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<p>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<sub>2</sub>O⋯H<sup>+</sup>⋯OH<sub>2</sub> 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<sup>+</sup>(H<sub>2</sub>O)<sub>6</sub>, 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.</p><p></p>

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Deciphering the infrared spectrum of the hydrated proton using full-dimensional quantum dynamics

  • 期刊论文

  • 出版模式：

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  • 发表日期：

    2026年7月27日

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  • David Mendive-Tapia,
  • Christoph Schran,
  • Banshi Das,
  • Fabien Gatti,
  • Markus Schröder,
  • Dominik Marx,
  • Oriol Vendrell

摘要

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 H2O⋯H+⋯OH2 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+(H2O)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.