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Title: Communication: On the stability of ice 0, ice i, and I{sub h}

Using ab initio methods, we examine the stability of ice 0, a recently proposed tetragonal form of ice implicated in the homogeneous freezing of water [J. Russo, F. Romano, and H. Tanaka, Nat. Mater. 13, 670 (2014)]. Vibrational frequencies are computed across the complete Brillouin Zone using Density Functional Theory (DFT), to confirm mechanical stability and quantify the free energy of ice 0 relative to ice I{sub h}. The robustness of this result is tested via dispersion corrected semi-local and hybrid DFT, and Quantum Monte-Carlo calculation of lattice energies. Results indicate that popular molecular models only slightly overestimate the stability of ice zero. In addition, we study all possible realisations of proton disorder within the ice zero unit cell, and identify the ground state as ferroelectric. Comparisons are made to other low density metastable forms of ice, suggesting that the ice i structure [C. J. Fennel and J. D. Gezelter, J. Chem. Theory Comput. 1, 662 (2005)] may be equally relevant to ice formation.
Authors:
 [1] ;  [2] ;  [3]
  1. Department of Physics and Centre for Scientific Computing, University of Warwick, Coventry CV4 7AL (United Kingdom)
  2. Department of Earth Sciences and Department of Physics and Astronomy, University College London, Gower Street, London WC1E 6BT (United Kingdom)
  3. Department of Chemistry, University College London, 20 Gordon Street, London WC1H 0AJ (United Kingdom)
Publication Date:
OSTI Identifier:
22310720
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 16; Other Information: (c) 2014 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BRILLOUIN ZONES; COMPARATIVE EVALUATIONS; DENSITY; DENSITY FUNCTIONAL METHOD; DISPERSIONS; FERROELECTRIC MATERIALS; FREE ENERGY; GROUND STATES; HYBRIDIZATION; ICE; MOLECULAR MODELS; MONTE CARLO METHOD; PROTONS; STABILITY