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Abstract Methanesulfinic acid (MSIA), an organic sulfur compound, is mainly produced in the oxidation process of dimethyl sulfide in the atmosphere. The properties of MSIA at the air-water interface were studied using molecular dynamics (MD) simulations. The result shows that the lowest system free energy is located at the interface. Because the free energy difference between the interface and water phase is 3.2 kJ mol−1, the MSIA molecule can easily get out of the free energy well and travel to water phase by the thermal motion, leading to only a 21% probability of its occurrence at the interface. The MSIA molecule tends to tilt at the interface with the sulfino group (-S(O)-OH) pointing toward the water phase. The feature of hydration status at the air-water interface may be favorable to the heterogeneous oxidation of MSIA. Graphical abstract Unlabelled Image Highlights • The properties of MSIA at the air-water interface are studied using MD simulations. • The lowest free energy is located at the air-water interface. • Probability of MSIA at the interface is about 21%. • The tilted orientation at the interface is predominant. • The feature of hydration status at the interface is found. [ABSTRACT FROM AUTHOR]

In recent years, Criegee chemistry has become an important research focus due to its relevance in regulating concentrations of tropospheric OH radicals, hydroperoxides, sulfates, nitrates, and aerosols. However, to date, its interface behavior remains poorly understood. Thus, in this study, we used the Born-Oppenheimer molecular dynamics (BOMD) simulation method to explore the reaction mechanisms between Criegee intermediates (CIs) and methylsulfonic acid (MSA) at the air-water interface, then compared the observed behaviors with those in the gas phase. The addition of Criegee intermediates to MSA is nearly a barrierless reaction and follows a loop-structure mechanism in the gas phase. The high rate constants indicate that the Criegee intermediates and MSA reactions are the main acid removal channels. At the water's surface, the interaction of Criegee intermediates with MSA includes three main channels: 1) direct addition reaction, 2) H 2 O-mediated hydroperoxide formation, and 3) MSA-mediated Criegee hydration. These reaction channels follow a loop-structure or a stepwise mechanism and proceed at the picosecond time-scale. The results of this work broaden our understanding of Criegee atmospheric behaviors in polluted urban and marine areas, which in turn will aid in developing more effective pollution control measures. Unlabelled Image • The ab initio dynamics simulation was adopted to simulate the reactions at the air-water interface. • The reaction of MSA with CH 3 CHOO plays an active role in the MSA removal channel. • At the water's surface, the reaction channels follow a loop-structure or a stepwise mechanism. • MSA also acts as a trigger to promote Criegee hydration at the air-water interface. [ABSTRACT FROM AUTHOR]