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Autoxidation of Organic Compounds in the Atmosphere

Crounse, John D. and Nielsen, Lasse B. and Jørgensen, Solvejg and Kjaergaard, Henrik G. and Wennberg, Paul O. (2013) Autoxidation of Organic Compounds in the Atmosphere. Journal of Physical Chemistry Letters, 4 (20). pp. 3513-3520. ISSN 1948-7185. doi:10.1021/jz4019207.

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We present a hypothesis that autoxidation (inter- and intramolecular hydrogen abstraction by peroxy radicals) plays an important role in the oxidation of organic compounds in the atmosphere, particularly organic matter associated with aerosol. In the laboratory, we determine the rate of this process at room temperature for a model system, 3-pentanone. We employ ab initio calculations to investigate H-shifts within a broader group of substituted organic compounds. We show that the rate of abstraction of hydrogen by peroxy radicals is largely determined by the thermochemistry of the nascent alkyl radicals and thus is highly influenced by neighboring substituents. As a result, autoxidation rates increase rapidly as oxygen-containing functional groups (carbonyl, hydroxy, and hydroperoxy) are added to organic compounds. This mechanism is consistent with formation of the multifunctional hydroperoxides and carbonyls often found in atmospheric aerosol particles.

Item Type:Article
Related URLs:
URLURL TypeDescription
Crounse, John D.0000-0001-5443-729X
Kjaergaard, Henrik G.0000-0002-7275-8297
Wennberg, Paul O.0000-0002-6126-3854
Additional Information:© 2013 American Chemical Society. Received: September 6, 2013; Accepted: September 30, 2013; Published: September 30, 2013. The authors thank NASA (NNX12AC06G) and NSF (AGS-1240604), the Danish Council for Independent Research - Natural Sciences, and the Danish Center for Scientific Computing (DCSC) for their support of this research. Additional information on the instrumental calibration, timeline of 3-PN oxidation products, RO₂ H-shift barriers as a function of the number of atoms in the cyclic transition state, stereoselectivity of the RO₂ H-shift reactions, hydrogen abstraction in 3-pentanone oxidation by OH, and theoretical calculations for additional RO₂ H-shift reactions.
Funding AgencyGrant Number
Danish Council for Independent Research - Natural SciencesUNSPECIFIED
Danish Center for Scientific Computing (DCSC)UNSPECIFIED
Subject Keywords:Environmental and Atmospheric Chemistry, Aerosol Processes, Geochemistry, and Astrochemistry
Issue or Number:20
Record Number:CaltechAUTHORS:20131121-161549474
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Official Citation:Autoxidation of Organic Compounds in the Atmosphere John D. Crounse, Lasse B. Nielsen, Solvejg Jørgensen, Henrik G. Kjaergaard, and Paul O. Wennberg The Journal of Physical Chemistry Letters 2013 4 (20), 3513-3520
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:42636
Deposited By: David McCaslin
Deposited On:22 Nov 2013 16:14
Last Modified:10 Nov 2021 16:26

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