Revealing the Complex Nature of Bonding in the Binary High-Pressure Compound FeO_{2}.

Extreme pressures and temperatures are known to drastically affect the chemistry of iron oxides, resulting in numerous compounds forming homologous series nFeOmFe_{2}O_{3} and the appearance of FeO_{2}. Here, based on the results of in situ single-crystal x-ray diffraction, Mössbauer spectroscopy, x-ray absorption spectroscopy, and density-functional theory+dynamical mean-field theory calculations, we demonstrate that iron in high-pressure cubic FeO_{2} and isostructural FeO_{2}H_{0.5} is ferric (Fe^{3+}), and oxygen has a formal valence less than 2. Reduction of oxygen valence from 2, common for oxides, down to 1.5 can be explained by a formation of a localized hole at oxygen sites.

Melting Curve and Isostructural Solid Transition in Superionic Ice.

The phase diagram and melting curve of water ice is investigated up to 45 GPa and 1600 K by synchrotron x-ray diffraction in the resistively and laser heated diamond anvil cell. Our melting data evidence a triple point at 14.6 GPa, 850 K. The latter is shown to be related to a first-order solid transition from the dynamically disordered form of ice VII, denoted ice VII^{'}, toward a high-temperature phase with the same bcc oxygen lattice but larger volume and higher entropy. Our experiments are compared to ab initio molecular dynamics simulations, enabling us to identify the high-temperature bcc phase with the predicted superionic ice VII^{''} phase [J.-A. Hernandez and R. Caracas, Phys. Rev. Lett. 117, 135503 (2016).PRLTAO0031-900710.1103/PhysRevLett.117.135503].

New dynamic diamond anvil cells for tera-pascal per second fast compression x-ray diffraction experiments.

Fast compression experiments performed using dynamic diamond anvil cells (dDACs) employing piezoactuators offer the opportunity to study compression-rate dependent phenomena. In this paper, we describe an experimental setup which allows us to perform time-resolved x-ray diffraction during the fast compression of materials using improved dDACs. The combination of the high flux available using a 25.6 keV x-ray beam focused with a linear array of compound refractive lenses and the two fast GaAs LAMBDA detectors available at the Extreme Conditions Beamline (P02.2) at PETRA III enables the collection of x-ray diffraction patterns at an effective repetition rate of up to 4 kHz. Compression rates of up to 160 TPa/s have been achieved during the compression of gold in a 2.5 ms fast compression using improved dDAC configurations with more powerful piezoactuators. The application of this setup to low-Z compounds at lower compression rates is described, and the high temporal resolution of the setup is demonstrated. The possibility of applying finely tuned pressure profiles opens opportunities for future research, such as using oscillations of the piezoactuator to mimic propagation of seismic waves in the Earth.

Metastable silica high pressure polymorphs as structural proxies of deep Earth silicate melts.

Modelling of processes involving deep Earth liquids requires information on their structures and compression mechanisms. However, knowledge of the local structures of silicates and silica (SiO2) melts at deep mantle conditions and of their densification mechanisms is still limited. Here we report the synthesis and characterization of metastable high-pressure silica phases, coesite-IV and coesite-V, using in situ single-crystal X-ray diffraction and ab initio simulations. Their crystal structures are drastically different from any previously considered models, but explain well features of pair-distribution functions of highly densified silica glass and molten basalt at high pressure. Built of four, five-, and six-coordinated silicon, coesite-IV and coesite-V contain SiO6 octahedra, which, at odds with 3rd Pauling's rule, are connected through common faces. Our results suggest that possible silicate liquids in Earth's lower mantle may have complex structures making them more compressible than previously supposed.

Pressure-Induced Ferromagnetism due to an Anisotropic Electronic Topological Transition in Fe_{1.08}Te.

