Atmospheric fate of methacrolein: 2. Formation of lactone and implications for organic aerosol production

Henrik Grum Kjærgaard; Hasse Christian Knap; Kristian B. Ørnsø; Solvejg Jørgensen; John D. Crounse; Fabien Paulot; Paul O. Wennberg

doi:10.1021/jp210853h

Atmospheric fate of methacrolein: 2. Formation of lactone and implications for organic aerosol production

Henrik Grum Kjærgaard, Hasse Christian Knap, Kristian B. Ørnsø, Solvejg Jørgensen, John D. Crounse, Fabien Paulot, Paul O. Wennberg

Kemisk Institut

42 Citationer (Scopus)

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).

Originalsprog	Engelsk
Tidsskrift	Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory
Vol/bind	116
Udgave nummer	24
Sider (fra-til)	5763-5768
Antal sider	6
ISSN	1089-5639
DOI	https://doi.org/10.1021/jp210853h
Status	Udgivet - 21 jun. 2012

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10.1021/jp210853h

Citationsformater

Kjærgaard, H. G., Knap, H. C., Ørnsø, K. B., Jørgensen, S., Crounse, J. D., Paulot, F., & Wennberg, P. O. (2012). Atmospheric fate of methacrolein: 2. Formation of lactone and implications for organic aerosol production. Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, 116(24), 5763-5768. https://doi.org/10.1021/jp210853h

Atmospheric fate of methacrolein: 2. Formation of lactone and implications for organic aerosol production. / Kjærgaard, Henrik Grum; Knap, Hasse Christian; Ørnsø, Kristian B. et al.
I: Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, Bind 116, Nr. 24, 21.06.2012, s. 5763-5768.

Publikation: Bidrag til tidsskrift › Tidsskriftartikel › Forskning › peer review

Kjærgaard, HG, Knap, HC, Ørnsø, KB, Jørgensen, S, Crounse, JD, Paulot, F & Wennberg, PO 2012, 'Atmospheric fate of methacrolein: 2. Formation of lactone and implications for organic aerosol production', Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory, bind 116, nr. 24, s. 5763-5768. https://doi.org/10.1021/jp210853h

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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).",

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T2 - 2. Formation of lactone and implications for organic aerosol production

AU - Kjærgaard, Henrik Grum

AU - Knap, Hasse Christian

AU - Ørnsø, Kristian B.

AU - Jørgensen, Solvejg

AU - Crounse, John D.

AU - Paulot, Fabien

AU - Wennberg, Paul O.

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N2 - 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).

AB - 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).

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DO - 10.1021/jp210853h

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JO - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

JF - Journal of Physical Chemistry Part A: Molecules, Spectroscopy, Kinetics, Environment and General Theory

IS - 24

ER -

Atmospheric fate of methacrolein: 2. Formation of lactone and implications for organic aerosol production

Abstract

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