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

Micheal Francis Vansco, Barbara Marchetti, Marsha I Lester

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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 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.
Original languageEnglish
Article number244309
Number of pages10
JournalJournal of Chemical Physics
Volume149
Issue number24
DOIs
Publication statusPublished - 2018

Bibliographical note

This publications reports experimental and theoretical studies carried out as part of the following postdoctoral fellowship within Marie Skłodowska-Curie Action: Photo- and Radical- Induced reactions of Atmospheric Oxydants (PhARRAO) - grant No 746593)

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