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Unimolecular Reactions Following Indoor and Outdoor Limonene Ozonolysis

Chen, Jing and Møller, Kristian H. and Wennberg, Paul O. and Kjaergaard, Henrik G. (2021) Unimolecular Reactions Following Indoor and Outdoor Limonene Ozonolysis. Journal of Physical Chemistry A, 125 (2). pp. 669-680. ISSN 1089-5639. doi:10.1021/acs.jpca.0c09882.

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Limonene is one of the monoterpenes with the largest biogenic emissions and is also widely used as an additive in cleaning products, leading to significant indoor emissions. Studies have found that the formation of secondary organic aerosols (SOAs) from limonene oxidation has important implications for indoor air quality. Although ozonolysis is considered the major limonene oxidation pathway under most indoor conditions, little is known about the mechanisms for SOA formation from limonene ozonolysis. Here, we calculate the rate coefficients of the possible unimolecular reactions of the first-generation peroxy radicals formed by limonene ozonolysis using a high-level multiconformer transition state theory approach. We find that all of the peroxy radicals formed initially in the ozonolysis of limonene react unimolecularly with rates that are competitive both indoors and outdoors, except under highly polluted conditions. Differences in reactivity between the peroxy radicals from ozonolysis and those formed by OH, NO₃, and Cl oxidation are discussed. Finally, we sketch possible oxidation mechanisms for the different peroxy radicals under both indoor and pristine atmospheric conditions and in more polluted environments. In environments with low concentrations of HO₂ and NO, efficient autoxidation will lead to the formation of highly oxygenated organic compounds and thus likely aid in the growth of SOA.

Item Type:Article
Related URLs:
URLURL TypeDescription ItemOutput files from all calculations including the B3LYP/6-31+G(d) and ωB97X-D/aug-cc-pVTZ xyz-geometries
Chen, Jing0000-0001-6545-6197
Møller, Kristian H.0000-0001-8070-8516
Wennberg, Paul O.0000-0002-6126-3854
Kjaergaard, Henrik G.0000-0002-7275-8297
Additional Information:© 2021 American Chemical Society. Received: November 2, 2020; Revised: December 21, 2020; Published: January 12, 2021. The authors are grateful for the funding from the Independent Research Fund Denmark and the University of Copenhagen. This work is supported by the Alfred P. Sloan Foundation under Award no. G-2019-12281 and the California Institute of Technology. The authors declare no competing financial interest.
Funding AgencyGrant Number
Independent Research Fund DenmarkUNSPECIFIED
University of CopenhagenUNSPECIFIED
Alfred P. Sloan FoundationG-2019-12281
Subject Keywords:Redox reactions, Chemical reactions, Oxidation, Molecular structure, Organic reactions
Issue or Number:2
Record Number:CaltechAUTHORS:20210115-132720425
Persistent URL:
Official Citation:Unimolecular Reactions Following Indoor and Outdoor Limonene Ozonolysis. Jing Chen, Kristian H. Møller, Paul O. Wennberg, and Henrik G. Kjaergaard. The Journal of Physical Chemistry A 2021 125 (2), 669-680; DOI: 10.1021/acs.jpca.0c09882
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:107511
Deposited By: George Porter
Deposited On:19 Jan 2021 15:46
Last Modified:16 Nov 2021 19:03

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