References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-11-29647-2011

Structures and reaction rates of the gaseous oxidation of SO2 by an O3−(H2O)0–5 cluster – a density functional theory investigation

Bork

¹ ² Kurtén

² ³ Enghoff

M. B.

¹ Pedersen

J. O. P.

¹ Mikkelsen

K. V.

³ Svensmark

National Space Institute, Technical University of Denmark, Juliane Maries Vej 30, 2100 Copenhagen Ø, Denmark

Division of Atmospheric Sciences and Geophysics, Department of Physics, P.O. Box 64, 00014 University of Helsinki, Finland

Department of Chemistry, H.C. Ørsted Institute, University of Copenhagen, Universitetsparken 5, 2100 Copenhagen Ø, Denmark

03 11 2011

11 11 29647 29679

This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

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Based on density functional theory calculations we present a study of the gaseous oxidation of SO2 to SO3 by an anionic O3−(H2On cluster, n=0–5. The configurations of the most relevant reactants, transition states, and products are discussed and compared to previous findings. Two different classes of transition states have been identified. One class is characterized by strong networks of hydrogen bonds, very similar to the reactant complexes. The other class is characterized by loose structures of hydration water and is stabilized by high entropy. At temperatures relevant for atmospheric chemistry, the most energetically favorable class of transition states vary with the number of water molecules attached. A kinetic model is utilized, taking into account the most likely outcomes of the initial SO2O3−(H2O)n collision complexes. This model shows that the reaction takes place at collision rates regardless of the number of water molecules involved. A lifetime analysis of the collision complexes supports this conclusion. Hereafter, the thermodynamics of water and O2 condensation and evaporation from the product SO3−O2(H2O)n cluster is considered and the final products are predicted to be O2SO3− and O2SO3−(H2O)1. The low degree of hydration is rationalized through a charge analysis of the relevant complexes. Finally, the thermodynamics of a few relevant reactions of the O2SO3− and O2SO3−(H2O)1 complexes are considered.

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