should be the dominant pathway, in disagreement with existing experimental results. Our large active space multireference configuration interaction calculations agree with the experimental results that the formation of CH3 and SO2 is the dominant route and the formation of CH2S and HO2 can, at most, be a minor pathway. We support the calculations with new experiments starting from the OH + CH3SH reaction for CH3S formation under low NOx conditions and find a SO2 yield of 0.86 +/- 0.18 within our reaction time of 7.9 s. Model simulations of our experiments show that the SO2 yield converges to 0.98. This combined theoretical and experimental study thus furthers the understanding of the general oxidation mechanisms of sulfur compounds in the atmosphere.