Atmos. Chem. Phys. Discuss., 11, 13947-13973, 2011
www.atmos-chem-phys-discuss.net/11/13947/2011/
doi:10.5194/acpd-11-13947-2011
© Author(s) 2011. This work is distributed
under the Creative Commons Attribution 3.0 License.
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Ab initio studies of O2(H2O)n and O3(H2O)n anionic molecular clusters, n≤12
N. Bork1, T. Kurtén2,3, M. B. Enghoff1, J. O. P. Pedersen1, K. V. Mikkelsen2, and H. Svensmark1
1National Space Institute, Technical University of Denmark, Juliane Maries Vej 30, 2100 Copenhagen Ø, Denmark
2Department of Chemistry, H.C. Ørsted Institute, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen Ø, Denmark
3Division of Atmospheric Sciences and Geophysics, Dept. of Physics, P.O. Box 64, 00014 University of Helsinki, Finland

Abstract. An ab initio study of gaseous clusters of O2 and O2 with water is presented. Based on thorough scans of configurational space, we determine the thermodynamics of cluster growth. The results are in good agreement with benchmark computational methods and existing experimental data. We find that anionic O2(H2O)n and O3(H2O)n clusters are thermally stabilized at typical atmospheric conditions for at least n = 5. The first 4 water molecules are strongly bound to the anion due to delocalization of the excess charge while stabilization of more than 4 H2O is due to normal hydrogen bonding. Although clustering up to 12 H2O, we find that the O2 and O3 anions retain at least ca. 80 % of the charge and are located at the surface of the cluster. The O2 and O3 speicies are thus accessible for further reactions. Finally, the thermodynamics of a few relevant cluster reactions are considered.

Citation: Bork, N., Kurtén, T., Enghoff, M. B., Pedersen, J. O. P., Mikkelsen, K. V., and Svensmark, H.: Ab initio studies of O2(H2O)n and O3(H2O)n anionic molecular clusters, n≤12, Atmos. Chem. Phys. Discuss., 11, 13947-13973, doi:10.5194/acpd-11-13947-2011, 2011.
 
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