Nature of the Volume Isotope Effect in Ice.

The substitution of hydrogen (H) by deuterium (D) in ice Ih and in its H-ordered version, ice XI, produces an anomalous form of volume isotope effect (VIE), i.e., volume expansion. This VIE contrasts with the normal VIE (volume contraction) predicted in ice-VIII and in its H-disordered form, ice VII. Here we investigate the VIE in ice XI and in ice VIII using first principles quasiharmonic calculations. We conclude that normal and anomalous VIEs can be produced in ice VIII and ice XI in sequence by application of pressure (ice XI starting at negative pressures) followed by a third type-anomalous VIE with zero-point volume contraction. The latter should also contribute to the isotope effect in the ice VII → ice X transition. The predicted change between normal and anomalous VIE in ice VIII at 14.3 GPa and 300 K is well reproduced experimentally in ice VII using x-ray diffraction measurements. The present discussion of the VIE is general, and conclusions should be applicable to other solid phases of H(2)O, possibly to liquid water under pressure, and to other H-bonded materials.

Experimental evidence of superionic conduction in H2O ice.

Ionic conductivity and molar volume measurements were performed on H(2)O ice at high pressure (P) and temperature (T) in a resistive-heated diamond anvil cell. The conductivity data obtained at P = 20-62 GPa, T = 304-930 K are well fitted with a single Arrhenius equation. Isothermal volume measurements at T = 873 K, P = 30-101 GPa indicate that H(2)O ice undergoes phase transitions at P = 50 GPa and 53 GPa due to hydrogen-bond symmetrization. Combining these results, we suggest that the conduction mechanism does not change with pressure-induced hydrogen-bond symmetrization. Along the Arrhenius behavior of conductivity data, the experimental evidence for superionic conduction (>10(-1) S/cm) was found at T = 739 K, P = 56 GPa and T = 749 K, P = 62 GPa, which is significantly low temperature compared with earlier theoretical estimates resorted to the observation of a drastic rise of the melting curve. We infer that the sudden increase of the melting temperature is not related to the onset of superionic conduction, but is attributed to the phase change regarding to the symmetrization.