{
  "abstract": "L 3 -edge valence-to-core resonant inelastic X-ray scattering (V2C-RIXS) is applied to thorium for the first time, demonstrating the technique’s sensitivity to actinide 6d-orbital participation in bonding. This sensitivity is exploited to identify states arising from delocalized valence molecular orbitals of predominantly 6d character in two trithorium clusters, [{Th(η 8 -C 8 H 8 )(µ 3 -Cl) 2 } 3 {K(DME) 2 } 2 ] 2b and [K(2.2.2-cryptand)] [{Th(η 8 -C 8 H 8 )(µ 3 -Cl) 2 } 3 ] 3 . Density functional theory based restricted open-shell configuration interaction with singles (DFT/ROCIS) accurately reproduces the V2C-RIXS spectra of 2b and 3 , enabling the quantitative assignment of inelastic intensity to the population of a delocalized three-center 6d z2 σ-bonding molecular orbital. In contrast, L 3 -edge high-energy-resolution fluorescence detection (HERFD) XANES spectra exhibit negligible sensitivity to 6d electron population in these compounds. This study, thus, establishes a clear distinction between the two techniques and identifies V2C-RIXS as a unique probe of 6d orbital contributions to bonding in actinide compounds.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry",
    "University of Manchester",
    "University of Manchester at Harwell",
    "Centre for Radiochemistry Research, University of Manchester, Oxford Road, Manchester, UK, M13 9PL",
    "Harwell Science and Innovation Campus"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 11,
  "authors": [
    {
      "affs": [
        0,
        1,
        2,
        3
      ],
      "name": "Charles P. Moir"
    },
    {
      "affs": [
        0,
        1,
        3
      ],
      "name": "Josef Tomeček"
    },
    {
      "affs": [
        0,
        1,
        2,
        3
      ],
      "name": "Nathan M. Alcock"
    },
    {
      "affs": [
        0,
        1,
        3
      ],
      "name": "John A. Seed"
    },
    {
      "affs": [
        0,
        1,
        3
      ],
      "name": "Xinglan Deng"
    },
    {
      "affs": [
        0,
        1,
        2,
        3,
        4
      ],
      "name": "Zhibo Qi"
    },
    {
      "affs": [
        0,
        1,
        2,
        3
      ],
      "name": "Myron S. Huzan"
    },
    {
      "affs": [
        4
      ],
      "name": "Shusaku Hayama"
    },
    {
      "affs": [
        0,
        1,
        3
      ],
      "name": "Stephen T. Liddle"
    },
    {
      "affs": [
        0,
        1,
        3
      ],
      "name": "Nikolas Kaltsoyannis"
    },
    {
      "affs": [
        0,
        1,
        2,
        3
      ],
      "name": "Michael L. Baker",
      "orcid": "0000-0002-8246-3177"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/aczsmyf0kgn08.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008222/v1",
  "fulltext_url": null,
  "id": "aczsmyf0kgn08",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008222/v1",
  "language": null,
  "licence": "CC-BY",
  "licence_label": "CC BY",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "3108|X-ray Spectroscopy and Fluorescence Analysis"
    ]
  ],
  "openalex": "W7207763288",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008222/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-02",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/aczsmyf0kgn08.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:17Z",
      "native_id": "10.26434/chemrxiv.15008222",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008222/v1"
    }
  ],
  "subjects": [
    {
      "field": "physics",
      "origin": "openalex:3108|X-ray Spectroscopy and Fluorescence Analysis",
      "subfield": "applied-instrumentation"
    }
  ],
  "title": "Valence Delocalization in Trithorium Clusters Identified via Valence-to-Core Resonant Inelastic X-ray Scattering",
  "title_text": "Valence Delocalization in Trithorium Clusters Identified via Valence-to-Core Resonant Inelastic X-ray Scattering",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:17Z",
  "url": "https://research.draconitic.com/paper/aczsmyf0kgn08",
  "venue": "ChemRxiv",
  "versions": []
}