{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,4,5]],"date-time":"2026-04-05T18:17:05Z","timestamp":1775413025301,"version":"3.50.1"},"reference-count":61,"publisher":"Wiley","issue":"4","license":[{"start":{"date-parts":[[2022,11,12]],"date-time":"2022-11-12T00:00:00Z","timestamp":1668211200000},"content-version":"am","delay-in-days":351,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#am"},{"start":{"date-parts":[[2021,11,26]],"date-time":"2021-11-26T00:00:00Z","timestamp":1637884800000},"content-version":"vor","delay-in-days":0,"URL":"http:\/\/onlinelibrary.wiley.com\/termsAndConditions#vor"}],"funder":[{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["2003422"],"award-info":[{"award-number":["2003422"]}],"id":[{"id":"10.13039\/100000001","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/100000001","name":"National Science Foundation","doi-asserted-by":"publisher","award":["DGE\u20101845298"],"award-info":[{"award-number":["DGE\u20101845298"]}],"id":[{"id":"10.13039\/100000001","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":[[2022,7]]},"abstract":"<jats:title>ABSTRACT<\/jats:title><jats:p>Criegee intermediates make up a class of molecules that are of significant atmospheric importance. Understanding their electronically excited states guides experimental detection and provides insight into whether solar photolysis plays a role in their removal from the troposphere. The latter is particularly important for large and functionalized Criegee intermediates. In this study, the excited state chemistry of two small Criegee intermediates, formaldehyde oxide (CH<jats:sub>2<\/jats:sub>OO) and acetaldehyde oxide (CH<jats:sub>3<\/jats:sub>CHOO), was modeled to compare their specific dynamics and mechanisms following excitation to the bright \u03c0\u03c0* state and to assess the involvement of triplet states to the excited state decay process. Following excitation to the bright \u03c0\u03c0* state, the photoexcited population exclusively evolves to form oxygen plus aldehyde products without the involvement of triplet states. This occurs despite the presence of a more thermodynamically stable triplet path and several singlet\/triplet energy crossings at the Franck\u2010Condon geometry and contrasts with the photodynamics of related systems such as acetaldehyde and acetone. This work sets the foundations to study Criegee intermediates with greater molecular complexity, wherein a bathochromic shift in the electron absorption profiles may ensure greater removal <jats:italic>via<\/jats:italic> solar photolysis.<\/jats:p>","DOI":"10.1111\/php.13560","type":"journal-article","created":{"date-parts":[[2021,11,12]],"date-time":"2021-11-12T18:30:34Z","timestamp":1636741834000},"page":"763-772","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":21,"title":["Insights into the Ultrafast Dynamics of CH<sub>2<\/sub>OO and CH<sub>3<\/sub>CHOO Following Excitation to the Bright <sup>1<\/sup>\u03c0\u03c0* State: The Role of Singlet and Triplet States"],"prefix":"10.1111","volume":"98","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-6035-3869","authenticated-orcid":false,"given":"Vincent J.","family":"Esposito","sequence":"first","affiliation":[{"name":"University of Pennsylvania  Philadelphia PA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Olivia","family":"Werba","sequence":"additional","affiliation":[{"name":"University of Pennsylvania  Philadelphia PA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sarah A.","family":"Bush","sequence":"additional","affiliation":[{"name":"University of Louisiana at Lafayette  Lafayette LA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Barbara","family":"Marchetti","sequence":"additional","affiliation":[{"name":"University of Louisiana at Lafayette  Lafayette