{
  "abstract": "The oxidation of water at surfaces requires reactive and metastable intermediates such as surface adsorbed and often electron deficient oxygen. An outstanding question is whether forming these intermediates depends primarily on the energetics of adsorption associated with the reorganization of bonds at a vacuum interface, or whether it must include contributions from the re-orientation of water dipoles and ions within the aqueous electrolyte that could lower the free energy. Time-resolved mid-infrared experiments in an attenuated total reflection geometry have detected the terminal oxygen, the titanium oxyl, by a vibration that forms underneath it. The vibration was shown to couple to the librational modes of water by a Fano resonance. Here, we show that the picosecond formation of the titanium oxyl’s vibration is invariant across interfaces that change the density of librational modes (air, pH 7, pH 13, and pD 13), as detected by significant modifications of the coupled line-shape. Across the interfaces, we report a common rate constant (0.56 +/- 0.08 ps) and half rise (1.76 +/- 0.39 ps). This demonstrates that the reorganizational energy associated with solvent re-orientation is limited to affecting the ultrafast (400 fs) time resolution of the experiment characteristic of activation-less reactions and bond-reorganization. Furthermore, the formation kinetics are well-fit by a logistic function that describes an autocatalytic reaction and the surface population of titanium oxyl with excitation is well modelled by the Langevin equation. Both suggest that the invariant picosecond rise is due to a re-orientation of the titanium oxyl and its p-polarized vibrational dipole with respect to the strong Helmholtz electric field common to the probed interfaces.",
  "abstract_shown": true,
  "affiliations": [],
  "article_type": null,
  "arxiv": null,
  "author_total": 3,
  "authors": [
    {
      "name": "Paul Zayka"
    },
    {
      "name": "James Stewart"
    },
    {
      "name": "Tanja Cuk"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/a7weegpqz4dc1.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008992/v1",
  "fulltext_url": null,
  "id": "a7weegpqz4dc1",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008992/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|Spectroscopy and Quantum Chemical Studies"
    ]
  ],
  "openalex": "W7213461450",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15008992/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-17",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/a7weegpqz4dc1.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv.15008992",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008992/v1"
    }
  ],
  "subjects": [
    {
      "field": "physics",
      "origin": "openalex:3107|Spectroscopy and Quantum Chemical Studies",
      "subfield": "amo"
    }
  ],
  "title": "Formation of the titanium oxyl at an electrochemical interface: limiting the role of solvent re-orientation in strong electric fields",
  "title_text": "Formation of the titanium oxyl at an electrochemical interface: limiting the role of solvent re-orientation in strong electric fields",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:19Z",
  "url": "https://research.draconitic.com/paper/a7weegpqz4dc1",
  "venue": "ChemRxiv",
  "versions": []
}