{
  "abstract": "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+-nitrate complexes beyond a scalar static-field description. A 12-6-4 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-1. Despite large changes in nitrate proximity, the total electric-field magnitude at Eu3+ remains essentially invariant: the inner-far contrast is only 0.0022 V Å-1, with a negligible standardized effect (d = 0.02). The same near invariance holds for the inner-far 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-anion 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 (Δp0 = 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-nitrate C4 coefficients are coherently scaled by ±20%. CASSCF/SC-NEVPT2 calculations including spin-orbit coupling provide a consistent description of the low-lying 4f6 manifolds, whereas an explicit quantitative treatment of 4f6-4f55d1 opposite-parity mixing remains beyond the balanced active-space description achieved here. These results show that hydrated Eu3+-nitrate 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.",
  "abstract_shown": true,
  "affiliations": [
    "Programa de Pós─Graduação em Ciência dos Materiais (PROMAT) Centro das Ciências Exatas e das Tecnologias (CCET), Universidade Federal do Oeste da Bahia (UFOB), Rua da Prainha, 1326, Morada Nobre, CEP 47810-047Barreiras, Bahia, Brazil."
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 1,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Murilo Sodré Marques",
      "orcid": "0000-0001-7857-4539"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/dske2n7ap0waq.bib",
  "cited_by": 0,
  "doi": "10.1021/acs.jpcb.6c05370",
  "fulltext_url": "https://europepmc.org/articles/PMC13700006",
  "id": "dske2n7ap0waq",
  "issns": [
    "1520-6106",
    "1520-5207"
  ],
  "landing_url": "https://europepmc.org/article/MED/42910878",
  "language": "eng",
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "heading",
      "Article"
    ],
    [
      "heading",
      "B: Liquids; Chemical and Dynamical Processes in Solution"
    ],
    [
      "openalex",
      "2505|Lanthanide and Transition Metal Complexes"
    ]
  ],
  "openalex": "W7221711804",
  "pdf_url": "https://europepmc.org/articles/PMC13700006?pdf=render",
  "pmcid": "PMC13700006",
  "pmid": "42910878",
  "published": "2026-10-01",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/dske2n7ap0waq.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:20:14Z",
      "native_id": "MED:42910878",
      "source": "europepmc",
      "url": "https://europepmc.org/article/MED/42910878"
    },
    {
      "first_seen": "2026-10-30T12:20:31Z",
      "native_id": "PMC13700006",
      "source": "pmc",
      "url": "https://doi.org/10.1021/acs.jpcb.6c05370"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2505|Lanthanide and Transition Metal Complexes",
      "subfield": "materials-polymers"
    }
  ],
  "title": "Beyond |E|2: Tensorial Electrostatic Reorganization in Hydrated Eu3+-Nitrate Complexes and Its Implications for Hypersensitive Luminescence.",
  "title_text": "Beyond |E|2: Tensorial Electrostatic Reorganization in Hydrated Eu3+-Nitrate Complexes and Its Implications for Hypersensitive Luminescence.",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:36:29Z",
  "url": "https://research.draconitic.com/paper/dske2n7ap0waq",
  "venue": "The journal of physical chemistry. B",
  "versions": []
}