{
  "abstract": "Semilocal density-functional approximations fail to describe the formation of anionic enolates in thio-Michael additions, the bond-forming step of covalent-inhibitor warheads; range-separated hybrids, which reintroduce long-range exact exchange, are required. Across the published CCSD(T)validated reaction pathways of eight warheads, we show that Skala—a deep-learned semilocal functional containing no exact exchange—matches the range-separated hybrid reference for the activation barriers, enolate geometries and relaxed reactant structures, outperforming the global hybrid B3LYP at meta-GGA cost. The one signature it does not reproduce is the orbital one: its Koopmans ionization potential stays at the semilocal scale, because the ionization-potential theorem constrains the exchange potential, not the energy. Skala thus captures the effect of exact exchange in the total energy, from training data alone.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 5,
  "authors": [
    {
      "name": "Connor Williamson"
    },
    {
      "name": "Ross Amory"
    },
    {
      "name": "David M. Rogers"
    },
    {
      "name": "Katherine Inzani"
    },
    {
      "name": "Jonathan D. Hirst",
      "orcid": "0000-0002-2726-0983"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/awhmm2dassr2p.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009612/v1",
  "fulltext_url": null,
  "id": "awhmm2dassr2p",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009612/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": "W7214730341",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009612/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-29",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/awhmm2dassr2p.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:21Z",
      "native_id": "10.26434/chemrxiv.15009612",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009612/v1"
    }
  ],
  "subjects": [
    {
      "field": "physics",
      "origin": "openalex:3107|Advanced Chemical Physics Studies",
      "subfield": "amo"
    }
  ],
  "title": "Capturing the Effect of Exact Exchange in Thio-Michael Additions with a Machine-Learned Functional at Meta-GGA Cost",
  "title_text": "Capturing the Effect of Exact Exchange in Thio-Michael Additions with a Machine-Learned Functional at Meta-GGA Cost",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:21Z",
  "url": "https://research.draconitic.com/paper/awhmm2dassr2p",
  "venue": "ChemRxiv",
  "versions": []
}