{
  "abstract": "In Marcus theory, reorganization energy links thermodynamics and kinetics for outer-sphere electron transfer, in which the redox centre exchanges an electron without changing its bonding to the electrode. Most electrocatalytic elementary steps are instead inner-sphere processes: the reacting intermediate is part of the interface, and surface bonding changes with charge transfer. A general thermodynamic definition of the full nonequilibrium preparation cost of such a bonded interface is lacking, leaving equilibrium descriptors and measured rates without a common theoretical basis. Here we define this quantity thermodynamically and provide a first-principles procedure for its calculation. A Legendre transform of fixed-potential thermodynamics yields an internal free-energy surface in which interfacial polarization and surface bond state are coupled variables, while electrode potential remains an external control. For a specified elementary event, inner-sphere reorganization energy is the finite free-energy cost of preparing a product-like interface before relaxation. Writing this cost as a Bregman difference separates it from the reaction driving force and relates it to a weighted integral of local interfacial stiffness. The classical Marcus expression is recovered as the one-dimensional harmonic charge-only limit of this framework. Applied to Volmer hydrogen oxidation on",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 3,
  "authors": [
    {
      "name": "Kaicong Yang"
    },
    {
      "name": "Bing Huang"
    },
    {
      "name": "Lin Zhuang",
      "orcid": "0000-0002-5642-6735"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/5tfwrh3g4k0xx.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009169/v1",
  "fulltext_url": null,
  "id": "5tfwrh3g4k0xx",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009169/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",
      "2105|Electrocatalysts for Energy Conversion"
    ]
  ],
  "openalex": "W7213865816",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009169/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-21",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/5tfwrh3g4k0xx.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv.15009169",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009169/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "openalex:2105|Electrocatalysts for Energy Conversion",
      "subfield": "electrochemistry-energy"
    }
  ],
  "title": "A theory of inner-sphere reorganization energy for electrocatalysis",
  "title_text": "A theory of inner-sphere reorganization energy for electrocatalysis",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:19Z",
  "url": "https://research.draconitic.com/paper/5tfwrh3g4k0xx",
  "venue": "ChemRxiv",
  "versions": []
}