Nature of the Volume Isotope Effect in Ice

Koichiro Umemoto, Emiko Sugimura, Stefano de Gironcoli, Yoichi Nakajima, Kei Hirose, Yasuo Ohishi, and Renata M. Wentzcovitch
Phys. Rev. Lett. 115, 173005 – Published 22 October 2015
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Abstract

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

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  • Received 16 October 2014

DOI:https://doi.org/10.1103/PhysRevLett.115.173005

© 2015 American Physical Society

Authors & Affiliations

Koichiro Umemoto1,2, Emiko Sugimura3, Stefano de Gironcoli4, Yoichi Nakajima5, Kei Hirose2,6, Yasuo Ohishi7, and Renata M. Wentzcovitch2,4,8

  • 1Department of Earth Sciences, University of Minnesota, 310 Pillsbury Drive SE, Minneapolis, Minnesota 55455, USA
  • 2Earth-Life Science Institute, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan
  • 3Department of Earth and Planetary Sciences, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan
  • 4Scuola Internazionale Superiore di Studi Avanzati (SISSA) and CNR-IOM DEMOCRITOS Simulation Centre, Via Bononea 265, 34146 Trieste, Italy
  • 5Materials Dynamics Laboratory, RIKEN SPring-8 Center, RIKEN, 1-1-1 Kouto Hyogo 679-5148, Japan
  • 6Laboratory of Ocean-Earth Life Evolution Research, Japan Agency for Marine-Earth Science and Technology, Yokosuka, Kanagawa 237-0061, Japan
  • 7Japan Synchrotron Radiation Research Institute, Sayo-cho, Hyogo 679-5198, Japan
  • 8Department of Chemical Engineering and Materials Science and Minnesota Supercomputing Institute, University of Minnesota, 421 Washington Avenue SE, Minneapolis, Minnesota 55455, USA

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Issue

Vol. 115, Iss. 17 — 23 October 2015

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