Welcome to the new version of CaltechAUTHORS. Login is currently restricted to library staff. If you notice any issues, please email coda@library.caltech.edu
Published June 21, 2012 | Supplemental Material
Journal Article Open

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

Files

jp210853h_si_001.pdf
Files (778.8 kB)
Name Size Download all
md5:b060951aaf0378fd99401af98b6c34cc
778.8 kB Preview Download

Additional details

Created:
August 22, 2023
Modified:
October 18, 2023