Nitrate radical addition-elimination reactions of atmospherically relevant sulfur-containing molecules

TY - JOUR

T1 - Nitrate radical addition-elimination reactions of atmospherically relevant sulfur-containing molecules

AU - Kurten, Theo

AU - Lane, Joseph R.

AU - Jørgensen, Solvejg

AU - Kjærgaard, Henrik Grum

PY - 2010/10/21

Y1 - 2010/10/21

N2 - We have used different computational methods, including B3LYP, CCSD(T)-F12 and CBS-QB3, to study and compare the addition-elimination reaction of the nitrate radical NO3 with four sulfur-containing species relevant to atmospheric chemistry: hydrogen sulfide (H2S), dimethyl sulfide [(CH3)2S], dimethyl sulfoxide [(CH3) 2SO] and sulfur dioxide (SO2). We find that the reaction with (CH3)2SO to give NO2 + (CH 3)2SO2 has a very low barrier, and is likely to be the dominant oxidation mechanism for (CH3)2SO in the atmosphere. In agreement with previous experimental data and computational results, we find that the reaction with H2S and SO2 is very slow, and the reaction with (CH3)2S is not competitive with the hydrogen abstraction route. The differences in reaction energetics and rates between the four species are explained in terms of stabilizing interactions in the transition states and differences in sulfur-oxygen bond strengths.

AB - We have used different computational methods, including B3LYP, CCSD(T)-F12 and CBS-QB3, to study and compare the addition-elimination reaction of the nitrate radical NO3 with four sulfur-containing species relevant to atmospheric chemistry: hydrogen sulfide (H2S), dimethyl sulfide [(CH3)2S], dimethyl sulfoxide [(CH3) 2SO] and sulfur dioxide (SO2). We find that the reaction with (CH3)2SO to give NO2 + (CH 3)2SO2 has a very low barrier, and is likely to be the dominant oxidation mechanism for (CH3)2SO in the atmosphere. In agreement with previous experimental data and computational results, we find that the reaction with H2S and SO2 is very slow, and the reaction with (CH3)2S is not competitive with the hydrogen abstraction route. The differences in reaction energetics and rates between the four species are explained in terms of stabilizing interactions in the transition states and differences in sulfur-oxygen bond strengths.

M3 - Journal article

SN - 1463-9076

VL - 12

SP - 12833

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

ER -