title: Nitrate radical addition-elimination reactions of atmospherically relevant sulfur-containing molecules.
abstract: 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 NO(3) with four sulfur-containing species relevant to atmospheric chemistry: hydrogen sulfide (H(2)S), dimethyl sulfide [(CH(3))(2)S], dimethyl sulfoxide [(CH(3))(2)SO] and sulfur dioxide (SO(2)). We find that the reaction with (CH(3))(2)SO to give NO(2) + (CH(3))(2)SO(2) has a very low barrier, and is likely to be the dominant oxidation mechanism for (CH(3))(2)SO in the atmosphere. In agreement with previous experimental data and computational results, we find that the reaction with H(2)S and SO(2) is very slow, and the reaction with (CH(3))(2)S 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.
authors.affiliation: Department of Chemistry, University of Copenhagen, Universitetsparken 5, 2100 København, ∅, Denmark. theo.kurten@helsinki.fi
authors.forename: Theo
authors.initials: T
authors.lastname: Kurtén
authors.forename: Joseph R
authors.initials: JR
authors.lastname: Lane
authors.forename: Solvejg
authors.initials: S
authors.lastname: Jørgensen
authors.forename: Henrik G
authors.initials: HG
authors.lastname: Kjaergaard
mesh_terms: D000393:Air Pollutants / Q000737:chemistry; D001272:Atmosphere / Q000737:chemistry*; D003198:Computer Simulation; D004121:Dimethyl Sulfoxide / Q000737:chemistry; D006862:Hydrogen Sulfide / Q000737:chemistry; D008956:Models, Chemical; D009566:Nitrates / Q000737:chemistry*; D013440:Sulfides / Q000737:chemistry; D013457:Sulfur Compounds / Q000737:chemistry*; D013458:Sulfur Dioxide / Q000737:chemistry
chemical_list: D000393:Air Pollutants; D009566:Nitrates; D013440:Sulfides; D013457:Sulfur Compounds; D013458:Sulfur Dioxide; C004784:dimethyl sulfide; D004121:Dimethyl Sulfoxide; D006862:Hydrogen Sulfide