Abstract
The structure of the minimum unit of the radical cationic water clusters, the (H(2)O)(2)(+) dimer, has attracted much attention because of its importance for the radiation chemistry of water. Previous spectroscopic studies indicated that the dimers have a proton-transferred structure (H(3)O(+)·OH), though the alternate metastable hemibonded structure (H(2)O·OH(2))(+) was also predicted based on theoretical calculations. Here, we produce (H(2)O)(2)(+) dimers in superfluid helium nanodroplets and study their infrared spectra in the range of OH stretching vibrations. The observed spectra indicate the coexistence of the two structures in the droplets, supported by density functional theory calculations. This is the first spectroscopic identification of the hemibonded isomer of water radical cation dimers. The observation of the higher-energy isomer reveals efficient kinetic trapping for metastable ionic clusters due to the rapid cooling in helium droplets.