{
  "abstract": "Lithium–sulfur cycle life is limited by dissolved LiyS q x polysulfides whose speciation remains disputed. We benchmark the complete matrix (y = 0–2, q = 0 to −2, x = 1–8) in the gas phase, tetraglyme and dimethyl sulfoxide: 248 M06-2X/SMD thermochemistries, 132 refined by single-point CCSD. The convex hull, S8 → Li2S6 → Li2S4 → Li2S3 → Li2S2 → Li2S, is identical in both solvents, and every exergonic long-chain comproportionation delivers Li2S6. QTAIM analysis of the CCSD densities separates covalent S–S from electrostatic Li–S bonding, transferably between solvents. Solvation makes S 2–x the dominant lithium-free 1 charge state and places both legs of the shuttle on that branch. Infrared and Raman spectra of prepared solutions test the vibrational predictions and track the chain-length distribution through one band envelope. The open dataset is a calibrated reference for force-field, machine-learned and continuum battery models.",
  "abstract_shown": true,
  "affiliations": [
    "International Center of Physics",
    "Institute of Physics, University of Brasília",
    "National Laboratory of the Rockies",
    "Brigham Young University",
    "Federal Institute of Education, Science and Technology of Goiás",
    "Theoretical and Structural Chemistry Group of Anápolis",
    "State University of Goiás",
    "Department of Chemical Engineering",
    "University of Colorado Boulder",
    "Institute of Physics",
    "University of Brasília"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 13,
  "authors": [
    {
      "name": "Rafael Ferreira Ferreira de Menezes"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Tiago Cassiano"
    },
    {
      "affs": [
        2
      ],
      "name": "Lydia Meyer"
    },
    {
      "affs": [
        3
      ],
      "name": "Jason Porter"
    },
    {
      "affs": [
        4,
        5,
        6
      ],
      "name": "Flavio O. Sanches-Neto"
    },
    {
      "affs": [
        3
      ],
      "name": "Benjamin Diehl"
    },
    {
      "affs": [
        3
      ],
      "name": "Joanna Maratos"
    },
    {
      "affs": [
        3
      ],
      "name": "Tristan Schiess"
    },
    {
      "affs": [
        3
      ],
      "name": "Jared Landetta Espinoza"
    },
    {
      "name": "Ana Costa"
    },
    {
      "affs": [
        2
      ],
      "name": "Andrew Colclasure"
    },
    {
      "affs": [
        7,
        8,
        9,
        10
      ],
      "name": "Ricardo Gargano"
    },
    {
      "affs": [
        7,
        8,
        9,
        10
      ],
      "name": "Kayla G. Sprenger"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/emb8r3c16y5t4.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15010681/v1",
  "fulltext_url": null,
  "id": "emb8r3c16y5t4",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010681/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",
      "2208|Advanced Battery Materials and Technologies"
    ]
  ],
  "openalex": "W7223070971",
  "pdf_url": null,
  "pmcid": null,
  "pmid": null,
  "published": "2026-10-19",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/emb8r3c16y5t4.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:24Z",
      "native_id": "10.26434/chemrxiv.15010681",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15010681/v1"
    }
  ],
  "subjects": [
    {
      "field": "chemistry",
      "origin": "source:chemrxiv",
      "subfield": "general"
    }
  ],
  "title": "Lithium Polysulfide Speciation in Lithium–Sulfur Batteries: A First-Principles Benchmark of Thermodynamics, Bonding, and Solvent Control",
  "title_text": "Lithium Polysulfide Speciation in Lithium–Sulfur Batteries: A First-Principles Benchmark of Thermodynamics, Bonding, and Solvent Control",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:24Z",
  "url": "https://research.draconitic.com/paper/emb8r3c16y5t4",
  "venue": "ChemRxiv",
  "versions": []
}