{
  "abstract": "Two benchmark sets of dissociation energies of diatomic transition-metal complexes have been assembled from previously published data, with selected reference values reassessed or updated where necessary, and used to evaluate a variety of density functionals. The BDE41 set of 41 3d complexes based on both experimental data and phaseless auxiliary-field quantum Monte Carlo reference data is the statistically more robust of the two sets. A number of local hybrid functionals top the list with the smallest deviations, including the strong-correlation (sc) corrected scLH22t and scLH22ta, and the range-separated variant ωLH23tP, followed by the previous top-performing global hybrids B97 and B97-1. While global hybrids and local hybrids without sc-corrections tend to underbind on average, sc-corrections may shift this to moderate overbinding. Nitride and oxide complexes account for much of the underbinding. Functionals based on neural-network local mixing functions underbind more clearly also in other cases, confirming that for these very flexible constructions a lack of transition-metal training data is more harmful to transferability than for less flexible functionals with heuristic mixing functions. The smaller and somewhat less reliable HBDE17 set of 4d/5d complexes reinforces several of the observations but appears to disfavor large exact-exchange admixtures even more strongly. In this case carbide and oxide complexes provide the most pronounced challenges. Nevertheless, several functionals perform not much worse than the most sophisticated post-Hartree-Fock reference calculations currently available based on CCSD(T) with multi-reference corrections. These benchmark sets may also prove useful for training and evaluating new approximate methods, an application we intend to explore in future work.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 4,
  "authors": [
    {
      "name": "Adrian Rodriguez Weber"
    },
    {
      "name": "Nóra Kovács"
    },
    {
      "name": "Artur Wodyński"
    },
    {
      "name": "Martin Kaupp",
      "orcid": "0000-0003-1582-2819"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/5axv72mjd8g88.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15011045/v1",
  "fulltext_url": null,
  "id": "5axv72mjd8g88",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011045/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",
      "3107|Advanced Chemical Physics Studies"
    ]
  ],
  "openalex": "W7223710326",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15011045/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-26",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/5axv72mjd8g88.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:26Z",
      "native_id": "10.26434/chemrxiv.15011045",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011045/v1"
    }
  ],
  "subjects": [
    {
      "field": "physics",
      "origin": "openalex:3107|Advanced Chemical Physics Studies",
      "subfield": "amo"
    }
  ],
  "title": "An Evaluation of Modern Density Functionals for the Bond Dissociation Energies of Diatomic Transition Metal Complexes.",
  "title_text": "An Evaluation of Modern Density Functionals for the Bond Dissociation Energies of Diatomic Transition Metal Complexes.",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:26Z",
  "url": "https://research.draconitic.com/paper/5axv72mjd8g88",
  "venue": "ChemRxiv",
  "versions": []
}