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While HFOs\u2019 rapid degradation minimizes their direct environmental accumulation, the ecological risks posed by their reactive degradation intermediates\u2014particularly hydrofluorocarbonyl oxide (HFCOO), a fluorinated Criegee intermediate generated via HFO-ozone reactions\u2014require urgent mechanistic clarification. The atmospheric persistence and chemical reactivity of HFCOO are intrinsically governed by its excited-state dynamics, where competing photochemical pathways determine whether it undergoes ultrafast dissociation or survives to mediate secondary pollutant formation. In this paper, we examine the deactivation mechanism of HFCOO by employing high-level electronic structure calculations and on-the-fly surface hopping dynamic simulations. Our results reveal that the first excited singlet state (S1) of HFCOO is a dark state populated via n\u03c0* transitions, while the second excited singlet state (S2), accessed through \u03c0\u03c0* transitions, is crucial for O\u2013O bond cleavage. We find that both syn- and anti-configurations of the S2 state exhibit rapid O\u2013O bond dissociation, producing hydrofluorocarbonyl (HFCO) and excited oxygen atoms within 30 and 50\u00a0fs, respectively. Our study underscores the ultrafast photodissociation dynamics of HFCOO in the atmosphere, contributing valuable insights into the environmental safety assessment of HFOs and improving atmospheric models for predicting their ecological impacts.<\/jats:p>","DOI":"10.1063\/5.0284203","type":"journal-article","created":{"date-parts":[[2025,8,11]],"date-time":"2025-08-11T12:08:23Z","timestamp":1754914103000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":4,"title":["Theoretical investigation of the photolysis mechanism of fluorinated Criegee intermediate HFCOO"],"prefix":"10.1063","volume":"163","author":[{"given":"Wenhui","family":"Yan","sequence":"first","affiliation":[{"name":"College of Science, China University of Petroleum (East China) 1 , Qingdao 266580, Shandong,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuxuan","family":"Liu","sequence":"additional","affiliation":[{"name":"College of Science, China University of Petroleum (East China) 1 , Qingdao 266580, Shandong,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Aihua","family":"Gao","sequence":"additional","affiliation":[{"name":"School of Physics and Optoelectronics Engineering, Ludong University 2 , Yantai 264025, Shandong,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Yuying","family":"Liu","sequence":"additional","affiliation":[{"name":"College of Science, China University of Petroleum (East China) 1 , Qingdao 266580, Shandong,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Xiaoqian","family":"Li","sequence":"additional","affiliation":[{"name":"College of Science, China University of Petroleum (East China) 1 , Qingdao 266580, Shandong,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3475-8245","authenticated-orcid":false,"given":"Zhijie","family":"Xu","sequence":"additional","affiliation":[{"name":"College of Science, China University of Petroleum (East China) 1 , Qingdao 266580, Shandong,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-2149-1702","authenticated-orcid":false,"given":"Li","family":"Zhao","sequence":"additional","affiliation":[{"name":"College of Science, China University of Petroleum (East China) 1 , Qingdao 266580, Shandong,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2025,8,11]]},"reference":[{"key":"2025081108081679500_c1","doi-asserted-by":"publisher","first-page":"107","DOI":"10.1016\/j.atmosenv.2014.01.060","article-title":"Gas-phase reactivity study of a series of hydrofluoroolefins (HFOs) toward OH radicals and Cl atoms at atmospheric pressure and 298 K","volume":"88","year":"2014","journal-title":"Atmos. 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