{
  "abstract": "A comprehensive understanding of the microscopic processes governing ion transport in concentrated electrolyte solutions is essential for developing efficient, water-based batteries and energy storage devices. LiTFSI has emerged as a model system for Waterin-Salt (WiS) electrolytes because it can be investigated over a wide concentration range. Here, we combine Raman and THz spectroscopy with classical MD simulations to elucidate the reorganization of the water network across concentrations ranging from 1 to 21 mol·kg-1. Isotopic substitution of H2O by D2O allows us to disentangle the distinct spectroscopic contributions of ion rattling modes and H-bond motifs in the THz frequency range. The analysis reveals two solvent-dependent modes in the region of the translational and librational water network modes, rationalized as an overall strengthening of directional H-bonds and a decrease in orientational preference. This picture is consistent with the accompanying molecular dynamics simulations, which predict a continuous shift from solvent-separated to solvent-shared to contact ion pairs, alongside a softening of water-water H-bonds and a broadening in the angular distributions within the water-water H-bond network. A thermodynamic decomposition further reveals correlations among the number of H-bonds, the observed spectroscopic nonlinearities, and the concentration-dependent conductivity. Our findings reveal a gradual, continuous reorganization of the water network as LiTFSI concentration increases: the red-shifted librational mode indicates a lower barrier for the angular part of the intermolecular potential, consistent with the simulated broadening of the angular distributions within the H-bond network. The impact on water dynamics and charge transport is discussed.",
  "abstract_shown": true,
  "affiliations": [
    "Department of Physical Chemistry II",
    "Ruhr University Bochum",
    "Sorbonne Université",
    "Laboratoire PHENIX (Physicochimie des Électrolytes et Nanosystèmes Interfaciaux",
    "Réseau sur le Stockage Électrochimique de l’Énergie (RS2E), FR CNRS"
  ],
  "article_type": null,
  "arxiv": null,
  "author_total": 6,
  "authors": [
    {
      "affs": [
        0,
        1
      ],
      "name": "Melinda Nolten"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Marinella de Giovanetti"
    },
    {
      "affs": [
        2,
        3
      ],
      "name": "Matthieu Wolf"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Gerhard Schwaab",
      "orcid": "0000-0003-2136-907X"
    },
    {
      "affs": [
        2,
        3,
        4
      ],
      "name": "Benjamin Rotenberg"
    },
    {
      "affs": [
        0,
        1
      ],
      "name": "Martina Havenith"
    }
  ],
  "bibtex": "https://research.draconitic.com/paper/d53wq59mwz3qw.bib",
  "cited_by": 0,
  "doi": "10.26434/chemrxiv.15008623/v1",
  "fulltext_url": null,
  "id": "d53wq59mwz3qw",
  "issns": [],
  "landing_url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008623/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": "W7212154806",
  "pdf_url": null,
  "pmcid": null,
  "pmid": null,
  "published": "2026-09-10",
  "publisher": "American Chemical Society (ACS)",
  "ris": "https://research.draconitic.com/paper/d53wq59mwz3qw.ris",
  "sources": [
    {
      "first_seen": "2026-10-30T12:17:19Z",
      "native_id": "10.26434/chemrxiv.15008623",
      "source": "chemrxiv",
      "url": "https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008623/v1"
    }
  ],
  "subjects": [
    {
      "field": "physics",
      "origin": "openalex:3107|Spectroscopy and Quantum Chemical Studies",
      "subfield": "amo"
    }
  ],
  "title": "Weakening H-bonds facilitate Li+ transport in concentrated aqueous LiTFSI solutions",
  "title_text": "Weakening H-bonds facilitate Li+ transport in concentrated aqueous LiTFSI solutions",
  "type": "preprint",
  "updated_at": "2026-10-30T12:17:19Z",
  "url": "https://research.draconitic.com/paper/d53wq59mwz3qw",
  "venue": "ChemRxiv",
  "versions": []
}