Thermalized Epoxide Formation in the Atmosphere

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dc.contributor.author Moller, Kristian H.
dc.contributor.author Kurten, Theo
dc.contributor.author Bates, Kelvin H.
dc.contributor.author Thornton, Joel A.
dc.contributor.author Kjaergaard, Henrik G.
dc.date.accessioned 2020-11-30T11:39:01Z
dc.date.available 2020-11-30T11:39:01Z
dc.date.issued 2019-12-12
dc.identifier.citation Moller , K H , Kurten , T , Bates , K H , Thornton , J A & Kjaergaard , H G 2019 , ' Thermalized Epoxide Formation in the Atmosphere ' , Journal of Physical Chemistry A , vol. 123 , no. 49 , pp. 10620-10630 . https://doi.org/10.1021/acs.jpca.9b09364
dc.identifier.other PURE: 129679140
dc.identifier.other PURE UUID: 6755191a-c157-4005-b458-d59f7f4dedc5
dc.identifier.other WOS: 000503114800018
dc.identifier.other ORCID: /0000-0002-6416-4931/work/67134485
dc.identifier.uri http://hdl.handle.net/10138/322132
dc.description.abstract Epoxide formation was established a decade ago as a possible reaction pathway for beta-hydroperoxy alkyl radicals in the atmosphere. This epoxide-forming pathway required excess energy to compete with O-2 addition, as the thermal reaction rate coefficient is many orders of magnitude too slow. However, recently, a thermal epoxide forming reaction was discovered in the ISOPOOH + OH oxidation pathway. Here, we computationally investigate the effect of substituents on the epoxide formation rate coefficient of a series of substituted beta-hydroperoxy alkyl radicals. We find that the thermal reaction is likely to be competitive with O-2 addition when the alkyl radical carbon has a OH group, which is able to form a hydrogen bond to a substituent on the other carbon atom in the epoxide ring being formed. Reactants fulfilling these requirements can be formed in the OH-initiated oxidation of many biogenic hydrocarbons. Further, we find that beta-OOR alkyl radicals react similarly to beta-OOH alkyl radicals, making epoxide formation a possible decomposition pathway in the oxidation of ROOR peroxides. GEOS-Chem modeling shows that the total annual production of isoprene dihydroxy hydroperoxy epoxide is 23 Tg, making it by far the most abundant C-5-tetrafunctional species from isoprene oxidation. en
dc.format.extent 11
dc.language.iso eng
dc.relation.ispartof Journal of Physical Chemistry A
dc.rights.uri info:eu-repo/semantics/openAccess
dc.subject SECONDARY ORGANIC AEROSOL
dc.subject MOLECULAR-ORBITAL METHODS
dc.subject CYCLIC ETHER FORMATION
dc.subject BASIS-SETS
dc.subject ISOPRENE EPOXYDIOLS
dc.subject TROPOSPHERIC CHEMISTRY
dc.subject ARRHENIUS PARAMETERS
dc.subject REACTIVE UPTAKE
dc.subject MODEL
dc.subject EMISSIONS
dc.subject 116 Chemical sciences
dc.subject 114 Physical sciences
dc.title Thermalized Epoxide Formation in the Atmosphere en
dc.type Article
dc.contributor.organization Department of Chemistry
dc.description.reviewstatus Peer reviewed
dc.relation.doi https://doi.org/10.1021/acs.jpca.9b09364
dc.relation.issn 1089-5639
dc.rights.accesslevel openAccess
dc.type.version acceptedVersion

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