{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,7]],"date-time":"2026-08-07T16:00:25Z","timestamp":1786118425735,"version":"build-2736575974"},"reference-count":46,"publisher":"AIP Publishing","issue":"5","funder":[{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["92461301"],"award-info":[{"award-number":["92461301"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100001809","name":"National Natural Science Foundation of China","doi-asserted-by":"publisher","award":["U25D8003"],"award-info":[{"award-number":["U25D8003"]}],"id":[{"id":"10.13039\/501100001809","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":["pubs.aip.org"],"crossmark-restriction":true},"short-container-title":[],"published-print":{"date-parts":[[2026,8,7]]},"abstract":"<jats:p>We investigate the electronic structure of PtO via cryogenic anion photoelectron spectroscopy combined with relativistic multireference calculations, clarifying long-standing ambiguities in the assignment of its low-lying electronic manifold. Vibrationally resolved spectra covering the low-lying states are obtained via 193\u00a0nm photodetachment and 400\u00a0nm velocity map imaging (VMI) of PtO\u2212 anions cooled to 13\u00a0K. The adiabatic and vertical detachment energies are measured to be 2.16 and 2.29\u00a0eV, respectively, in good agreement with relativistic SOC-NEVPT2 predictions within 0.12\u00a0eV. High-resolution VMI reveals a fine-structure splitting of 1008 \u00b1 30\u00a0cm\u22121 in the X3\u03a3\u2212 ground state, quantitatively reproduced by SOC-NEVPT2 as a 959\u00a0cm\u22121 second-order spin\u2013orbit splitting. The two components display nearly identical vibrational structure, confirmed by Franck\u2013Condon simulations. At higher binding energy, an intense \u03c3-detachment feature is observed at 3.27\u00a0eV, providing a decisive spectroscopic anchor for reassessing the electronic manifold. Together with theoretical results, this feature establishes that the band at 2.73\u00a0eV corresponds to the A1\u0394 singlet state rather than to a widely split 3\u03a0-state manifold, as previously proposed. These results establish a revised, experimentally benchmarked electronic structure of PtO and demonstrate that cryogenic cooling combined with high-energy photodetachment is essential for resolving spin-orbit-coupled manifolds in heavy transition-metal oxides.<\/jats:p>","DOI":"10.1063\/5.0343681","type":"journal-article","created":{"date-parts":[[2026,8,6]],"date-time":"2026-08-06T15:52:05Z","timestamp":1786031525000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["Revisiting the electronic structure of PtO: Cryogenic photoelectron spectroscopy and relativistic insights"],"prefix":"10.1063","volume":"165","author":[{"ORCID":"https:\/\/orcid.org\/0009-0006-9908-2641","authenticated-orcid":false,"given":"Xueying","family":"Li","sequence":"first","affiliation":[{"name":"State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University 1 , Shanghai 200241,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8490-3773","authenticated-orcid":false,"given":"Zhubin","family":"Hu","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University 1 , Shanghai 200241,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-9644-1868","authenticated-orcid":false,"given":"Jian","family":"Zhang","sequence":"additional","affiliation":[{"name":"College of Chemistry and Chemical Engineering, Donghua University 2 , Shanghai 201620,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Zhenrong","family":"Sun","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University 1 , Shanghai 200241,","place":["China"]},{"name":"Collaborative Innovation Center of Extreme Optics, Shanxi University 3 , Taiyuan, Shanxi 030006,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1141-1193","authenticated-orcid":false,"given":"Yan","family":"Yang","sequence":"additional","affiliation":[{"name":"State Key Laboratory of Precision Spectroscopy, School of Physics and Electronic Science, East China Normal University 1 , Shanghai 200241,","place":["China"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"317","published-online":{"date-parts":[[2026,8,6]]},"reference":[{"key":"2026080611515721600_c1","doi-asserted-by":"publisher","first-page":"563","DOI":"10.1021\/cr00085a006","article-title":"Relativistic effects in structural chemistry","volume":"88","year":"1988","journal-title":"Chem. 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