New Mechanistic Insight into the Reaction of Organic Acids with SO3 at the Air‐Water Interface

: The gas-phase reaction of organic acids with SO3 has been recognized as essential in promoting aerosol-particle formation. However, at the air-water interface, this reaction is much less understood. We performed systematic Born-Oppenheimer molecular dynamics (BOMD) simulations to study the reaction of various organic acids with SO3 on a water droplet. The results show that with the involvement of interfacial water molecules, organic acids can react with SO3 and form the ion pair of sulfuric-carboxylic anhydride and hydronium. This mechanism is in contrast to the gas-phase reaction mechanisms in which the organic acid either serves as a catalyst for the reaction between SO3 and H2 O or reacts with SO3 directly. The distinct reaction at the water surface has important atmospheric implications, for example, promoting water condensation, uptaking atmospheric condesation species, and incorporating "SO42- " into organic species in aerosol particles. Therefore, this reaction, typically occurring within a few picoseconds, provides another pathway towards aerosol formation.