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Title: Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis

Abstract

Ozonolysis of isoprene, one of the most abundant volatile organic compounds in the atmosphere, proceeds through methyl vinyl ketone oxide (MVK-oxide), methacrolein oxide, and formaldehyde oxide (CH2OO) Criegee intermediates. The present study focuses on MVK-oxide, a four-carbon unsaturated carbonyl oxide intermediate, using vacuum ultraviolet photoionization at 118 nm and UV-visible induced depletion of the m/z = 86 mass channel to characterize its first π* ← π electronic transition. The electronic spectrum is broad and unstructured with its peak at 388 nm (3.2 eV). The MVK-oxide spectrum is shifted to a significantly longer wavelength than CH2OO and alkyl-substituted Criegee intermediates studied previously due to extended conjugation across the vinyl and carbonyl oxide groups. Electronic excitation results in rapid dissociation at λ ≤ 430 nm to methyl vinyl ketone and O 1D products, the latter detected by 2 + 1 resonance enhanced multiphoton ionization using velocity map imaging. Complementary electronic structure calculations (CASPT2(12,10)/AVDZ) predict two π* ← π transitions with significant oscillator strength for each of the four conformers of MVK-oxide with vertical excitation energies (and corresponding wavelengths) in the 3.1-3.6 eV (350-400 nm) and 4.5-5.5 eV (220-280 nm) regions. The computed electronic absorption profile of MVK-oxide, based on a Wigner distributionmore » of ground state configurations and summed over the four conformers, is predicted to peak at 397 nm. UV-visible spectroscopy on the first π* ← π transition is shown by a combination of experiment and theory to provide a sensitive method for detection of the MVK-oxide Criegee intermediate that will enable further studies of its photochemistry and unimolecular and bimolecular reaction dynamics.« less

Authors:
ORCiD logo [1];  [1]; ORCiD logo [1]
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  1. Univ. of Pennsylvania, Philadelphia, PA (United States)
Publication Date:
Research Org.:
Univ. of Pennsylvania, Philadelphia, PA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
OSTI Identifier:
1598271
Alternate Identifier(s):
OSTI ID: 1782232
Grant/Contract Number:  
FG02-87ER13792; CHE-1664572
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 24; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Electronic excitation; UV-visible spectroscopy; Oscillator strengths; Photoionization

Citation Formats

Vansco, Michael F., Marchetti, Barbara, and Lester, Marsha I. Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis. United States: N. p., 2018. Web. doi:10.1063/1.5064716.
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Vansco, Michael F., Marchetti, Barbara, & Lester, Marsha I. Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis. United States. https://doi.org/10.1063/1.5064716
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Vansco, Michael F., Marchetti, Barbara, and Lester, Marsha I. Fri . "Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis". United States. https://doi.org/10.1063/1.5064716. https://www.osti.gov/servlets/purl/1598271.
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@article{osti_1598271,
title = {Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis},
author = {Vansco, Michael F. and Marchetti, Barbara and Lester, Marsha I.},
abstractNote = {Ozonolysis of isoprene, one of the most abundant volatile organic compounds in the atmosphere, proceeds through methyl vinyl ketone oxide (MVK-oxide), methacrolein oxide, and formaldehyde oxide (CH2OO) Criegee intermediates. The present study focuses on MVK-oxide, a four-carbon unsaturated carbonyl oxide intermediate, using vacuum ultraviolet photoionization at 118 nm and UV-visible induced depletion of the m/z = 86 mass channel to characterize its first π* ← π electronic transition. The electronic spectrum is broad and unstructured with its peak at 388 nm (3.2 eV). The MVK-oxide spectrum is shifted to a significantly longer wavelength than CH2OO and alkyl-substituted Criegee intermediates studied previously due to extended conjugation across the vinyl and carbonyl oxide groups. Electronic excitation results in rapid dissociation at λ ≤ 430 nm to methyl vinyl ketone and O 1D products, the latter detected by 2 + 1 resonance enhanced multiphoton ionization using velocity map imaging. Complementary electronic structure calculations (CASPT2(12,10)/AVDZ) predict two π* ← π transitions with significant oscillator strength for each of the four conformers of MVK-oxide with vertical excitation energies (and corresponding wavelengths) in the 3.1-3.6 eV (350-400 nm) and 4.5-5.5 eV (220-280 nm) regions. The computed electronic absorption profile of MVK-oxide, based on a Wigner distribution of ground state configurations and summed over the four conformers, is predicted to peak at 397 nm. UV-visible spectroscopy on the first π* ← π transition is shown by a combination of experiment and theory to provide a sensitive method for detection of the MVK-oxide Criegee intermediate that will enable further studies of its photochemistry and unimolecular and bimolecular reaction dynamics.},
doi = {10.1063/1.5064716},
journal = {Journal of Chemical Physics},
number = 24,
volume = 149,
place = {United States},
year = {Fri Dec 28 00:00:00 EST 2018},
month = {Fri Dec 28 00:00:00 EST 2018}
}
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    Unimolecular decay dynamics of Criegee intermediates: Energy-resolved rates, thermal rates, and their atmospheric impact
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