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

Vansco, Michael F.; Marchetti, Barbara; Lester, Marsha I.

doi:10.1063/1.5064716

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

Journal Article · Fri Dec 28 00:00:00 EST 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5064716· OSTI ID:1598271

^[1]; Marchetti, Barbara ^[1];

^[1]

Univ. of Pennsylvania, Philadelphia, PA (United States)

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.

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Research Organization:: Univ. of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)

Grant/Contract Number:: FG02-87ER13792; CHE-1664572

OSTI ID:: 1598271

Alternate ID(s):: OSTI ID: 1782232

Journal Information:: Journal of Chemical Physics, Vol. 149, Issue 24; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 34 works

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