{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,6,4]],"date-time":"2026-06-04T20:08:37Z","timestamp":1780603717951,"version":"3.54.1"},"reference-count":45,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2022,11,23]],"date-time":"2022-11-23T00:00:00Z","timestamp":1669161600000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/501100008982","name":"National Science Foundation of Sri Lanka","doi-asserted-by":"publisher","award":["2003422"],"award-info":[{"award-number":["2003422"]}],"id":[{"id":"10.13039\/501100008982","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["onlinelibrary.wiley.com"],"crossmark-restriction":true},"short-container-title":["Photochem &amp; Photobiology"],"published-print":{"date-parts":[[2023,7]]},"abstract":"<jats:title>Abstract<\/jats:title><jats:p>Isoprene is the most abundant nonmethane volatile organic compound emitted into the troposphere by terrestrial vegetation. Reaction with ozone represents an important isoprene removal process from the troposphere and is a well\u2010known source of Criegee intermediates (CIs), which are reactive carbonyl oxides. Three CIs, formaldehyde oxide (CH<jats:sub>2<\/jats:sub>OO), methyl vinyl ketone oxide (MVK\u2010oxide) and methacrolein oxide (MACR\u2010oxide) are formed during isoprene ozonolysis. All three CIs contain strongly absorbing \u03c0\u03c0* states, electronic excitation, which leads to dissociation to form aldehyde\/ketone + oxygen products. Here, we compare the excited state chemistry of CH<jats:sub>2<\/jats:sub>OO, MVK\u2010oxide and MACR\u2010oxide in order to ascertain how increasing molecular complexity affects their photodynamics. In CH<jats:sub>2<\/jats:sub>OO, vertical excitation to the S<jats:sub>2<\/jats:sub> state leads to prompt O\u2010O bond fission with a unity quantum yield. Branching into both the O\u00a0(<jats:sup>1<\/jats:sup>D)\u2009+\u2009H<jats:sub>2<\/jats:sub>CO (S<jats:sub>0<\/jats:sub>) and O (<jats:sup>3<\/jats:sup>P)\u2009+\u2009H<jats:sub>2<\/jats:sub>CO (T<jats:sub>1<\/jats:sub>) product channels is predicted, with 80% of trajectories dissociating to form the former product pair. Analogous vertical excitation of the lowest energy conformers of MVK\u2010oxide and MACR\u2010oxide also undergoes O\u2010O bond fission to form O\u2009+\u2009MVK\/MACR products\u2014albeit with a nonunity quantum yield. In the latter case, <jats:italic>ca.<\/jats:italic> 10% and 25% of trajectories remain as the parent MVK\u2010oxide and MACR\u2010oxide molecules, respectively. Additionally, at most only 5% of the dissociating trajectories form O (<jats:sup>3<\/jats:sup>P)\u2009+\u2009MVK\/MACR (T<jats:sub>1<\/jats:sub>) products, with a greater fraction forming O (<jats:sup>1<\/jats:sup>D)\u2009+\u2009MVK\/MACR (S<jats:sub>0<\/jats:sub>) products (<jats:italic>cf.<\/jats:italic> CH<jats:sub>2<\/jats:sub>OO). This latter observation coupled with the greater fraction of undissociated trajectories aligns with the\u00a0bathochromic shift in the electronic absorption of the MACR\u2010oxide and MVK\u2010oxide (<jats:italic>cf.<\/jats:italic> CH<jats:sub>2<\/jats:sub>OO). We discuss the implications of the results in a broader context, including those that are relevant to the atmosphere.<\/jats:p>","DOI":"10.1111\/php.13736","type":"journal-article","created":{"date-parts":[[2022,10,29]],"date-time":"2022-10-29T13:54:57Z","timestamp":1667051697000},"page":"1072-1079","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":6,"title":["Insights into the Ultrafast Photodissociation Dynamics of Isoprene\u2010Derived Criegee Intermediates"],"prefix":"10.1111","volume":"99","author":[{"given":"Ernest","family":"Antwi","sequence":"first","affiliation":[{"name":"University of Louisiana at Lafayette  Lafayette LA USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Niamh A.","family":"Packer","sequence":"additional","affiliation":[{"name":"University of Louisiana at Lafayette  Lafayette LA USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Jordyn M.","family":"Ratliff","sequence":"additional","affiliation":[{"name":"University of Louisiana at Lafayette  Lafayette LA USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Barbara","family":"Marchetti","sequence":"additional","affiliation":[{"name":"University of Louisiana at Lafayette  Lafayette LA USA"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-0583-3824","authenticated-orcid":false,"given":"Tolga N. V.","family":"Karsili","sequence":"additional","affiliation":[{"name":"University of Louisiana at Lafayette  Lafayette LA USA"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,11,23]]},"reference":[{"key":"e_1_2_5_2_1","doi-asserted-by":"publisher","DOI":"10.5194\/acp-14-9317-2014"},{"key":"e_1_2_5_3_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6CP00053C"},{"key":"e_1_2_5_4_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.8b06759"},{"key":"e_1_2_5_5_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CP00877D"},{"key":"e_1_2_5_6_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CP04408H"},{"key":"e_1_2_5_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/jz402191w"},{"key":"e_1_2_5_8_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.1916711117"},{"key":"e_1_2_5_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/jccs.201700049"},{"key":"e_1_2_5_10_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4892582"},{"key":"e_1_2_5_11_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cplett.2016.04.082"},{"key":"e_1_2_5_12_1","doi-asserted-by":"publisher","DOI":"10.1038\/s42004-021-00451-z"},{"key":"e_1_2_5_13_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.5064716"},{"key":"e_1_2_5_14_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CP00988A"},{"key":"e_1_2_5_15_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.5b05058"},{"key":"e_1_2_5_16_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CP00476C"},{"key":"e_1_2_5_17_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CP00199E"},{"key":"e_1_2_5_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja510736d"},{"key":"e_1_2_5_19_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0301-0104(02)00804-2"},{"key":"e_1_2_5_20_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CP04977F"},{"key":"e_1_2_5_21_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.1c01074"},{"key":"e_1_2_5_22_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.1c08381"},{"key":"e_1_2_5_23_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja310603j"},{"key":"e_1_2_5_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b05193"},{"key":"e_1_2_5_25_1","doi-asserted-by":"publisher","DOI":"10.1111\/php.13665"},{"key":"e_1_2_5_26_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.8b06010"},{"key":"e_1_2_5_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.0c02867"},{"key":"e_1_2_5_28_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.1916711117"},{"key":"e_1_2_5_29_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.0c02138"},{"key":"e_1_2_5_30_1","doi-asserted-by":"publisher","DOI":"10.3390\/molecules26103058"},{"key":"e_1_2_5_31_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.1c03643"},{"key":"e_1_2_5_32_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0068664"},{"key":"e_1_2_5_33_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CP01860H"},{"key":"e_1_2_5_34_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.201702722"},{"key":"e_1_2_5_35_1","doi-asserted-by":"publisher","DOI":"10.1111\/php.13560"},{"key":"e_1_2_5_36_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.2148954"},{"key":"e_1_2_5_37_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.456153"},{"key":"e_1_2_5_38_1","doi-asserted-by":"publisher","DOI":"10.1039\/D2CP01860H"},{"key":"e_1_2_5_39_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.jphotochem.2006.12.008"},{"key":"e_1_2_5_40_1","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.1158"},{"key":"e_1_2_5_41_1","doi-asserted-by":"publisher","DOI":"10.1145\/321250.321261"},{"key":"e_1_2_5_42_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.7b00018"},{"key":"e_1_2_5_43_1","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.1331"},{"key":"e_1_2_5_44_1","unstructured":"Werner H.\u2010J. 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