Abstract:A computational investigation of the high-pressure phase sequence of the heaviest alkali hydroxides, RbOH and CsOH, shows that the phase diagram of both compounds is richer than hitherto thought. First-principles calculations suggest, based on energetics and comparisons to experimental diffraction and spectroscopy signatures, that the high-pressure phase RbOH-VI, stable above 6 GPa in experiment, should be assigned the KOH-VI structure type, and features localised hydrogen-bonded (OH)4 units. Meanwhile, a new … Show more
“…Solid crystalline structures were searched for using the particle swarm optimization algorithm as implemented in CALYPSO (crystal structure analysis by particle swarm optimization). [21,22] Structure predictions were performed with up to 16 formula units of (H 2 O) X (NH 3 ) Y , where X and Y are integers, and at 5,10,20,30,50,80, and 100 -1000 GPa in increments of 100 GPa. These searches were performed for the three canonical ammonia-water mixing ratios.…”
While ammonia and water readily form hydrogen-bonded molecular mixtures at ambient conditions, their miscibility under pressure is not well understood, yet crucial e.g. to model the interior of icy planets. We report here on the behaviour of ammonia-water mixtures under extreme pressure conditions, based on first-principles calculations of 15 stoichiometries in the pressure range of 1 atm to 10 Mbar. We show that compression facilitates proton transfer from water to ammonia in all relevant mixtures. This favors ammonia-rich hydrates above 1 Mbar, stabilized by complete de-protonation of water and the formation of the unusual structural motifs O 2− •(NH + 4) 2 and O 2− •(N 2 H + 7) 2. The hydronitrogen cations persist to the highest pressures studied. We predict a new ammonia-rich 4:1-hydrate at intermediate pressures and find that by 5.5 Mbar, close to the core-mantle boundary of Neptune, all cold ammonia-water mixtures are unstable against decomposition into their constituents.
“…Solid crystalline structures were searched for using the particle swarm optimization algorithm as implemented in CALYPSO (crystal structure analysis by particle swarm optimization). [21,22] Structure predictions were performed with up to 16 formula units of (H 2 O) X (NH 3 ) Y , where X and Y are integers, and at 5,10,20,30,50,80, and 100 -1000 GPa in increments of 100 GPa. These searches were performed for the three canonical ammonia-water mixing ratios.…”
While ammonia and water readily form hydrogen-bonded molecular mixtures at ambient conditions, their miscibility under pressure is not well understood, yet crucial e.g. to model the interior of icy planets. We report here on the behaviour of ammonia-water mixtures under extreme pressure conditions, based on first-principles calculations of 15 stoichiometries in the pressure range of 1 atm to 10 Mbar. We show that compression facilitates proton transfer from water to ammonia in all relevant mixtures. This favors ammonia-rich hydrates above 1 Mbar, stabilized by complete de-protonation of water and the formation of the unusual structural motifs O 2− •(NH + 4) 2 and O 2− •(N 2 H + 7) 2. The hydronitrogen cations persist to the highest pressures studied. We predict a new ammonia-rich 4:1-hydrate at intermediate pressures and find that by 5.5 Mbar, close to the core-mantle boundary of Neptune, all cold ammonia-water mixtures are unstable against decomposition into their constituents.
“…Under pressure, the alkali hydroxides tend not only to form hydrogen bonds between the layers, but undergo transitions to 3D network structures, with 0-, 1-, or 2-dimensional hydrogen-bonded sublattices (17)(18)(19)(20). The rationale from the high-pressure behavior of those systems is that layered phases are ultimately too loosely packed to survive under pressure.…”
We investigate the high-pressure phase diagram of the hydrous mineral brucite, Mg(OH) 2 , using structure search algorithms and ab initio simulations. We predict a high-pressure phase stable at pressure and temperature conditions found in cold subducting slabs in Earth's mantle transition zone and lower mantle. This prediction implies that brucite can play a much more important role in water transport and storage in Earth's interior than hitherto thought. The predicted high-pressure phase, stable in calculations between 20 and 35 GPa and up to 800 K, features MgO 6 octahedral units arranged in the anatase-TiO 2 structure. Our findings suggest that brucite will transform from a layered to a compact 3D network structure before eventual decomposition into periclase and ice. We show that the high-pressure phase has unique spectroscopic fingerprints that should allow for straightforward detection in experiments. The phase also has distinct elastic properties that might make its direct detection in the deep Earth possible with geophysical methods.brucite | pressure | phase transition | electronic structure calculations W ater plays an important role in sustaining geological activity. For instance, water helps in lowering the mantle's melting temperature, enhancing diffusion and creep thus affecting rheology of rocks, and also influences mineral phase boundaries. Current estimates suggest that the Earth's mantle is likely to contain a mass of water equivalent to the mass of the world's oceans (1, 2). The exchange of water between the surface and deep mantle reservoirs is vital for the sustenance of surface water over geological time scales (3). Hydrous minerals stable in the hydrated oceanic crust and mantle play an important role in transporting water into the Earth's interior. Hydrated peridotite, the major mantle rock type, can be understood by considering mineral phases stable in the ternary system of MgO-SiO 2 -H 2 O (MSH). Brucite, Mg(OH) 2 , is arguably the simplest hydrous mineral in the MSH system. Brucite is also the most important MgO-H 2 O binary and the most water-rich phase within the MSH ternary system.The crystal structure of brucite consists of Mg 2+ cations and OH − anions arranged in layers, in an overall trigonal structure (space group symmetry P 3m1); Fig. 1. The common ionic compound CdI 2 is the archetype crystal structure for brucite as well as for portlandite [Ca(OH) 2 )] and several other transition metal hydroxides M(OH) 2 where M = Mn, Ni, Co, Fe, Cd,. In brucite, the crystal structure comprises layers of edge-sharing MgO 6 polyhedra. The interaction between the layers is weak at ambient conditions, where each upward-pointing OH group is surrounded by three downward-pointing OH groups in the adjacent layer and vice versa. Under compression the H-H repulsive interactions lead to positional disordering of the protons, which are displaced from the 2d Wyckoff site into one of three equivalent 6i sites as documented from neutron diffraction studies (11,12). Vibrational spectroscopic studies incl...
“…2d ) returns to the ionic (NH 4 ) + (SH) − motif while Cmma (Fig. 2e ) has kinked infinite –(H–S)- chains with symmetric buckled S–H-S bonds in a matrix of NH 4 + cations; structural motifs seen for instance throughout the alkali hydroxides M + (OH − ) 47 . Fig.…”
Studies of molecular mixtures containing hydrogen sulfide (H2S) could open up new routes towards hydrogen-rich high-temperature superconductors under pressure. H2S and ammonia (NH3) form hydrogen-bonded molecular mixtures at ambient conditions, but their phase behavior and propensity towards mixing under pressure is not well understood. Here, we show stable phases in the H2S–NH3 system under extreme pressure conditions to 4 Mbar from first-principles crystal structure prediction methods. We identify four stable compositions, two of which, (H2S) (NH3) and (H2S) (NH3)4, are stable in a sequence of structures to the Mbar regime. A re-entrant stabilization of (H2S) (NH3)4 above 300 GPa is driven by a marked reversal of sulfur-hydrogen chemistry. Several stable phases exhibit metallic character. Electron–phonon coupling calculations predict superconducting temperatures up to 50 K, in the Cmma phase of (H2S) (NH3) at 150 GPa. The present findings shed light on how sulfur hydride bonding and superconductivity are affected in molecular mixtures. They also suggest a reservoir for hydrogen sulfide in the upper mantle regions of icy planets in a potentially metallic mixture, which could have implications for their magnetic field formation.
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