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Atmospheric Fate of Methacrolein. 2. Formation of Lactone and Implications for Organic Aerosol Production

Kjaergaard, Henrik G. and Knap, Hasse C. and Ørnsø, Kristian B. and Jørgensen, Solvejg and Crounse, John D. and Paulot, Fabien and Wennberg, Paul O. (2012) Atmospheric Fate of Methacrolein. 2. Formation of Lactone and Implications for Organic Aerosol Production. Journal of Physical Chemistry A, 116 (24). pp. 5763-5768. ISSN 1089-5639. https://resolver.caltech.edu/CaltechAUTHORS:20120716-083627902

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Abstract

We investigate the oxidation of methacryloylperoxy nitrate (MPAN) and methacrylicperoxy acid (MPAA) by the hydroxyl radical (OH) theoretically, using both density functional theory [B3LYP] and explicitly correlated coupled cluster theory [CCSD(T)-F12]. These two compounds are produced following the abstraction of a hydrogen atom from methacrolein (MACR) by the OH radical. We use a RRKM master equation analysis to estimate that the oxidation of MPAN leads to formation of hydroxymethyl–methyl-α-lactone (HMML) in high yield. HMML production follows a low potential energy path from both MPAN and MPAA following addition of OH (via elimination of the NO_3 and OH from MPAN and MPAA, respectively). We suggest that the subsequent heterogeneous phase chemistry of HMML may be the route to formation of 2-methylglyceric acid, a common component of organic aerosol produced in the oxidation of methacrolein. Oxidation of acrolein, a photo-oxidation product from 1,3-butadiene, is found to follow a similar route generating hydroxymethyl-α-lactone (HML).


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1021/jp210853hDOIArticle
http://pubs.acs.org/doi/abs/10.1021/jp210853hPublisherArticle
ORCID:
AuthorORCID
Kjaergaard, Henrik G.0000-0002-7275-8297
Crounse, John D.0000-0001-5443-729X
Paulot, Fabien0000-0001-7534-4922
Wennberg, Paul O.0000-0002-6126-3854
Additional Information:© 2012 American Chemical Society. Special Issue: A. R. Ravishankara Festschrift. Received: November 11, 2011. Revised: March 27, 2012. Publication Date (Web): March 27, 2012. We are grateful to the reviewers for suggesting the RRKM master equation analysis and to John Barker for helpful discussions regarding the MultiWell program. We thank The Danish Council for Independent Research - Natural Sciences, the Danish Center for Scientific Computing (DCSC), NASA (NNX08AD29G), and NSF (ATM-0934408) for funding. F.P. is supported by a Ziff environmental fellowship through the Harvard University Center for the Environment.
Funders:
Funding AgencyGrant Number
Danish Council for Independent Research-Natural SciencesUNSPECIFIED
Danish Center for Scientific Computing (DCSC)UNSPECIFIED
NASANNX08AD29G
NSFATM-0934408
Harvard UniversityUNSPECIFIED
Issue or Number:24
Record Number:CaltechAUTHORS:20120716-083627902
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20120716-083627902
Official Citation:Atmospheric Fate of Methacrolein. 2. Formation of Lactone and Implications for Organic Aerosol Production Henrik G. Kjaergaard, Hasse C. Knap, Kristian B. Ørnsø, Solvejg Jørgensen, John D. Crounse, Fabien Paulot, and Paul O. Wennberg The Journal of Physical Chemistry A 2012 116 (24), 5763-5768
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:32453
Collection:CaltechAUTHORS
Deposited By: Ruth Sustaita
Deposited On:16 Jul 2012 15:54
Last Modified:09 Mar 2020 13:19

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