{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,8,31]],"date-time":"2026-08-31T09:18:38Z","timestamp":1788167918157,"version":"build-2803163510"},"reference-count":98,"publisher":"American Chemical Society (ACS)","issue":"33","license":[{"start":{"date-parts":[[2026,8,9]],"date-time":"2026-08-09T00:00:00Z","timestamp":1786233600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/100009042","name":"Universidad de Sevilla","doi-asserted-by":"publisher","award":["NA"],"award-info":[{"award-number":["NA"]}],"id":[{"id":"10.13039\/100009042","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,8,24]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>Plutonium speciation in high-salinity media remains difficult to characterize, yet it largely governs the geochemical fate of PuO22+ in marine environments. EXAFS and UV\u2013vis measurements established that the evolution of specific spectral features correlates with the formation of successive aqua\u2013chloro complexes. These signals represent a superposition of coexisting species in equilibrium, masking the individual contributions of each complex. In this work, we address this limitation with a combination of the nuclear ensemble approach (NEA) and high-level quantum-mechanical calculations, accounting for the relativistic Hamiltonian, spin\u2013orbit coupling, and electron correlation, to isolate these overlapping contributions of the [PuO2(H2O)mCln]2\u2013n series and clarify the observed plutonyl speciation. The sensitivity of our methodology is quantified by comparing Wigner sampling against classical molecular dynamics (MD) trajectories. The results establish UV\u2013vis spectroscopy as a high-resolution probe of the equatorial ligand field and provide a molecular basis for Pu(VI) speciation in saline environments.<\/jats:p>","DOI":"10.1021\/acs.inorgchem.6c02837","type":"journal-article","created":{"date-parts":[[2026,8,9]],"date-time":"2026-08-09T20:01:43Z","timestamp":1786305703000},"page":"19417-19428","source":"Crossref","is-referenced-by-count":0,"title":["Aqua\u2013Chloro\nComplexes of Plutonyl in Hydrochloric\nAqueous Solutions: Theoretical Study of Individual Contributions to\nXAS and UV\u2013Vis Spectra"],"prefix":"10.1021","volume":"65","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7461-664X","authenticated-orcid":true,"given":"Gema","family":"Raposo-Herna\u0301ndez","sequence":"first","affiliation":[{"name":"University of Seville , , ,","place":["Seville, Spain, 41012"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3751-2395","authenticated-orcid":true,"given":"Rafael R.","family":"Pappalardo","sequence":"additional","affiliation":[{"name":"University of Seville , , ,","place":["Seville, Spain, 41012"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-5265-1396","authenticated-orcid":true,"given":"Andrea","family":"Melchior","sequence":"additional","affiliation":[{"name":"Universita\u0300 di Udine , , ,","place":["Udine, Italy, 33100"]}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-8367-9105","authenticated-orcid":true,"given":"Enrique Sa\u0301nchez","family":"Marcos","sequence":"additional","affiliation":[{"name":"University of Seville , , ,","place":["Seville, Spain, 41012"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,8,9]]},"reference":[{"key":"2026083104370010200_cit1","doi-asserted-by":"publisher","first-page":"22","DOI":"10.7185\/geochemlet.1814","article-title":"Toxic Anthropogenic\nPollutants Reach the Deepest Ocean on Earth","volume":"7","author":"Dasgupta","year":"2018","journal-title":"Geochem. 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