Abstract

H2O will be more resistant to metallization than previously thought. From computational evolutionary structure searches, we find a sequence of new stable and meta-stable structures for the ground state of ice in the 1–5 TPa (10 to 50 Mbar) regime, in the static approximation. The previously proposed Pbcm structure is superseded by a Pmc21 phase at p = 930 GPa, followed by a predicted transition to a P21 crystal structure at p = 1.3 TPa. This phase, featuring higher coordination at O and H, is stable over a wide pressure range, reaching 4.8 TPa. We analyze carefully the geometrical changes in the calculated structures, especially the buckling at the H in O-H-O motifs. All structures are insulating—chemistry burns a deep and (with pressure increase) lasting hole in the density of states near the highest occupied electronic levels of what might be component metallic lattices. Metallization of ice in our calculations occurs only near 4.8 TPa, where the metallic C2/m phase becomes most stable. In this regime, zero-point energies much larger than typical enthalpy differences suggest possible melting of the H sublattice, or even the entire crystal.

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Acknowledgments.

Andreas Hermann wishes to acknowledge Peter Schwerdtfeger for piquing his interest in high pressure studies of water and ice. We thank two reviewers for their comments. Our work was supported by EFree, an Energy Frontier Research Center funded by the Department of Energy (Award Number DESC0001057 at Cornell) and the National Science Foundation through Grants CHE-0910623 and DMR-0907425. Computational resources provided by the Cornell NanoScale Facility (supported by the National Science Foundation through Grant ECS-0335765), and by the TeraGrid network (provided by the National Center for Supercomputer Applications through Grant TG-DMR060055N), are gratefully acknowledged.

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Supporting Information

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Published in

Go to Proceedings of the National Academy of Sciences
Go to Proceedings of the National Academy of Sciences
Proceedings of the National Academy of Sciences
Vol. 109 | No. 3
January 17, 2012
PubMed: 22207625

Classifications

Submission history

Published online: December 29, 2011
Published in issue: January 17, 2012

Keywords

  1. hydrogen bonds
  2. compressed water

Acknowledgments

Andreas Hermann wishes to acknowledge Peter Schwerdtfeger for piquing his interest in high pressure studies of water and ice. We thank two reviewers for their comments. Our work was supported by EFree, an Energy Frontier Research Center funded by the Department of Energy (Award Number DESC0001057 at Cornell) and the National Science Foundation through Grants CHE-0910623 and DMR-0907425. Computational resources provided by the Cornell NanoScale Facility (supported by the National Science Foundation through Grant ECS-0335765), and by the TeraGrid network (provided by the National Center for Supercomputer Applications through Grant TG-DMR060055N), are gratefully acknowledged.

Authors

Affiliations

Andreas Hermann
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853; and
N. W. Ashcroft1 [email protected]
Laboratory of Atomic and Solid State Physics, Cornell University, Ithaca, NY 14853
Roald Hoffmann1 [email protected]
Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY 14853; and

Notes

1
To whom correspondence may be addressed. E-mail: [email protected] or [email protected].
Contributed by Roald Hoffmann, November 16, 2011 (sent for review September 9, 2011)
Author contributions: A.H., N.W.A., and R.H. designed research; A.H. and R.H. performed research; A.H. contributed new reagents/analytic tools; A.H., N.W.A., and R.H. analyzed data; and A.H., N.W.A., and R.H. wrote the paper.

Competing Interests

The authors declare no conflict of interest.

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    High pressure ices
    Proceedings of the National Academy of Sciences
    • Vol. 109
    • No. 3
    • pp. 647-995

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