title: Computational study of the reaction between biogenic stabilized Criegee intermediates and sulfuric acid.
abstract: We have postulated a mechanism for the reaction of sulfuric acid with stabilized Criegee intermediates (sCIs). We have computed Gibbs free energies for the reaction of sulfuric acid with two biogenic sCIs and three smaller model species. We have also calculated Gibbs free energies for two competing sink reactions. Due to the large size of the biogenic sCIs, the computations have been performed at the relatively modest B3LYP/6-31G(d,p) and B3LYP/6-311+G(2d,p) levels. However, single-point RI-CC2/def2-QZVPP calculations for the (CH3)(2)COO model species are in good agreement with the B3LYP results. The reaction is found to be strongly exothermic for all studied species. Activation barrier calculations on the (CH3)(2)COO model species further indicate that the reaction with sulfuric acid may proceed significantly faster than the sink reaction with water. If the same applies to the biogenic sCIs, the proposed reactions could account for some part of the organically assisted new particle formation events observed in the atmosphere.
authors.affiliation: Department of Physical Sciences, University of Helsinki, P. O. Box 64, FIN-00014 Helsinki, Finland. theo.kurten@helsinki.fi
authors.forename: Theo
authors.initials: T
authors.lastname: Kurtén
authors.forename: Boris
authors.initials: B
authors.lastname: Bonn
authors.forename: Hanna
authors.initials: H
authors.lastname: Vehkamäki
authors.forename: Markku
authors.initials: M
authors.lastname: Kulmala
mesh_terms: D003198:Computer Simulation; D004583:Electrons; D006571:Heterocyclic Compounds / Q000737:chemistry; D008958:Models, Molecular; D015394:Molecular Structure; D010713:Phosphatidylcholines; D013464:Sulfuric Acids / Q000737:chemistry*; D013696:Temperature
chemical_list: C503429:1,2,4-trioxane; D006571:Heterocyclic Compounds; D010713:Phosphatidylcholines; D013464:Sulfuric Acids; C033158:sulfuric acid