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However, to accurately resolve the fingerprints of the spectra for compounds containing transition-metal remains a formidable challenge because of the high density of low-lying states caused by the partially filled d- and s-orbitals. In our experiments, two adjacent peaks with a separation of 190 \u00b1 16\u00a0cm\u22121 of X band were observed in the photoelectron velocity map imaging of gas-phase RhO\u2212. The theoretical calculations, including spin\u2013orbit effects, predicted the zero-field splitting of the spatially nondegenerate ground states of the anion (3\u03a3\u2212) and its corresponding neutral molecule (4\u03a3\u2212) to be 133 and 32\u00a0cm\u22121, respectively. Based on our theoretical calculations, we suggest that the zero-field split states (\u03a341\/2\u2212 and 4\u03a33\/2\u2212) of RhO\u2212 coexist in the gas phase under our experimental condition, and the experimentally observed separation of the X band primarily stems from the detachment of the electron from the two spin\u2013orbit split states of the anion to those of the neutral species. The experimental spectra were further used to determine the electron affinity of RhO (1.581 \u00b1 0.002\u00a0eV). Accompanying harmonic vibrational frequencies \u03c9e and anharmonic constants \u03c9e\u03c7e of the two species are also obtained.<\/jats:p>","DOI":"10.1063\/5.0314997","type":"journal-article","created":{"date-parts":[[2026,2,13]],"date-time":"2026-02-13T12:24:49Z","timestamp":1770985489000},"update-policy":"https:\/\/doi.org\/10.1063\/aip-crossmark-policy-page","source":"Crossref","is-referenced-by-count":0,"title":["Observation of zero-field splitting in the anion photoelectron spectra of RhO\u2212: A combined experimental and theoretical study"],"prefix":"10.1063","volume":"164","author":[{"given":"Teng","family":"Cheng","sequence":"first","affiliation":[{"name":"Sino-French Institute of Nuclear Engineering and Technology, Sun Yat-sen University 1 , Zhuhai 519082,","place":["People\u2019s Republic of 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