Supporting data for Formation of Highly Oxidized Molecules from NO3 Radical Oxidation of Δ-3-Carene: A Computational Mechanism

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dc.contributor.affiliationUniversity of California, Irvine - Draper, Danielle
dc.contributor.affiliationUniversity of California, Irvine - Smith, James
dc.contributor.affiliationReed College - Fry, Juliane
dc.contributor.affiliationUniversity of Helsinki - Kurten, Theo
dc.contributor.affiliationUniversity of Copenhagen - Kjaergaard, Henrik
dc.contributor.authorDraper, Danielle
dc.contributor.authorSmith, James
dc.contributor.authorFry, Juliane
dc.contributor.authorKurten, Theo
dc.contributor.authorKjaergaard, Henrik
dc.date.accessioned2025-03-24T15:20:54Z
dc.date.issued2019-05-03
dc.date.issued2019-05-03
dc.descriptionNO3 radical oxidation of most monoterpenes is a significant source of secondary organic aerosol (SOA) in many regions influenced by both biogenic and anthropogenic emissions, but there are very few published mechanistic studies of NO3 chemistry beyond 1st generation products. Here, we present a computationally-derived mechanism detailing the unimolecular pathways available to 2nd generation peroxy radicals following NO3 oxidation of Δ-3-carene. We assess five different types of unimolecular reactions, including peroxy and alkoxy radical (RO2 and RO) hydrogen shifts, RO­2 and RO ring closing (e.g. endoperoxide formation), and RO decomposition. Rate constants calculated using quantum chemical methods indicate that this chemical system has significant contribution from both bimolecular and unimolecular pathways. The dominant unimolecular reactions are endoperoxide formation, RO H-shifts, and RO decomposition. However, the complexity of the overall reaction is tempered as only 1 or 2 radical propagation pathways dominate the fate of each radical intermediate. Chemical Ionization Mass Spectrometry (CIMS) measurements using the NO3- reagent ion during Δ-3-carene + NO3 chamber experiments show products consistent with each of the three types of unimolecular reactions predicted to be important from the computational mechanism. Moreover, the SIMPOL group contribution method for predicting vapor pressures suggests that a majority of the closed-shell products inferred from these unimolecular reactions are likely to have low enough vapor pressure to be able to contribute to SOA formation.
dc.identifierhttps://doi.org/10.7280/D1VT0B
dc.identifier.urihttps://hydatakatalogi-test-24.it.helsinki.fi/handle/123456789/10576
dc.rightsOpen
dc.rights.licensecc-by-4.0
dc.titleSupporting data for Formation of Highly Oxidized Molecules from NO3 Radical Oxidation of Δ-3-Carene: A Computational Mechanism
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