LA"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"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"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2021,11,26]]},"reference":[{"key":"e_1_2_7_2_1","doi-asserted-by":"publisher","DOI":"10.1039\/c0cp02564j"},{"key":"e_1_2_7_3_1","doi-asserted-by":"publisher","DOI":"10.1039\/b704260b"},{"key":"e_1_2_7_4_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.atmosenv.2009.03.042"},{"key":"e_1_2_7_5_1","doi-asserted-by":"publisher","DOI":"10.5194\/acp-7-167-2007"},{"key":"e_1_2_7_6_1","doi-asserted-by":"publisher","DOI":"10.1039\/c0cp02342f"},{"key":"e_1_2_7_7_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp408745h"},{"key":"e_1_2_7_8_1","doi-asserted-by":"publisher","DOI":"10.1029\/2001JD000597"},{"key":"e_1_2_7_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/acsearthspacechem.8b00215"},{"key":"e_1_2_7_10_1","doi-asserted-by":"publisher","DOI":"10.1038\/nature11278"},{"key":"e_1_2_7_11_1","doi-asserted-by":"publisher","DOI":"10.1002\/jccs.201700049"},{"key":"e_1_2_7_12_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.8b06759"},{"key":"e_1_2_7_13_1","doi-asserted-by":"publisher","DOI":"10.1039\/C5CP04977F"},{"key":"e_1_2_7_14_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CP00877D"},{"key":"e_1_2_7_15_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4892582"},{"key":"e_1_2_7_16_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.cplett.2016.04.082"},{"key":"e_1_2_7_17_1","doi-asserted-by":"publisher","DOI":"10.1039\/C4CP04408H"},{"key":"e_1_2_7_18_1","doi-asserted-by":"publisher","DOI":"10.1021\/jz402191w"},{"key":"e_1_2_7_19_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CP00199E"},{"key":"e_1_2_7_20_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja510736d"},{"key":"e_1_2_7_21_1","doi-asserted-by":"publisher","DOI":"10.1016\/S0301-0104(02)00804-2"},{"key":"e_1_2_7_22_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4923165"},{"key":"e_1_2_7_23_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.atmosenv.2018.08.014"},{"key":"e_1_2_7_24_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp412726z"},{"key":"e_1_2_7_25_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4810865"},{"key":"e_1_2_7_26_1","doi-asserted-by":"publisher","DOI":"10.1039\/C6CP00807K"},{"key":"e_1_2_7_27_1","doi-asserted-by":"publisher","DOI":"10.1021\/ja310603j"},{"key":"e_1_2_7_28_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.5b05352"},{"key":"e_1_2_7_29_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4824655"},{"key":"e_1_2_7_30_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4977987"},{"key":"e_1_2_7_31_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4894746"},{"key":"e_1_2_7_32_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpclett.8b00023"},{"key":"e_1_2_7_33_1","doi-asserted-by":"publisher","DOI":"10.1039\/C8CP02015A"},{"key":"e_1_2_7_34_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1234689"},{"key":"e_1_2_7_35_1","doi-asserted-by":"publisher","DOI":"10.1039\/c2cp40294g"},{"key":"e_1_2_7_36_1","doi-asserted-by":"publisher","DOI":"10.1126\/science.1213229"},{"key":"e_1_2_7_37_1","doi-asserted-by":"publisher","DOI":"10.1039\/c1cp20872a"},{"key":"e_1_2_7_38_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4998170"},{"key":"e_1_2_7_39_1","doi-asserted-by":"publisher","DOI":"10.1039\/C7CS00336F"},{"key":"e_1_2_7_40_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.5064716"},{"key":"e_1_2_7_41_1","doi-asserted-by":"publisher","DOI":"10.1021\/jacs.9b05193"},{"key":"e_1_2_7_42_1","doi-asserted-by":"publisher","DOI":"10.1039\/D0CP01873B"},{"key":"e_1_2_7_43_1","doi-asserted-by":"publisher","DOI":"10.1039\/b810189b"},{"key":"e_1_2_7_44_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.1672392"},{"key":"e_1_2_7_45_1","doi-asserted-by":"publisher","DOI":"10.1016\/0301-0104(82)88019-1"},{"key":"e_1_2_7_46_1","doi-asserted-by":"publisher","DOI":"10.1021\/j100377a012"},{"key":"e_1_2_7_47_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.462209"},{"key":"e_1_2_7_48_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.1c03643"},{"key":"e_1_2_7_49_1","unstructured":"Mai