title: The reaction of Criegee intermediates with NO, RO2, and SO2, and their fate in the atmosphere.
abstract: The reaction of Criegee intermediates (CI) with NO and RO(2) radicals is studied for the first time by theoretical methodologies; additionally, the reaction of CI with SO(2) molecules is re-examined. The reaction of CI with NO was found to be slow, with a distinct energy barrier. Their reaction with RO(2) radicals proceeds by the formation of a pre-reactive complex followed by addition of the RO(2) radical on the CI carbon over a submerged barrier, leading to a larger peroxy radical and opening the possibility for oligomer formation in agreement with experiment. The impact of singlet biradicals on the reaction of CI with SO(2) is examined, finding a different reaction mechanism compared to earlier work. For larger CI, the reaction with SO(2) at atmospheric pressures mainly yields thermalized sulfur-bearing secondary ozonides. The fate of the CI in the atmosphere is examined in detail, based on observed concentration of a multitude of coreactants in the atmosphere, and estimated rate coefficients available from literature data. The impact of SCI on tropospheric chemistry is discussed.
authors.affiliation: Max Planck Institute for Chemistry, Mainz, Germany. Luc.Vereecken@mpic.de
authors.forename: L
authors.initials: L
authors.lastname: Vereecken
authors.forename: H
authors.initials: H
authors.lastname: Harder
authors.forename: A
authors.initials: A
authors.lastname: Novelli
mesh_terms: D001272:Atmosphere / Q000737:chemistry*; D009569:Nitric Oxide / Q000737:chemistry*; D009930:Organic Chemicals / Q000737:chemistry*; D013458:Sulfur Dioxide / Q000737:chemistry*
chemical_list: D009930:Organic Chemicals; D013458:Sulfur Dioxide; D009569:Nitric Oxide