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Publication Abstract: Dinitrogen pentoxide (N2O5) is an extremely important species in the chemistry of the atmosphere. Reactions of N2O5 greatly affect, either directly or indirectly, the concentrations of NO3, ozone, OH radicals, methane, and more. Of great importance are the heterogeneous reactions with Cl– and other anions, but a microscopic understanding of these reactions is not yet at hand. In this work, we employ ab initio molecular dynamics (AIMD) and other tools of computational chemistry to explore reactions of N2O5 with anions hydrated by 12 water molecules, in order to shed light on this important class of reactions. The ions investigated are Cl–, SO42–, ClO4–, and RCOO– (R = H, CH3, C2H5). The following main results are obtained: (i) all the reactions take place with an SN2 type mechanism, with a transition state that involves a contact ion pair (NO2+NO3–) that interacts strongly with water molecules. (ii) Reactions of a solvent separated nitronium ion (NO2+) are not observed in any of the cases. (iii) Recent experiments reported the suppression of ClNO2 formation from N2O5 reacting with salty water when sulfate or acetate ions are present. The results of the simulations provide an explanation for these findings in terms of competing reactions. (iv) Formation of novel intermediate species, such as (SO4NO2–) and RCOONO2, in these reactions is predicted. Finally, results suggest atomistic-level mechanisms for the reactions studied here provide interpretations for experimental findings and may be useful for the development of improved modeling of reaction kinetics in aerosol particles. This work used the Extreme Science and Engineering Discovery Environment (XSEDE) which is supported by grant number TGCHE17006. Research Data Curation Program, UC San Diego, La Jolla, 92093-0175 (https://lib.ucsd.edu/rdcp) Karimova, Natalia V.; Chen, James; Gord, Joseph R.; Staudt, Sean; Bertram, Timothy H.; Nathanson, Gilbert M.; Gerber, R. Benny (2020). Data from: SN2 Reactions of N2O5 with Ions in Water: Microscopic Mechanisms, Intermediates, and Products. In Center for Aerosol Impacts on Chemistry of the Environment (CAICE). UC San Diego Library Digital Collections. https://doi.org/10.6075/J0RN367K
Type
dataset
Identifier
ark:/20775/bb2360347m
Language
English
Subject
Water clusters Dinitrogen pentoxide Atmospheric chemistry Reactions mechanisms Heterogeneous reactions
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