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Despite numerous studies, major aspects of its ultrafast photochemistry remain unresolved because the early excited-state dynamics have so far eluded spectroscopic observation. This has led to the long-held assumption that ultrafast dissociation of gas-phase Fe(CO)5 proceeds exclusively on the singlet manifold. Herein, we present a combined experimental\u2013theoretical study employing ultrafast extreme ultraviolet transient absorption spectroscopy near the Fe M2,3-edge, which features spectral evolution on 100 fs and 3 ps time scales, alongside high-level electronic structure theory, which enables characterization of the molecular geometries and electronic states involved in the ultrafast photodissociation of Fe(CO)5. We assign the 100 fs evolution to spectroscopic signatures associated with intertwined structural and electronic dynamics on the singlet metal-centered states during the first CO loss and the 3 ps evolution to the competing dissociation of Fe(CO)4 along the lowest singlet and triplet surfaces to form Fe(CO)3. Calculations of transient spectra in both singlet and triplet states as well as spin\u2013orbit coupling constants along key structural pathways provide evidence for intersystem crossing to the triplet ground state of Fe(CO)4. Thus, our work presents the first spectroscopic detection of transient excited states during ultrafast photodissociation of gas-phase Fe(CO)5 and challenges the long-standing assumption that triplet states do not play a role in the ultrafast dynamics.<\/jats:p>","DOI":"10.1021\/jacs.4c07523","type":"journal-article","created":{"date-parts":[[2024,8,2]],"date-time":"2024-08-02T08:42:13Z","timestamp":1722588133000},"page":"22711-22723","source":"Crossref","is-referenced-by-count":20,"title":["Femtosecond Core-Level Spectroscopy Reveals Involvement of Triplet States in the Gas-Phase Photodissociation of Fe(CO)5"],"prefix":"10.1021","volume":"146","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-8845-8881","authenticated-orcid":true,"given":"Jan","family":"Tro\u00df","sequence":"first","affiliation":[{"name":"Sandia National Laboratories , , , ,","place":["Livermore, California, United States, 94550"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Juan E.","family":"Arias-Martinez","sequence":"additional","affiliation":[{"name":"University of California, Berkeley , , , ,","place":["Berkeley, California, United States, 94720"]},{"name":"Lawrence Berkeley National Laboratory , , , ,","place":["Berkeley, California, United States, 94720"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8302-4750","authenticated-orcid":true,"given":"Kay","family":"Carter-Fenk","sequence":"additional","affiliation":[{"name":"University of California, Berkeley , , , ,","place":["Berkeley, California, United States, 94720"]},{"name":"Lawrence Berkeley National Laboratory , , , ,","place":["Berkeley, California, United States, 94720"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-3619-8915","authenticated-orcid":true,"given":"Neil C.","family":"Cole-Filipiak","sequence":"additional","affiliation":[{"name":"Sandia National Laboratories , , , ,","place":["Livermore, California, United States, 94550"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Paul","family":"Schrader","sequence":"additional","affiliation":[{"name":"Sandia National Laboratories , , , ,","place":["Livermore, California, United States, 94550"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-6705-8755","authenticated-orcid":true,"given":"Laura M.","family":"McCaslin","sequence":"additional","affiliation":[{"name":"Sandia National Laboratories , , , ,","place":["Livermore, California, United States, 94550"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-4309-6669","authenticated-orcid":true,"given":"Martin","family":"Head-Gordon","sequence":"additional","affiliation":[{"name":"University of California, Berkeley , , , ,","place":["Berkeley, California, United States, 94720"]},{"name":"Lawrence Berkeley National Laboratory , , , ,","place":["Berkeley, California, United States, 94720"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-5076-3725","authenticated-orcid":true,"given":"Krupa","family":"Ramasesha","sequence":"additional","affiliation":[{"name":"Sandia National Laboratories , , , ,","place":["Livermore, California, United States, 94550"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2024,8,2]]},"reference":[{"key":"2026080614063240600_cit1","doi-asserted-by":"publisher","first-page":"101","DOI":"10.1016\/S0010-8545(98)00201-X","article-title":"Homogeneous photo catalysis by transition metal complexes","volume":"182","author":"Hennig","year":"1999","journal-title":"Coord. 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