Dinitrogen pentoxide (N2O5) is an important species in the atmospheric chemistry. This reactive intermediate play a significant role is the destruction of ozone, halogen activation and nitrate loadings. Nevertheless, many aspects such as the microscopic mechanisms of the heterogeneous reactions between N2O5 and ions presented in seawater are still unknown. Additionally, it should be noted, that recent experiments find interest effects of sulfate ions on the production of nitryl chloride (ClNO2) in such systems. The presence of sulfate ion reduces the yield of nitryl chloride. In this study, to gain insight at the microscopic level of this and related effects, simulations are carries out of the reaction pathways and the dynamics of the processes in sulfates. Performed Reactions of N2O5 with ions at the surface of seawater aerosols play an important role in the chemistry of the atmosphere. However, little is known yet on the microscopic mechanisms of there processes. To gain insights into these reactions, simulations are carried out for the reactions of N2O5 with Cl –, SO42–, and ClO4– hydrated by 12 water molecules. The results unravel the mechanisms of the reactions, predict products and intermediates of potential atmospheric importance and provide interpretations for resent interesting experimental findings.Obtained theoretical results are in a good agreement with experimental data. It was showed that the reactions of N2O5 with chloride and sulfate ions both have an SN2-type substitution reaction mechanism. Also, simulations showed that reaction of N2O5 with (SO42–) is fast and has a smaller barrier than reaction with (Cl–). Additionally, formation of the novel intermediate species (SO4NO2–) was theoretically predicted during the reaction of sulfate ion with N2O5. The results, obtained in this work, unravel the mechanisms of the reactions, predict products and intermediates of potential atmospheric importance and provide interpretations for resent interesting experimental findings.

Reactions of N2O5 with ions in water: Computational studies of mechanisms and dynamics for Cl –, SO42–, and ClO4–

2019 Fall National Meeting

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