{
  "abstract": "In carbonate-rich aqueous environments relevant to spent nuclear fuel storage, radiolytic H2O2 and carbonate species promote the formation of uranyl peroxo-carbonate complexes under mild conditions. These complexes are poorly characterized spectroscopically, with many assignments remaining controversial. This work presents the first isotope validated solution-phase identification of the peroxo-dicarbonato species Mx[UO2(O2)­(CO3)2](4–x)– (M = Na+ or K+) achieved through Raman and 18O-labeled H2O2 Fourier-transform infrared (FTIR) spectroscopy, combined with density functional theory (DFT) calculations. Key vibrational signatures distinguish the peroxo-dicarbonato complex from those of the tricarbonato complex [UO2(CO3)3]4–, including the νs(U–Oyl) stretch at 765–769 cm–1, the ν­(U–Operoxo) mode at 400–452 cm–1, and the ν­(O–O) stretch at 845–850 cm–1, which shifts upon 18O substitution. FTIR data further confirm these assignments, providing the first infrared evidence of a uranyl peroxo-carbonato complex in aqueous solution. DFT calculations validate the observed frequencies and isotope shifts, clarifying the role of solvation and countercation effects. These results clarify uranyl peroxo-carbonato speciation, resolving long-standing ambiguities and establishing a robust spectroscopic framework for applications in uranium fuel dissolution, environmental mobility, and long-term waste stability.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 8,
  "authors": [
    {
      "name": "Julien Margate"
    },
    {
      "name": "Leonard Floarea"
    },
    {
      "name": "Charles Coubronne"
    },
    {
      "name": "Elise Berrier"
    },
    {
      "name": "Gaëlle Milanole"
    },
    {
      "name": "Florent Réal"
    },
    {
      "name": "Murielle Rivenet"
    },
    {
      "name": "Valérie Vallet"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/644f9s920rgf4.bib",
  "cited_by": 0,
  "doi": "10.1021/acs.inorgchem.6c00907",
  "fulltext_url": null,
  "id": "644f9s920rgf4",
  "issns": [
    "0020-1669",
    "1520-510X"
  ],
  "landing_url": "https://hal.science/hal-05513260v1",
  "language": "en",
  "licence": "CC-BY-NC-SA-4.0",
  "licence_label": "CC BY-NC-SA 4.0",
  "licence_source": "article",
  "licence_url": "https://creativecommons.org/licenses/by-nc-sa/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "hal",
      "0.chim"
    ],
    [
      "hal",
      "0.phys"
    ],
    [
      "hal",
      "1.chim.theo"
    ],
    [
      "hal",
      "1.phys.phys"
    ],
    [
      "hal",
      "2.phys.phys.phys-chem-ph"
    ],
    [
      "openalex",
      "1604|Radioactive element chemistry and processing"
    ]
  ],
  "openalex": "W7162415297",
  "pdf_url": "https://hal.science/hal-05513260/document",
  "pmcid": null,
  "pmid": null,
  "published": "2026-05-26",
  "publisher": "American Chemical Society",
  "ris": "https://research.draconitic.com/paper/644f9s920rgf4.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:42Z",
      "native_id": "hal-05513260",
      "source": "hal",
      "url": "https://hal.science/hal-05513260v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "hal:2.phys.phys.phys-chem-ph",
      "subfield": "physical"
    },
    {
      "field": "chemistry",
      "origin": "hal:1.chim.theo",
      "subfield": "theoretical"
    },
    {
      "field": "physics",
      "origin": "hal:0.phys",
      "subfield": "general"
    }
  ],
  "title": "Synthesis and Vibrational Identification of the Uranyl Peroxodicarbonato [UO2(O2)(CO3)2]4–: Insights into Peroxide-Carbonate Bonding from 18O Labeling, DFT, and QTAIM Analysis",
  "title_text": "Synthesis and Vibrational Identification of the Uranyl Peroxodicarbonato [UO2(O2)(CO3)2]4–: Insights into Peroxide-Carbonate Bonding from 18O Labeling, DFT, and QTAIM Analysis",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:17:42Z",
  "url": "https://research.draconitic.com/paper/644f9s920rgf4",
  "venue": "Inorganic Chemistry",
  "versions": []
}