Atmospheric Fate of Methacrolein. 2. Formation of Lactone and Implications for Organic Aerosol Production
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).
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.Attached Files
Supplemental Material - jp210853h_si_001.pdf
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Additional details
- Eprint ID
- 32453
- DOI
- 10.1021/jp210853h
- Resolver ID
- CaltechAUTHORS:20120716-083627902
- Danish Council for Independent Research-Natural Sciences
- Danish Center for Scientific Computing (DCSC)
- NASA
- NNX08AD29G
- NSF
- ATM-0934408
- Harvard University
- Created
-
2012-07-16Created from EPrint's datestamp field
- Updated
-
2021-11-09Created from EPrint's last_modified field
- Caltech groups
- Division of Geological and Planetary Sciences