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      Formation and properties of ice XVI obtained by emptying a type sII clathrate hydrate

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      Springer Science and Business Media LLC

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          Abstract

          Gas hydrates are ice-like solids, in which guest molecules or atoms are trapped inside cages formed within a crystalline host framework (clathrate) of hydrogen-bonded water molecules. They are naturally present in large quantities on the deep ocean floor and as permafrost, can form in and block gas pipelines, and are thought to occur widely on Earth and beyond. A natural point of reference for this large and ubiquitous family of inclusion compounds is the empty hydrate lattice, which is usually regarded as experimentally inaccessible because the guest species stabilize the host framework. However, it has been suggested that sufficiently small guests may be removed to leave behind metastable empty clathrates, and guest-free Si- and Ge-clathrates have indeed been obtained. Here we show that this strategy can also be applied to water-based clathrates: five days of continuous vacuum pumping on small particles of neon hydrate (of structure sII) removes all guests, allowing us to determine the crystal structure, thermal expansivity and limit of metastability of the empty hydrate. It is the seventeenth experimentally established crystalline ice phase, ice XVI according to the current ice nomenclature, has a density of 0.81 grams per cubic centimetre (making it the least dense of all known crystalline water phases) and is expected to be the stable low-temperature phase of water at negative pressures (that is, under tension). We find that the empty hydrate structure exhibits negative thermal expansion below about 55 kelvin, and that it is mechanically more stable and has at low temperatures larger lattice constants than the filled hydrate. These observations attest to the importance of kinetic effects and host-guest interactions in clathrate hydrates, with further characterization of the empty hydrate expected to improve our understanding of the structure, properties and behaviour of these unique materials.

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          Low-density framework form of crystalline silicon with a wide optical band gap

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            A guest-free germanium clathrate.

            The challenges associated with synthesizing expanded semiconductor frameworks with cage-like crystal structures continue to be of interest. Filled low-density germanium and silicon framework structures have distinct properties that address important issues in thermoelectric phonon glass-electron crystals, superconductivity and the possibility of Kondo insulators. Interest in empty framework structures of silicon and germanium is motivated by their predicted wide optical bandgaps of the same magnitude as quantum dots and porous silicon, making them and their alloys promising materials for silicon-based optoelectronic devices. Although almost-empty Na(1-x)Si136 has already been reported, the synthesis of guest-free germanium clathrate has so far been unsuccessful. Here we report the high-yield synthesis and characteristics of germanium with the empty clathrate-II structure through the oxidation of Zintl anions in ionic liquids under ambient conditions. The approach demonstrates the potential of ionic liquids as media for the reactions of polar intermetallic phases.
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              Thermodynamic stability and growth of guest-free clathrate hydrates: a low-density crystal phase of water.

              We use molecular dynamics simulations with the monatomic water (mW) model to investigate the phase diagram, metastability, and growth of guest-free water clathrates of structure sI and sII. At 1 atm pressure, the simulated guest-free water clathrates are metastable with respect to ice and stable with respect to the liquid up to their melting temperatures, 245+/-2 and 252+/-2 K for sI and sII, respectively. We characterize the growth of the sI and sII water crystals from supercooled water and find that the clathrates are unable to nucleate ice, the stable crystal. We computed the phase relations of ice, guest-free sII clathrate, and liquid water from -1500 to 500 atm. The resulting phase diagram indicates that empty sII may be the stable phase of water at pressures lower than approximately -1300 atm and temperatures lower than 275 K. The simulations show that, even in the region of stability of the empty clathrates, supercooled liquid water crystallizes to ice. This suggests that the barrier for nucleation of ice is lower than that for clathrates. We find no evidence for the existence of the characteristic polyhedral clathrate cages in supercooled extended water. Our results show that clathrates do not need the presence of a guest molecule to grow, but they need the guest to nucleate from liquid water. We conclude that nucleation of empty clathrates from supercooled liquid water would be extremely challenging if not impossible to attain in experiments. We propose two strategies to produce empty water clathrates in laboratory experiments at low positive pressures.
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                Author and article information

                Journal
                Nature
                Nature
                Springer Science and Business Media LLC
                0028-0836
                1476-4687
                December 2014
                December 10 2014
                December 2014
                : 516
                : 7530
                : 231-233
                Article
                10.1038/nature14014
                25503235
                a69285a5-1d0e-411f-8f13-bc2dbc27326f
                © 2014

                http://www.springer.com/tdm

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