Near-infrared spectra of H2O under high pressure and high temperature: implications for a transition from proton tunneling to hopping states.

The nature of protons in ice VII up to 368°C and 16GPa was investigated with synchrotron near-infrared spectroscopy. The absorption band of the first OH stretching overtone mode divided into doublet peaks above 5GPa at room temperature, suggesting that proton tunneling occurs at the overtone level. As the temperature increased, the doublet peaks gradually reduced to a singlet. This result implies that thermally activated protons hop between the two potential minima along the oxygen-oxygen axis. A pressure-temperature diagram for the proton state was constructed from the changing band shape of the overtone mode.