TY - JOUR
T1 - A computational study of the oxidation of SO2 to SO3 by gas -phase organic oxidants
AU - Kurten, T.
AU - Lane, J. R.
AU - Jørgensen, Solvejg
AU - Kjærgaard, Henrik Grum
PY - 2011/8/11
Y1 - 2011/8/11
N2 - We have studied the oxidation of SO2 to SO3 by four peroxyradicals and two carbonyl oxides (Criegee intermediates) using both density functional theory, B3LYP, and explicitly correlated coupled cluster theory, CCSD(T)-F12. All the studied peroxyradicals react very slowly with SO2 due to energy barriers (activation energies) of around 10 kcal/mol or more. We find that water molecules are not able to catalyze these reactions. The reaction of stabilized Criegee intermediates with SO2 is predicted to be fast, as the transition states for these oxidation reactions are below the free reactants in energy. The atmospheric relevance of these reactions depends on the lifetimes of the Criegee intermediates, which, at present, is highly uncertain.
AB - We have studied the oxidation of SO2 to SO3 by four peroxyradicals and two carbonyl oxides (Criegee intermediates) using both density functional theory, B3LYP, and explicitly correlated coupled cluster theory, CCSD(T)-F12. All the studied peroxyradicals react very slowly with SO2 due to energy barriers (activation energies) of around 10 kcal/mol or more. We find that water molecules are not able to catalyze these reactions. The reaction of stabilized Criegee intermediates with SO2 is predicted to be fast, as the transition states for these oxidation reactions are below the free reactants in energy. The atmospheric relevance of these reactions depends on the lifetimes of the Criegee intermediates, which, at present, is highly uncertain.
M3 - Journal article
SN - 1089-5639
VL - 115
SP - 8669
EP - 8681
JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
ER -