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

• The dynamical behavior of proton in ice VII was examined by NIR spectroscopy.
• Tunneling splitting of OH stretching overtone mode was observed above 4 GPa.
• The tunneling splitting disappeared from the NIR spectra measured above 200 °C.
• It implies a transition from proton tunneling to hopping states.

The nature of protons in ice VII up to 368 °C and 16 GPa was investigated with synchrotron near-infrared spectroscopy. The absorption band of the first OH stretching overtone mode divided into doublet peaks above 5 GPa 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.

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