he 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 H2O, possibly to liquid water under pressure, and to other H-bonded materials.

Nature of the Volume Isotope Effect in Ice / Umemoto, K; Sugimura, E; de Gironcoli, Stefano Maria; Nakajima, Y; Hirose, K; Ohishi, Y; Wentzcovitch, R. M.. - In: PHYSICAL REVIEW LETTERS. - ISSN 1079-7114. - 115:17(2015). [10.1103/PhysRevLett.115.173005]

Nature of the Volume Isotope Effect in Ice

de Gironcoli, Stefano Maria;
2015-01-01

Abstract

he 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 H2O, possibly to liquid water under pressure, and to other H-bonded materials.
2015
115
17
173005
https://link.aps.org/accepted/10.1103/PhysRevLett.115.173005
Umemoto, K; Sugimura, E; de Gironcoli, Stefano Maria; Nakajima, Y; Hirose, K; Ohishi, Y; Wentzcovitch, R. M.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/20.500.11767/14457
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