{
  "abstract": "Department of Chemistry, Emory University Abstract Reliable computational prediction of excited-state redox potentials is central to the rational design of photoredox catalysts and requires accurate treatment of both ground-state redox thermochemistry and excited-state energetics. Although time-dependent density functional theory (TDDFT) provides a practical computational framework, it remains unclear whether these two components should use the same range-separation treatment and how the tuning of 2 range-separated hybrid (RSH) functionals, solvent response, and vibrational corrections affect that choice. We address these questions using a controlled benchmark of 16 structurally related N-aryl phenoxazine photocatalysts with experimental data obtained in dimethylacetamide, comparing default range-separation parameters with gas-phase tuning (GPγT) and two solution-phase tuning schemes based on equilibrium (PVγT) and nonequilibrium (SVγT) polarizable continuum models. The optimal treatment is quantity dependent: default ω values give the lowest errors for ground-state oxidation potentials, whereas solution-phase tuning with PVγT or SVγT reduces the mean absolute errors (MAEs) of transition energies to 0.10–0.13 eV; combining these component-specific treatments with zero-point or full vibrational corrections yields excited-state oxidation-potential MAEs of 0.11–0.13 V, although the required frequency calculations substantially increase the computational cost. These results reveal that applying a single range-separation treatment throughout the calculation is suboptimal and provide a physically motivated, quantity-specific computational strategy for solution-phase excited-state redox predictions that can now be tested across broader photocatalyst classes and solvent environments. 1 Introduction Photocatalysis has emerged as a versatile strategy for promoting chemical transformations through photoinduced electron transfer (PET) under mild conditions.1-8 Although ruthenium and iridium complexes have traditionally been widely used as photoredox catalysts (PCs),5, 9-12 organic PCs are emerging as cheaper and greener alternatives because their photophysical and redox properties can be systematically tuned through molecular design.2, 4, 8, 13-19",
  "abstract_shown": true,
  "affiliations": [
    "Department of Chemistry, Emory University, 1515 Dickey Dr, Atlanta, GA, United States, 30097"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 3,
  "authors": [
    {
      "affs": [
        0
      ],
      "name": "Ariel Gale",
      "orcid": "0000-0002-5710-3380"
    },
    {
      "affs": [
        0
      ],
      "name": "Bushra Alam",
      "orcid": "0000-0002-2584-6059"
    },
    {
      "affs": [
        0
      ],
      "name": "Fang Liu",
      "orcid": "0000-0003-1322-4997"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/epyrp1kajs626.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15009133/v1",
  "fulltext_url": null,
  "id": "epyrp1kajs626",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009133/v1",
  "language": null,
  "licence": "CC-BY-NC-ND",
  "licence_label": "CC BY-NC-ND",
  "licence_source": "journal",
  "licence_url": "https://creativecommons.org/licenses/by-nc-nd/4.0/",
  "metadata_licence": null,
  "native_subjects": [
    [
      "openalex",
      "3107|Advanced Chemical Physics Studies"
    ]
  ],
  "openalex": "W7213957676",
  "pdf_url": "https://chemrxiv.org/doi/pdf/10.26434/chemrxiv.15009133/v1",
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-21",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/epyrp1kajs626.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv.15009133",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009133/v1"
    }
  ],
  "subjects": [
    {
      "field": "physics",
      "origin": "openalex:3107|Advanced Chemical Physics Studies",
      "subfield": "amo"
    }
  ],
  "title": "Dissecting the Roles of Optimal Tuning, Solvation, and Vibrational Corrections in Excited-State Redox Potential Prediction for Organic Photoredox Catalysts",
  "title_text": "Dissecting the Roles of Optimal Tuning, Solvation, and Vibrational Corrections in Excited-State Redox Potential Prediction for Organic Photoredox Catalysts",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:19Z",
  "url": "https://research.draconitic.com/paper/epyrp1kajs626",
  "venue": "ChemRxiv",
  "versions": []
}