{
  "abstract": "Point defects in solid-state materials are conventionally modeled as lattice-derived defects, generated by adding or removing atoms from symmetric bulk lattice structures, followed by local geometry optimization. This approach often yields symmetric, weakly relaxed local minima that remain close to the parent lattice. Here, we show that this assumption can fail qualitatively for vacancies in many metal oxides. Rather than retaining a lattice-derived geometry with localized holes on oxygen sites, cation vacancies can drive extensive reconstruction, producing defect configurations in which the O-O bonds and O-O-O chains become the preferred charge-compensation motifs. We combined the minima hopping (MH) structure prediction algorithm with machine-learned interatomic potentials (MLIPs), hybrid QM/MM embedded-cluster calculations, and periodic density functional theory (DFT) calculations to investigate cation vacancies across a broad series of metal oxides. Our results show a clear oxidation-state-dependent trend. In the charge-neutral state, cation vacancies in oxides with formal oxidation states of +4 or higher favor reconstructed defect configurations containing O-O bonds or O-O-O chains with bond lengths of approximately 1.4 Å, lowering the defect formation energy by up to several electronvolts relative to the conventional structure. By contrast, in oxides with lower cation oxidation states, such reconstructions are generally unfavorable at charge neutrality but can become energetically more favorable at positive charge states. These findings define oxygen-bond formation as a general reconstruction pathway for cation vacancies in metal oxides and show that global structure searches are essential for predictive defect modeling beyond conventional lattice-derived local minima.",
  "abstract_shown": true,
  "affiliations": [
    "National & Local Joint Engineering Research Center for Applied Technology of Hybrid Nanomaterials, Henan University, Kaifeng475004, P. R. China.",
    "Kathleen Lonsdale Materials Chemistry, Department of Chemistry, University College London, 20 Gordon Street, LondonWC1H0AJ, United Kingdom.",
    "Department of Physics, University of Basel, Klingelbergstrasse 82, CH-4056Basel, Switzerland.",
    "Institute of Photonic Chips, University of Shanghai for Science and Technology, 580 Jungong Road, Shanghai200093, China.",
    "Scientific Computing Department, STFC Daresbury Laboratory, WarringtonWA4 4AD, Cheshire, United Kingdom.",
    "School of Engineering and Design, London South Bank University, 103 Borough Road, LondonSE1 OAA, United Kingdom.",
    "School of Chemistry, Cardiff University, Park Place, CardiffCF10 1AT, United Kingdom."
  ],
  "article_type": "research article",
  "arxiv": null,
  "author_total": 14,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Taifeng Liu",
      "orcid": "0000-0002-6869-7022"
    },
    {
      "affs": [
        1,
        2
      ],
      "name": "Xingfan Zhang"
    },
    {
      "affs": [
        1
      ],
      "name": "Jamal Abdul Nasir",
      "orcid": "0000-0002-0474-1610"
    },
    {
      "affs": [
        1,
        3
      ],
      "name": "Qing Hou"
    },
    {
      "affs": [
        1,
        4
      ],
      "name": "Liam Morgan",
      "orcid": "0009-0009-3457-7581"
    },
    {
      "affs": [
        1
      ],
      "name": "Jingcheng Guan"
    },
    {
      "affs": [
        4
      ],
      "name": "Thomas Durrant"
    },
    {
      "affs": [
        4
      ],
      "name": "You Lu",
      "orcid": "0000-0002-7524-4179"
    },
    {
      "affs": [
        4
      ],
      "name": "Thomas W Keal",
      "orcid": "0000-0001-8747-3975"
    },
    {
      "affs": [
        5
      ],
      "name": "John Buckeridge",
      "orcid": "0000-0002-2537-5082"
    },
    {
      "affs": [
        1
      ],
      "name": "Scott M Woodley",
      "orcid": "0000-0003-3418-9043"
    },
    {
      "affs": [
        2
      ],
      "name": "Stefan Goedecker"
    },
    {
      "affs": [
        1,
        6
      ],
      "name": "C Richard A Catlow",
      "orcid": "0000-0002-1341-1541"
    },
    {
      "affs": [
        1
      ],
      "name": "Alexey A Sokol",
      "orcid": "0000-0003-0178-1147"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/6xypre0s3frq6.bib",
  "cited_by": 0,
  "doi": "10.1021/jacs.6c15378",
  "fulltext_url": "https://europepmc.org/articles/PMC13693452",
  "id": "6xypre0s3frq6",
  "issns": [
    "0002-7863",
    "1520-5126"
  ],
  "landing_url": "https://europepmc.org/article/MED/42912303",
  "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": [
    [
      "openalex",
      "2505|Machine Learning in Materials Science"
    ]
  ],
  "openalex": "W7220859257",
  "pdf_url": "https://europepmc.org/articles/PMC13693452?pdf=render",
  "pmcid": "PMC13693452",
  "pmid": "42912303",
  "published": "2026-10-01",
  "publisher": null,
  "ris": "https://research.draconitic.com/paper/6xypre0s3frq6.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:20:14Z",
      "native_id": "MED:42912303",
      "source": "europepmc",
      "url": "https://europepmc.org/article/MED/42912303"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2505|Machine Learning in Materials Science",
      "subfield": "materials-polymers"
    }
  ],
  "title": "Cation Vacancies with and without O-O Dimerization: Identifying Reconstructed Defect Configurations in Metal Oxides.",
  "title_text": "Cation Vacancies with and without O-O Dimerization: Identifying Reconstructed Defect Configurations in Metal Oxides.",
  "type": "peer-reviewed",
  "updated_at": "2026-10-30T12:20:14Z",
  "url": "https://research.draconitic.com/paper/6xypre0s3frq6",
  "venue": "Journal of the American Chemical Society",
  "versions": []
}