Anomalous hydrogen dynamics of the ice VII–VIII transition revealed by high-pressure neutron diffraction

Abstract

Above 2 GPa the phase diagram of water simplifies considerably and exhibits only two solid phases up to 60 GPa, ice VII and ice VIII. The two phases are related to each other by hydrogen ordering, with the oxygen sublattice being essentially the same. Here we present neutron diffraction data to 15 GPa which reveal that the rate of hydrogen ordering at the ice VII–VIII transition decreases strongly with pressure to reach timescales of minutes at 10 GPa. Surprisingly, the ordering process becomes more rapid again upon further compression. We show that such an unusual change in transition rate can be explained by a slowing down of the rotational dynamics of water molecules with a simultaneous increase of translational motion of hydrogen under pressure, as previously suspected. The observed cross-over in the hydrogen dynamics in ice is likely the origin of various hitherto unexplained anomalies of ice VII in the 10–15 GPa range reported by Raman spectroscopy, X-ray diffraction, and proton conductivity.