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| Titel |
Structures and reaction rates of the gaseous oxidation of SO2 by an O3−(H2O)0-5 cluster – a density functional theory investigation |
| VerfasserIn |
N. Bork, T. Kurtén, M. B. Enghoff, J. O. P. Pedersen, K. V. Mikkelsen, H. Svensmark |
| Medientyp |
Artikel
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| Sprache |
Englisch
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| ISSN |
1680-7316
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| Digitales Dokument |
URL |
| Erschienen |
In: Atmospheric Chemistry and Physics ; 12, no. 8 ; Nr. 12, no. 8 (2012-04-19), S.3639-3652 |
| Datensatznummer |
250011066
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| Publikation (Nr.) |
 copernicus.org/acp-12-3639-2012.pdf |
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| Zusammenfassung |
| Based on density functional theory calculations we present
a study of the gaseous oxidation of SO2 to SO3
by an anionic O3−(H2O)n 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 characterised by strong networks
of hydrogen bonds, very similar to the reactant complexes. The
other class is characterised by sparser structures of hydration water
and is stabilised by high entropy. At temperatures relevant
for atmospheric chemistry, the most energetically favourable
class of transition states vary with the number of water
molecules attached. A kinetic model is utilised, taking into
account the most likely outcomes of the initial
SO2 O3−(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 rationalised 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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