A rapid and anisotropic modification of the Fermi-surface shape can be associated with abrupt changes in crystalline lattice geometry or in the magnetic state of a material. We show that such an electronic topological transition is at the basis of the formation of an unusual pressure-induced tetragonal ferromagnetic phase in Fe_{1.08}Te. Around 2 GPa, the orthorhombic and incommensurate antiferromagnetic ground state of Fe_{1.08}Te is transformed upon increasing pressure into a tetragonal ferromagnetic state via a conventional first-order transition. On the other hand, an isostructural transition takes place from the paramagnetic high-temperature state into the ferromagnetic phase as a rare case of a "type-0" transformation with anisotropic properties. Electronic-structure calculations in combination with electrical resistivity, magnetization, and x-ray diffraction experiments show that the electronic system of Fe_{1.08}Te is instable with respect to profound topological transitions that can drive fundamental changes of the lattice anisotropy and the associated magnetic order.

Structural complexity of simple Fe2O3 at high pressures and temperatures.

Although chemically very simple, Fe2O3 is known to undergo a series of enigmatic structural, electronic and magnetic transformations at high pressures and high temperatures. So far, these transformations have neither been correctly described nor understood because of the lack of structural data. Here we report a systematic investigation of the behaviour of Fe2O3 at pressures over 100 GPa and temperatures above 2,500 K employing single crystal X-ray diffraction and synchrotron Mössbauer source spectroscopy. Crystal chemical analysis of structures presented here and known Fe(II, III) oxides shows their fundamental relationships and that they can be described by the homologous series nFeO·mFe2O3. Decomposition of Fe2O3 and Fe3O4 observed at pressures above 60 GPa and temperatures of 2,000 K leads to crystallization of unusual Fe5O7 and Fe25O32 phases with release of oxygen. Our findings suggest that mixed-valence iron oxides may play a significant role in oxygen cycling between earth reservoirs.

Pressure-induced non-superconducting phase of ß-Na0.33V2O5 and the mechanism of high-pressure phase transitions in ß-Na0.33V2O5 and ß-Li0.33V2O5 at room temperature.

The crystal structure of ß-Na0.33V2O5 (C2/m, Z = 6) has been studied on compression to 19 GPa at room temperature using synchrotron single-crystal diffraction in a diamond anvil cell. The vanadate bronze undergoes a phase transition to a non-superconducting phase at about 12 GPa due to changes of polyhedral connectivities in the vanadate framework and due to ordering of the Na(+) cations. This novel structure (Cm, Z = 6) is interpreted as an intermediate stage in the sequence of pressure-induced transformations in the ß-A0.33V2O5 bronzes (A: Li, Na) at room temperature. This study reveals the close relation between the loss of the two-leg ladder V-V system and non-superconducting state of the ß-A0.33V2O5 materials.

The most incompressible metal osmium at static pressures above 750 gigapascals.

Metallic osmium (Os) is one of the most exceptional elemental materials, having, at ambient pressure, the highest known density and one of the highest cohesive energies and melting temperatures. It is also very incompressible, but its high-pressure behaviour is not well understood because it has been studied so far only at pressures below 75 gigapascals. Here we report powder X-ray diffraction measurements on Os at multi-megabar pressures using both conventional and double-stage diamond anvil cells, with accurate pressure determination ensured by first obtaining self-consistent equations of state of gold, platinum, and tungsten in static experiments up to 500 gigapascals. These measurements allow us to show that Os retains its hexagonal close-packed structure upon compression to over 770 gigapascals. But although its molar volume monotonically decreases with pressure, the unit cell parameter ratio of Os exhibits anomalies at approximately 150 gigapascals and 440 gigapascals. Dynamical mean-field theory calculations suggest that the former anomaly is a signature of the topological change of the Fermi surface for valence electrons. However, the anomaly at 440 gigapascals might be related to an electronic transition associated with pressure-induced interactions between core electrons. The ability to affect the core electrons under static high-pressure experimental conditions, even for incompressible metals such as Os, opens up opportunities to search for new states of matter under extreme compression.

Importance of correlation effects in hcp iron revealed by a pressure-induced electronic topological transition.

