{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,10,22]],"date-time":"2026-10-22T12:47:29Z","timestamp":1792673249314,"version":"4.5.0"},"reference-count":33,"publisher":"American Chemical Society (ACS)","issue":"42","license":[{"start":{"date-parts":[[2026,10,13]],"date-time":"2026-10-13T00:00:00Z","timestamp":1791849600000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"funder":[{"DOI":"10.13039\/501100006181","name":"Funda??o de Amparo ? Pesquisa do Estado da Bahia","doi-asserted-by":"publisher","id":[{"id":"10.13039\/501100006181","id-type":"DOI","asserted-by":"publisher"}]},{"DOI":"10.13039\/501100003593","name":"Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico","doi-asserted-by":"publisher","award":["441728\/2023-5"],"award-info":[{"award-number":["441728\/2023-5"]}],"id":[{"id":"10.13039\/501100003593","id-type":"DOI","asserted-by":"publisher"}]}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":[],"published-print":{"date-parts":[[2026,10,22]]},"abstract":"<jats:title>Abstract<\/jats:title>\n                  <jats:p>The microscopic origin of the hypersensitive luminescence of Eu3+ remains closely connected to how the local coordination environment perturbs the 4f electronic manifold. Here, we combine molecular dynamics, free-energy calculations, a multipolar analysis of the local electrostatic environment, and multireference electronic-structure calculations to examine hydrated Eu3+\u2013nitrate complexes beyond a scalar static-field description. A 12\u20136\u20134 Eu3+ model combined with TIP4P-Ew water yields an approximately nine-coordinate hydration shell and predicts the local outer-sphere nitrate basin to be more stable than the inner-sphere basin by about 2.6 kcal mol\u20131. Despite large changes in nitrate proximity, the total electric-field magnitude at Eu3+ remains essentially invariant: the inner\u2013far contrast is only 0.0022 V \u00c5\u20131, with a negligible standardized effect (d = 0.02). The same near invariance holds for the inner\u2013far contrasts of the total rank-2 and rank-3 electrostatic tensor norms. In contrast, the nitrate contribution is amplified by factors of approximately 4.5, 9.8, and 23.7 from electrostatic ranks k = 1 to 3, respectively, but is masked by progressively stronger solvent\u2013anion cancellation. The odd-rank k = 3 tensor nevertheless retains a clear coordination signature in its angular composition: the broad interconversion-region conditional ensemble exhibits an enhanced axial q = 0 fraction relative to the far-window reference (\u0394p0 = 0.181, source-cluster 95% CI [0.086, 0.275], d = 0.83). This qualitative q = 0 enrichment persists in matched explicit-MD stress tests in which the transferred Eu\u2013nitrate C4 coefficients are coherently scaled by \u00b120%. CASSCF\/SC-NEVPT2 calculations including spin\u2013orbit coupling provide a consistent description of the low-lying 4f6 manifolds, whereas an explicit quantitative treatment of 4f6\u20134f55d1 opposite-parity mixing remains beyond the balanced active-space description achieved here. These results show that hydrated Eu3+\u2013nitrate speciation is poorly encoded in |E|2 alone and is instead expressed through rank-dependent cancellation and the angular structure of the local electrostatic potential. The resulting tensorial descriptors provide a symmetry-resolved electrostatic framework that may inform microscopic interpretations of Eu3+ hypersensitive luminescence, while a quantitative connection to transition intensities requires an explicit and balanced treatment of the relevant opposite-parity electronic configurations.<\/jats:p>","DOI":"10.1021\/acs.jpcb.6c05370","type":"journal-article","created":{"date-parts":[[2026,10,13]],"date-time":"2026-10-13T09:01:52Z","timestamp":1791882112000},"page":"11268-11285","source":"Crossref","is-referenced-by-count":0,"title":["Beyond |\n                    <b>E<\/b>\n                    |2: Tensorial Electrostatic\nReorganization in Hydrated Eu3+\u2013Nitrate Complexes\nand Its Implications for Hypersensitive Luminescence"],"prefix":"10.1021","volume":"130","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7857-4539","authenticated-orcid":true,"given":"Murilo Sodre\u0301","family":"Marques","sequence":"first","affiliation":[{"name":"Universidade Federal do Oeste da Bahia (UFOB) , , Rua da Prainha, 1326, Morada Nobre , , ,","place":["Barreiras, Bahia, Brazil, CEP 47810-047"]}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"316","published-online":{"date-parts":[[2026,10,13]]},"reference":[{"key":"2026102207424151400_cit1","doi-asserted-by":"publisher","first-page":"541","DOI":"10.1021\/cr00051a004","article-title":"Terbium(III)\nand Europium(III) Ions as Luminescent Probes and Structural Tools","volume":"82","author":"Richardson","year":"1982","journal-title":"Chem. Rev."