Insight into Chemistry on Cloud/Aerosol Water Surfaces.

Cloud/aerosol water surfaces exert significant influence over atmospheric chemical processes. Atmospheric processes at the water surface are observed to follow mechanisms that are quite different from those in the gas phase. This Account summarizes our recent findings of new reaction pathways on the water surface. We have studied these surface reactions using Born-Oppenheimer molecular dynamics simulations. These studies provide useful information on the reaction time scale, the underlying mechanism of surface reactions, and the dynamic behavior of the product formed on the aqueous surface. According to these studies, the aerosol water surfaces confine the atmospheric species into a specific orientation depending on the hydrophilicity of atmospheric species or the hydrogen-bonding interactions between atmospheric species and interfacial water. As a result, atmospheric species are activated toward a particular reaction on the aerosol water surface. For example, the simplest Criegee intermediate (CHOO) exhibits high reactivity toward the interfacial water and hydrogen sulfide, with the reaction times being a few picoseconds, 2-3 orders of magnitude faster than that in the gas phase. The presence of interfacial water molecules induces proton-transfer-based stepwise pathways for these reactions, which are not possible in the gas phase. The strong hydrophobicity of methyl substituents in larger Criegee intermediates (>C1), such as CHCHOO and (CH)COO, blocks the formation of the necessary prereaction complexes for the Criegee-water reaction to occur at the water droplet surface, which lowers their proton-transfer ability and hampers the reaction. The aerosol water surface provides a solvent medium for acids (e.g., HNO and HCOOH) to participate in reactions via mechanisms that are different from those in the gas and bulk aqueous phases. For example, the anti-CHCHOO-HNO reaction in the gas phase follows a direct reaction between anti-CHCHOO and HNO, whereas on a water surface, the HNO-mediated stepwise hydration of anti-CHCHOO is dominantly observed. The high surface/volume ratio of interfacial water molecules at the aerosol water surface can significantly lower the energy barriers for the proton transfer reactions in the atmosphere. Such catalysis by the aerosol water surface is shown to cause the barrier-less formation of ammonium bisulfate from hydrated NH and SO molecules rather than from the reaction of HSO with NH. Finally, an aerosol water droplet is a polar solvent, which would favorably interact with high polarity substrates. This can accelerate interconversion of different conformers (e.g., anti and syn) of atmospheric species, such as glyoxal, depending on their polarity. The results discussed here enable an improved understanding of atmospheric processes on the aerosol water surface.