Deciphering the infrared spectrum of the hydrated proton using full-dimensional quantum dynamics
Abstract
The nature of the aqueous proton has been traditionally interpreted through two limiting structural motifs: the Zundel and Eigen cations. However, experimental infrared (IR) spectra of the solvated proton reveal a far more dynamic character, as evidenced by distinct intensity modulations within the characteristic continuum absorption band. In fact, recent ultrafast two-dimensional IR spectroscopy suggests that solvation-induced structural distortions around H 2 O⋯H + ⋯OH 2 motifs critically shape the IR response. Here we investigate the role of such asymmetry through full-dimensional quantum dynamics simulations of the extended Zundel complex H + (H 2 O) 6 , which structurally encompasses both Zundel and Eigen motifs. Systematic removal of one water molecule from the second solvation shell gradually introduces deviations from the perfectly symmetric Zundel-like complex towards Eigen-like spectral features. These results provide a direct map between the asymmetric solvation environment and the structural response of the first and second solvation shells of the aqueous proton, offering a structural and dynamical basis for understanding how this asymmetry governs proton mobility in aqueous environments.
Related
- Thermo-elastic properties of hydrated epoxy-graphene nanocomposites from ensemble-based molecular dynamics simulations
- Hydrated porous substrates modulate the spatiotemporal dynamics of bacterial turbulence
- A Zero-Dimensional Hybrid Tin Halide with Efficient Near-Infrared Luminescence for Intelligent Defect Inspection
- Stochastic Bubble Completion in de Sitter Space: Power Spectrum, Bispectrum, and Infrared Moment Hierarchies
- Inferring Transition-Dipoles from Two-Dimensional Infrared Spectroscopy with Deep Learning
BibTeX
@article{mendivetapia2026deciphering,
title = {{Deciphering the infrared spectrum of the hydrated proton using full-dimensional quantum dynamics}},
author = {David Mendive-Tapia and Christoph Schran and Banshi Das and Fabien Gatti and Markus Schröder and Dominik Marx and Oriol Vendrell},
journal = {Nature Chemistry-},
year = {2026},
month = jul,
doi = {10.1038/s41557-026-02209-3},
url = {https://hal.science/hal-05769731v1},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - Deciphering the infrared spectrum of the hydrated proton using full-dimensional quantum dynamics
AU - David Mendive-Tapia
AU - Christoph Schran
AU - Banshi Das
AU - Fabien Gatti
AU - Markus Schröder
AU - Dominik Marx
AU - Oriol Vendrell
PY - 2026
DA - 2026/07/27
JO - Nature Chemistry-
DO - 10.1038/s41557-026-02209-3
UR - https://hal.science/hal-05769731v1
AB - The nature of the aqueous proton has been traditionally interpreted through two limiting structural motifs: the Zundel and Eigen cations. However, experimental infrared (IR) spectra of the solvated proton reveal a far more dynamic character, as evidenced by distinct intensity modulations within the characteristic continuum absorption band. In fact, recent ultrafast two-dimensional IR spectroscopy suggests that solvation-induced structural distortions around H 2 O⋯H + ⋯OH 2 motifs critically shape the IR response. Here we investigate the role of such asymmetry through full-dimensional quantum dynamics simulations of the extended Zundel complex H + (H 2 O) 6 , which structurally encompasses both Zundel and Eigen motifs. Systematic removal of one water molecule from the second solvation shell gradually introduces deviations from the perfectly symmetric Zundel-like complex towards Eigen-like spectral features. These results provide a direct map between the asymmetric solvation environment and the structural response of the first and second solvation shells of the aqueous proton, offering a structural and dynamical basis for understanding how this asymmetry governs proton mobility in aqueous environments.
SN - 1755-4330
SN - 1755-4349
ER -