Ionic Route to Atmospheric Relevant HO 2 and Protonated Formaldehyde from Methanol Cation and O 2 .

Gas-phase ion chemistry influences atmospheric processes, particularly in the formation of cloud condensation nuclei by producing ionic and neutral species in the upper troposphere-stratosphere region impacted by cosmic rays. This work investigates an exothermic ionic route to the formation of hydroperoxyl radical (HO 2 ) and protonated formaldehyde from methanol radical cation and molecular oxygen. Methanol, a key atmospheric component, contributes to global emissions and participates in various chemical reactions affecting atmospheric composition. The two reactant species are of fundamental interest due to their role in atmospheric photochemical reactions, and HO 2 is also notable for its production during lightning events. Our experimental investigations using synchrotron radiation reveal a fast hydrogen transfer from the methyl group of methanol to oxygen, leading to the formation of CH 2 OH + and HO 2 . Computational analysis corroborates the experimental findings, elucidating the reaction dynamics and hydrogen transfer pathway. The rate coefficients are obtained from experimental data and shows that this reaction is fast and governed by capture theory. Our study contributes to a deeper understanding of atmospheric processes and highlights the role of ion-driven reactions in atmospheric chemistry.