},{"key":"2026102207424151400_cit2","doi-asserted-by":"publisher","first-page":"1","DOI":"10.1016\/j.ccr.2015.02.015","article-title":"Interpretation\nof europium(III) spectra","volume":"295","author":"Binnemans","year":"2015","journal-title":"Coord. Chem. Rev."},{"key":"2026102207424151400_cit3","article-title":"Recent advances in the theoretical\nand experimental determination\nof intensity parameters for trivalent lanthanide complexes","volume":"475","author":"Dutra","year":"2023","journal-title":"Coord. Chem. Rev."},{"key":"2026102207424151400_cit4","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2024.215927","article-title":"Europium(III)\nCoordination Chemistry: Structure, Spectra and Hypersensitivity","volume":"517","author":"Thor","year":"2024","journal-title":"Coord. Chem. Rev."},{"key":"2026102207424151400_cit5","doi-asserted-by":"publisher","first-page":"750","DOI":"10.1103\/PhysRev.127.750","article-title":"Optical\nAbsorption Intensities of Rare-Earth Ions","volume":"127","author":"Judd","year":"1962","journal-title":"Phys.\nRev."},{"key":"2026102207424151400_cit6","doi-asserted-by":"publisher","first-page":"511","DOI":"10.1063\/1.1701366","article-title":"Intensities\nof Crystal Spectra of Rare-Earth Ions","volume":"37","author":"Ofelt","year":"1962","journal-title":"J. Chem.\nPhys."},{"key":"2026102207424151400_cit7","doi-asserted-by":"publisher","first-page":"1829","DOI":"10.1080\/00268977500103321","article-title":"Ligand-polarisation\nmodel for the\nintensities of 4f-4f transitions in lanthanide complexes","volume":"30","author":"Mason","year":"1975","journal-title":"Mol. Phys."},{"key":"2026102207424151400_cit8","first-page":"440","article-title":"Intensity\nparameters of 4f \u2013 4f transitions\nin the Eu3+ ion: A theoretical study including\noverlap effects","volume":"289","author":"Malta","year":"1998","journal-title":"Chem. Phys. Lett."},{"key":"2026102207424151400_cit9","first-page":"326","article-title":"Mechanisms\nof 4f \u2013 4f intensities","volume":"451","author":"Malta","year":"2008","journal-title":"J. Alloys Compd."},{"key":"2026102207424151400_cit10","doi-asserted-by":"publisher","first-page":"420","DOI":"10.1016\/j.jlumin.2015.08.016","article-title":"On the\ncalculation and interpretation of covalency in the intensity parameters\nof 4f\u20134f transitions in Eu3+ complexes based on\nthe chemical bond overlap polarizability","volume":"170","author":"Moura","year":"2016","journal-title":"J.\nLumin."},{"key":"2026102207424151400_cit11","first-page":"19450","article-title":"Theoretical\ninsights into the 4f-4f intensity parameters and luminescence quantum\nyields of lanthanide complexes","volume":"22","author":"Carneiro Neto","year":"2020","journal-title":"Phys. Chem.\nChem. Phys."},{"key":"2026102207424151400_cit12","doi-asserted-by":"crossref","first-page":"4830","DOI":"10.1063\/1.437372","article-title":"Hypersensitive\ntransitions in rare-earth ions","volume":"70","author":"Judd","year":"1979","journal-title":"J. Chem. 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Chem."},{"key":"2026102207424151400_cit17","doi-asserted-by":"publisher","first-page":"1923","DOI":"10.1021\/cr030726o","article-title":"Inorganic and bioinorganic\nsolvent exchange mechanisms","volume":"105","author":"Helm","year":"2005","journal-title":"Chem. Rev."},{"key":"2026102207424151400_cit18","first-page":"9665","article-title":"Metal Ion Modeling Using Classical\nForce Fields: Recent Advances and Future Directions","volume":"121","author":"Li","year":"2021","journal-title":"Chem. Rev."},{"key":"2026102207424151400_cit19","doi-asserted-by":"publisher","first-page":"883","DOI":"10.1021\/jp505875v","article-title":"Parameterization of Highly Charged\nMetal Ions Using the 12\u20136\u20134 LJ-Type Nonbonded Model\nin Explicit Water","volume":"119","author":"Li","year":"2015","journal-title":"J. Phys. Chem. 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