S. M.Richter M.Heindl M. F. S. J.Menger A. J.Atkins M.Ruckenbauer F.Plasser L. M.Ibele S.Kropf M.Oppel P.MarquetandandL.Gonz\u00e1lez. (2019)SHARC2.1: Surface Hopping Including Arbitrary Couplings \u2013 Program Package for Non\u2010Adiabatic Dynamics. Available at:http:\/\/sharc\u2010md.org."},{"key":"e_1_2_7_50_1","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.1370"},{"key":"e_1_2_7_51_1","doi-asserted-by":"publisher","DOI":"10.1063\/5.0004835"},{"key":"e_1_2_7_52_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jctc.9b00532"},{"key":"e_1_2_7_53_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.2715585"},{"key":"e_1_2_7_54_1","volume-title":"Gaussian 16, Revision C.01","author":"Frisch M. J.","year":"2016"},{"key":"e_1_2_7_55_1","volume-title":"MOLPRO, version 2018.1, A Package of ab\u00a0initio Programs","author":"Werner H.\u2010J.","year":"2018"},{"key":"e_1_2_7_56_1","doi-asserted-by":"publisher","DOI":"10.1002\/wcms.82"},{"key":"e_1_2_7_57_1","doi-asserted-by":"publisher","DOI":"10.1063\/1.4972015"},{"key":"e_1_2_7_58_1","doi-asserted-by":"publisher","DOI":"10.1021\/jp105358v"},{"key":"e_1_2_7_59_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.jpca.8b12324"},{"key":"e_1_2_7_60_1","doi-asserted-by":"crossref","first-page":"838","DOI":"10.1142\/5406","volume-title":"Conical Intersections: Electronic Structure, Dynamics & Spectroscopy","author":"Domcke W.","year":"2004"},{"key":"e_1_2_7_61_1","doi-asserted-by":"crossref","first-page":"249","DOI":"10.1142\/7803","volume-title":"Conical Intersections: Theory, Computation and Experiment","author":"Domcke W.","year":"2011"},{"key":"e_1_2_7_62_1","doi-asserted-by":"publisher","DOI":"10.1073\/pnas.0802769105"}],"container-title":["Photochemistry and Photobiology"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1111\/php.13560","content-type":"application\/pdf","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/full-xml\/10.1111\/php.13560","content-type":"application\/xml","content-version":"vor","intended-application":"text-mining"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/am-pdf\/10.1111\/php.13560","content-type":"application\/pdf","content-version":"am","intended-application":"syndication"},{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/pdf\/10.1111\/php.13560","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2023,8,23]],"date-time":"2023-08-23T23:10:36Z","timestamp":1692832236000},"score":1,"resource":{"primary":{"URL":"https:\/\/onlinelibrary.wiley.com\/doi\/10.1111\/php.13560"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2021,11,26]]},"references-count":61,"journal-issue":{"issue":"4","published-print":{"date-parts":[[2022,7]]}},"alternative-id":["10.1111\/php.13560"],"URL":"https:\/\/doi.org\/10.1111\/php.13560","archive":["Portico"],"relation":{},"ISSN":["0031-8655","1751-1097"],"issn-type":[{"value":"0031-8655","type":"print"},{"value":"1751-1097","type":"electronic"}],"subject":[],"published":{"date-parts":[[2021,11,26]]},"assertion":[{"value":"2021-10-15","order":0,"name":"received","label":"Received","group":{"name":"publication_history","label":"Publication History"}},{"value":"2021-11-09","order":1,"name":"accepted","label":"Accepted","group":{"name":"publication_history","label":"Publication History"}},{"value":"2021-11-26","order":2,"name":"published","label":"Published","group":{"name":"publication_history","label":"Publication History"}}]}}