The coupling of the hydrated proton to its first solvation shell

Abstract: The transfer of a hydrated proton between water molecules in aqueous solution is accompanied by the large-scale structural reorganization of the environment as the proton relocates, giving rise to the Grotthus mechanism. The Zundel (H5O2+) and Eigen (H9O4+) cations are the main intermediate structures in this process. They exhibit radically different gas-phase infrared (IR) spectra, indicating fundamentally different environments of the solvated proton in its first solvation shell. The question arises: is there a least common denominator structure that explains the IR spectra of the Zundel and Eigen cations, and hence of the solvated proton? Full dimensional quantum simulations of these protonated cations demonstrate that two dynamical water molecules embedded in the static environment of the parent Eigen cation constitute this fundamental subunit. It is sufficient to explain the spectral signatures and anharmonic couplings of the solvated proton in its first solvation shell. In particular, we identify the anharmonic vibrational modes that explain the large broadening of the proton transfer peak in the experimental IR spectrum of the Eigen cation, of which the origin remained so far unclear. Our findings about the quantum mechanical structure of the first solvation shell provide a starting point for further investigations of the larger protonated water clusters with second and additional solvation shells.