We discover that hcp phases of Fe and Fe(0.9)Ni(0.1) undergo an electronic topological transition at pressures of about 40 GPa. This topological change of the Fermi surface manifests itself through anomalous behavior of the Debye sound velocity, c/a lattice parameter ratio, and Mössbauer center shift observed in our experiments. First-principles simulations within the dynamic mean field approach demonstrate that the transition is induced by many-electron effects. It is absent in one-electron calculations and represents a clear signature of correlation effects in hcp Fe.

Pressure-dependent structural and electronic properties of quasi-one-dimensional (TMTTF)2PF6.

We have performed detailed x-ray investigations of the quasi-one-dimensional organic conductor (TMTTF)(2)PF(6) at room temperature and hydrostatic pressures up to 27 kbar. Based on the pressure-dependent crystal structure, the electronic band structure was calculated by density functional theory (DFT). Our systematic study provides important information on the coupling among the organic molecules but also to the anions. We discuss the consequences for the electronic properties and compare them with optical investigations under pressure. The increasing plasma frequency observed perpendicular to the stacks corresponds to a widening of the bands for the b-direction. Around 20 kbar a dimensional crossover occurs from a one-dimensional Mott insulator to a two-dimensional metal.

Portable double-sided laser-heating system for Mössbauer spectroscopy and X-ray diffraction experiments at synchrotron facilities with diamond anvil cells.

The diamond anvil cell (DAC) technique coupled with laser heating is a major method for studying materials statically at multimegabar pressures and at high temperatures. Recent progress in experimental techniques, especially in high-pressure single crystal X-ray diffraction, requires portable laser heating systems which are able to heat and move the DAC during data collection. We have developed a double-sided laser heating system for DACs which can be mounted within a rather small (~0.1 m(2)) area and has a weight of ~12 kg. The system is easily transferable between different in-house or synchrotron facilities and can be assembled and set up within a few hours. The system was successfully tested at the High Pressure Station of White Beam (ID09a) and Nuclear Resonance (ID18) beamlines of the European Synchrotron Radiation Facility. We demonstrate examples of application of the system to a single crystal X-ray diffraction investigation of (Mg(0.87),Fe(3+) (0.09),Fe(2+) (0.04))(Si(0.89),Al(0.11))O(3) perovskite (ID09a) and a Synchrotron Mössbauer Source (SMS) study of (Mg(0.8)Fe(0.2))O ferropericlase (ID18).

Plasmons in sodium under pressure: increasing departure from nearly free-electron behavior.

We have measured plasmon energies in Na under high pressure up to 43 GPa using inelastic x-ray scattering (IXS). The momentum-resolved results show clear deviations, growing with increasing pressure, from the predictions for a nearly free-electron metal. Plasmon energy calculations based on first-principles electronic band structures and a quasiclassical plasmon model allow us to identify a pressure-induced increase in the electron-ion interaction and associated changes in the electronic band structure as the origin of these deviations, rather than effects of exchange and correlation. Additional IXS results obtained for K and Rb are addressed briefly.

Crystal structures of dense lithium: a metal-semiconductor-metal transition.

Ab initio random structure searching and single-crystal x-ray diffraction have been used to determine the full structures of three phases of lithium, recently discovered at low temperature above 60 GPa. A structure with C2mb symmetry, calculated to be a poor metal, is proposed for the oC88 phase (60-65 GPa). The oC40 phase (65-95 GPa) is found to have a lowest-enthalpy structure with C2cb symmetry, in excellent agreement with the x-ray data. It is calculated to be a semiconductor with a band gap of ∼1 eV at 90 GPa. oC24, stable above 95 GPa, has the space group Cmca, and refined atomic coordinates are in excellent agreement with previous calculations.

Initial structure memory of pressure-induced changes in the phase-change memory alloy Ge2Sb2Te5.

We demonstrate that while the metastable face-centered cubic (fcc) phase of Ge2Sb2Te5 becomes amorphous under hydrostatic compression at about 15 GPa, the stable trigonal phase remains crystalline. Upon higher compression, a body-centered cubic phase is obtained in both cases around 30 GPa. Upon decompression, the amorphous phase is retained for the starting fcc phase while the initial structure is recovered for the starting trigonal phase. We argue that the presence of vacancies and associated subsequent large atomic displacements lead to nanoscale phase separation and loss of initial structure memory in the fcc staring phase of Ge2Sb2Te5.

