Eigen and Zundel forms of small protonated water clusters: structures and infrared spectra

The spectral properties of protonated water clusters, especially the difference between Eigen (H3O+) and Zundel (H5O2+) conformers and the difference between their unhydrated and dominant hydrated forms are investigated with the first principles molecular dynamics simulations as well as with the high level ab initio calculations. The vibrational modes of the excess proton in H3O+ are sensitive to the hydration, while those in H5O2+ are sensitive to the messenger atom such as Ar (which was assumed to be weakly bound to the water cluster during acquisitions of experimental spectra). The spectral feature around approximately 2700 cm-1 (experimental value: 2665 cm-1) for the Eigen moiety appears when H3O+ is hydrated. This feature corresponds to the hydrating water interacting with H3O+, so it cannot appear in the Eigen core. Thus, H3O+ alone would be somewhat different from the Eigen forms in water. For the Zundel form (in particular, H5O2+), there have been some differences in spectral features among different experiments as well as between experiments and theory. When an Ar messenger atom is introduced at a specific temperature corresponding to the experimental condition, the calculated vibrational spectra for H5O2+.Ar are in good agreement with the experimental infrared spectra showing the characteristic Zundel frequency at approximately 1770 cm-1. Thus, the effect of hydration, messenger atom Ar, and temperature are crucial to elucidating the nature of vibrational spectra of Eigen and Zundel forms and to assigning the vibrational modes of small protonated water clusters.