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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 \u03c0* \u2190 \u03c0 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 \u03bb \u2264 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 \u03c0* \u2190 \u03c0 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 \u03c0* \u2190 \u03c0 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.<\/jats:p>","DOI":"10.1063\/1.5064716","type":"journal-article","created":{"date-parts":[[2018,12,28]],"date-time":"2018-12-28T14:59:30Z","timestamp":1546009170000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":60,"title":["Electronic spectroscopy of methyl vinyl ketone oxide: A four-carbon unsaturated Criegee intermediate from isoprene ozonolysis"],"prefix":"10.1063","volume":"149","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-6189-6272","authenticated-orcid":false,"given":"Michael F.","family":"Vansco","sequence":"first","affiliation":[{"name":"Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Barbara","family":"Marchetti","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2367-3497","authenticated-orcid":false,"given":"Marsha I.","family":"Lester","sequence":"additional","affiliation":[{"name":"Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2018,12,28]]},"reference":[{"key":"2023062523091122000_c1","doi-asserted-by":"publisher","first-page":"9317","DOI":"10.5194\/acp-14-9317-2014","volume":"14","year":"2014","journal-title":"Atmos. 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