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@article{5576e32d965a400db3d1013528c0d027,
title = "Structures and reaction rates of the gaseous oxidation of SO2 by an O− 3 (H2O)0–5 cluster – a density functional theory investigation",
publisher = "Copernicus GmbH",
author = "Bork, {Nicolai Christian} and T. Kurten and Enghoff, {Martin Andreas Bødker} and Pedersen, {Jens Olaf Pepke} and Mikkelsen, {K. V.} and Henrik Svensmark",
year = "2011",
doi = "10.5194/acpd-11-29647-2011",
number = "11",
pages = "29647--29679",
journal = "Atmospheric Chemistry and Physics Discussions",
issn = "1680-7367",

}

RIS

TY - JOUR

T1 - Structures and reaction rates of the gaseous oxidation of SO2 by an O− 3 (H2O)0–5 cluster – a density functional theory investigation

A1 - Bork,Nicolai Christian

A1 - Kurten,T.

A1 - Enghoff,Martin Andreas Bødker

A1 - Pedersen,Jens Olaf Pepke

A1 - Mikkelsen,K. V.

A1 - Svensmark,Henrik

AU - Bork,Nicolai Christian

AU - Kurten,T.

AU - Enghoff,Martin Andreas Bødker

AU - Pedersen,Jens Olaf Pepke

AU - Mikkelsen,K. V.

AU - Svensmark,Henrik

PB - Copernicus GmbH

PY - 2011

Y1 - 2011

N2 - 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.

AB - 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.

U2 - 10.5194/acpd-11-29647-2011

DO - 10.5194/acpd-11-29647-2011

JO - Atmospheric Chemistry and Physics Discussions

JF - Atmospheric Chemistry and Physics Discussions

SN - 1680-7367

IS - 11

SP - 29647

EP - 29679

ER -