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Title: Four-Carbon Criegee Intermediate from Isoprene Ozonolysis: Methyl Vinyl Ketone Oxide Synthesis, Infrared Spectrum, and OH Production

Abstract

The reaction of ozone with isoprene, one of the most abundant volatile organic compounds in the atmosphere, produces three distinct carbonyl oxide species (RR'COO) known as Criegee intermediates: formaldehyde oxide (CH2OO), methyl vinyl ketone oxide (MVK-OO), and methacrolein oxide (MACR-OO). The nature of the substituents (R,R' = H, CH3, CH=CH2) and conformations of the Criegee intermediates control their subsequent chemistry in the atmosphere. In particular, unimolecular decay of MVK-OO is predicted to be the major source of hydroxyl radicals (OH) in isoprene ozonolysis. Our study reports the initial laboratory synthesis and direct detection of MVK-OO through reaction of a photolytically generated, resonance-stabilized monoiodoalkene radical with O2. MVK-OO is characterized utilizing infrared (IR) action spectroscopy, in which IR activation of MVK-OO with two quanta of CH stretch at ca. 6000 cm–1 is coupled with ultraviolet detection of the resultant OH products. MVK-OO is identified by comparison of the experimentally observed IR spectral features with theoretically predicted IR absorption spectra. For syn-MVK-OO, the rate of appearance of OH products agrees with the unimolecular decay rate predicted using statistical theory with tunneling. This validates the hydrogen atom transfer mechanism and computed transition-state barrier (18.0 kcal mol–1) leading to OH products. Theoretical calculations displaymore » a further roaming pathway between the separating radical fragments, which results in other products. Master equation modeling yields a thermal unimolecular decay rate for syn-MVK-OO of 33 s–1 (298 K, 1 atm). For anti-MVK-OO, theoretical exploration of several unimolecular decay pathways predicts that isomerization to dioxole is the most likely initial step to products.« less

Authors:
 [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Univ. of Pennsylvania, Philadelphia, PA (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1598267
Grant/Contract Number:  
FG02-87ER13792; AC02-06CH11357; CHE-1664572; CHE-1464744; DMR-1628407
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 34; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Barber, Victoria P., Pandit, Shubhrangshu, Green, Amy M., Trongsiriwat, Nisalak, Walsh, Patrick J., Klippenstein, Stephen J., and Lester, Marsha I. Four-Carbon Criegee Intermediate from Isoprene Ozonolysis: Methyl Vinyl Ketone Oxide Synthesis, Infrared Spectrum, and OH Production. United States: N. p., 2018. Web. https://doi.org/10.1021/jacs.8b06010.
Barber, Victoria P., Pandit, Shubhrangshu, Green, Amy M., Trongsiriwat, Nisalak, Walsh, Patrick J., Klippenstein, Stephen J., & Lester, Marsha I. Four-Carbon Criegee Intermediate from Isoprene Ozonolysis: Methyl Vinyl Ketone Oxide Synthesis, Infrared Spectrum, and OH Production. United States. https://doi.org/10.1021/jacs.8b06010
Barber, Victoria P., Pandit, Shubhrangshu, Green, Amy M., Trongsiriwat, Nisalak, Walsh, Patrick J., Klippenstein, Stephen J., and Lester, Marsha I. Fri . "Four-Carbon Criegee Intermediate from Isoprene Ozonolysis: Methyl Vinyl Ketone Oxide Synthesis, Infrared Spectrum, and OH Production". United States. https://doi.org/10.1021/jacs.8b06010. https://www.osti.gov/servlets/purl/1598267.
@article{osti_1598267,
title = {Four-Carbon Criegee Intermediate from Isoprene Ozonolysis: Methyl Vinyl Ketone Oxide Synthesis, Infrared Spectrum, and OH Production},
author = {Barber, Victoria P. and Pandit, Shubhrangshu and Green, Amy M. and Trongsiriwat, Nisalak and Walsh, Patrick J. and Klippenstein, Stephen J. and Lester, Marsha I.},
abstractNote = {The reaction of ozone with isoprene, one of the most abundant volatile organic compounds in the atmosphere, produces three distinct carbonyl oxide species (RR'COO) known as Criegee intermediates: formaldehyde oxide (CH2OO), methyl vinyl ketone oxide (MVK-OO), and methacrolein oxide (MACR-OO). The nature of the substituents (R,R' = H, CH3, CH=CH2) and conformations of the Criegee intermediates control their subsequent chemistry in the atmosphere. In particular, unimolecular decay of MVK-OO is predicted to be the major source of hydroxyl radicals (OH) in isoprene ozonolysis. Our study reports the initial laboratory synthesis and direct detection of MVK-OO through reaction of a photolytically generated, resonance-stabilized monoiodoalkene radical with O2. MVK-OO is characterized utilizing infrared (IR) action spectroscopy, in which IR activation of MVK-OO with two quanta of CH stretch at ca. 6000 cm–1 is coupled with ultraviolet detection of the resultant OH products. MVK-OO is identified by comparison of the experimentally observed IR spectral features with theoretically predicted IR absorption spectra. For syn-MVK-OO, the rate of appearance of OH products agrees with the unimolecular decay rate predicted using statistical theory with tunneling. This validates the hydrogen atom transfer mechanism and computed transition-state barrier (18.0 kcal mol–1) leading to OH products. Theoretical calculations display a further roaming pathway between the separating radical fragments, which results in other products. Master equation modeling yields a thermal unimolecular decay rate for syn-MVK-OO of 33 s–1 (298 K, 1 atm). For anti-MVK-OO, theoretical exploration of several unimolecular decay pathways predicts that isomerization to dioxole is the most likely initial step to products.},
doi = {10.1021/jacs.8b06010},
journal = {Journal of the American Chemical Society},
number = 34,
volume = 140,
place = {United States},
year = {2018},
month = {8}
}

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Works referencing / citing this record:

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Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis
journal, December 2018

  • Vansco, Michael F.; Marchetti, Barbara; Lester, Marsha I.
  • The Journal of Chemical Physics, Vol. 149, Issue 24
  • DOI: 10.1063/1.5064716

Calculation of the absolute photoionization cross-sections for C1–C4 Criegee intermediates and vinyl hydroperoxides
journal, April 2019

  • Huang, Can; Yang, Bin; Zhang, Feng
  • The Journal of Chemical Physics, Vol. 150, Issue 16
  • DOI: 10.1063/1.5088408

Unimolecular decay dynamics of Criegee intermediates: Energy-resolved rates, thermal rates, and their atmospheric impact
journal, December 2019