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 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. The infrared spectra of the aqueous proton show dynamic character beyond the classical Zundel H+(H2O)2 and Eigen H+(H2O)3 structural motifs. Fully quantum modelling the larger H+(H2O)6 complex provides a direct link between asymmetric solvation environments and the spectroscopic response of the solvated proton.