{
  "abstract": "The hydrogen evolution reaction is orders of magnitude faster in acid than in base on the same electrode, a pH effect that first-principles calculations have not quantitatively reproduced. We trace this failure to the treatment of the ions: standard density functionals with standard solvation treatments undersolvate hydroxide–the ionic product of alkaline hydrogen evolution–by more than 1 eV against experiment and coupled cluster benchmarks, an error that tracks the functional’s self-interaction error. A screened hybrid functional with reduced self-interaction error yields Au(111) Volmer barriers whose acidalkaline difference falls within the measured range of onset-potential separations, whereas semi-local functionals predict zero to three times the measured value. Quantitative computational electrocatalysis therefore demands functionals benchmarked jointly against ion solvation thermochemistry and molecule-surface energetics.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemical Engineering",
    "Texas Tech University",
    "Department of Chemical and Biological Engineering",
    "Northwestern University",
    "Mork Family Department of Chemical Engineering and Materials Science",
    "University of Southern California",
    "Department of Chemistry"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 8,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Samuel A. Olusegun"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Salem Rice"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Danielle Getz"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Veena S. Chauhan"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Luis H.Z. Feistel"
    },
    {
      "affs": [
        4,
        5,
        6
      ],
      "name": "Shaama M. Sharada"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Linsey C. Seitz"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Joseph A. Gauthier",
      "orcid": "0000-0001-9542-0988"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/2abkfpn1dvykd.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15007494/v2",
  "fulltext_url": null,
  "id": "2abkfpn1dvykd",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007494/v2",
  "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",
      "2105|Electrocatalysts for Energy Conversion"
    ]
  ],
  "openalex": "W7222217319",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15007494/v2",
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-15",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/2abkfpn1dvykd.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:24Z",
      "native_id": "10.26434/chemrxiv.15007494",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15007494/v2"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2105|Electrocatalysts for Energy Conversion",
      "subfield": "electrochemistry-energy"
    }
  ],
  "title": "The pH effect in hydrogen evolution is a consequence of creating a solvated hydroxide ion",
  "title_text": "The pH effect in hydrogen evolution is a consequence of creating a solvated hydroxide ion",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:24Z",
  "url": "https://research.draconitic.com/paper/2abkfpn1dvykd",
  "venue": "ChemRxiv",
  "versions": []
}