Superhard semiconducting optically transparent high pressure phase of boron.

An orthorhombic (space group Pnnm) boron phase was synthesized at pressures above 9 GPa and high temperature, and it was demonstrated to be stable at least up to 30 GPa. The structure, determined by single-crystal x-ray diffraction, consists of B12 icosahedra and B2 dumbbells. The charge density distribution obtained from experimental data and ab initio calculations suggests covalent chemical bonding in this phase. Strong covalent interatomic interactions explain the low compressibility value (bulk modulus is K300=227 GPa) and high hardness of high-pressure boron (Vickers hardness HV=58 GPa), after diamond the second hardest elemental material.

Superconducting and normal phases of FeSe single crystals at high pressure.

We report on the synthesis of superconducting single crystals of FeSe and their characterization by x-ray diffraction, magnetization and resistivity. We have performed ac susceptibility measurements under high pressure in a hydrostatic liquid argon medium up to 14 GPa and we find that T(C) increases up to 33-36 K in all samples, but with slightly different pressure dependences on different samples. Above 12 GPa no traces of superconductivity are found in any sample. We have also performed a room temperature high pressure x-ray diffraction study up to 12 GPa on a powder sample, and we find that, between 8.5 and 12 GPa, the tetragonal PbO structure undergoes a structural transition to a hexagonal structure. This transition results in a volume decrease of about 16% and is accompanied by the appearance of an intermediate, probably orthorhombic, phase.

High-pressure effect on PbTiO3: an investigation by Raman and x-ray scattering up to 63 GPa.

We report a room-temperature high-pressure x-ray and Raman scattering investigation of lead titanate (PbTiO3) up to 63 GPa. Three continuous phase transitions at 13, 20, and 45 GPa between tetragonal-like phases occur. As a result, no evidence is found for a pressure-induced morphotropic phase boundary. Our study provides experimental evidence that PbTiO3 presents a complex sequence of phases accommodating pressure through mechanisms involving oxygen octahedra tilting and reentrance of ferroelectricity.

Pressure-induced hydrogen-dominant metallic state in aluminum hydride.

Two structural transitions in covalent aluminum hydride AlH3 were characterized at high pressure. A metallic phase stable above 100 GPa is found to have a remarkably simple cubic structure with shortest first-neighbor H-H distances ever measured except in H2 molecule. Although the high-pressure phase is predicted to be superconductive, this was not observed experimentally down to 4 K over the pressure range 120-164 GPa. The results indicate that the superconducting behavior may be more complex than anticipated.

Competition of charge-density waves and superconductivity in sulfur.

A one-dimensional charge-density wave (CDW) instability is shown to be responsible for the formation of the incommensurate modulation of the atomic lattice in the high-pressure phase of sulfur. The coexistence of, and competition between, the CDW and the superconducting state leads to the previously observed increase of T{c} up to 17 K, which we attribute to the suppression of the CDW instability, the same phenomenology found in doped layered dichalcogenides.

High-pressure potato starch granule gelatinization: synchrotron radiation micro-SAXS/WAXS using a diamond anvil cell.

Potato starch granules have been examined by synchrotron radiation small- and wide-angle scattering in a diamond anvil cell (DAC) up to 750 MPa. Use of a 1 microm synchrotron radiation beam allowed the mapping of individual granules at several pressure levels. The data collected at 183 MPa show an increase in the a axis and lamellar period from the edge to the center of the granule, probably due to a gradient in water content of the crystalline and amorphous lamellae. The average granules radius increases up to the onset of gelatinization at about 500 MPa, but the a axis and the lamellar periodicity remain constant or even show a decrease, suggesting an initial hydration of amorphous growth rings. The onset of gelatinization is accompanied by (i) an increase in the average a axis and lamellar periodicity, (ii) the appearance of an equatorial SAXS streak, and (iii) additional short-range order peaks.