The crystal structure of methane B at 8 GPa--an α-Mn arrangement of molecules.

From a combination of powder and single-crystal synchrotron x-ray diffraction data we have determined the carbon substructure of phase B of methane at a pressure of ∼8 GPa. We find this substructure to be cubic with space group I4¯3m and 58 molecules in the unit cell. The unit cell has a lattice parameter a = 11.911(1) Å at 8.3(2) GPa, which is a factor of √2 larger than had previously been proposed by Umemoto et al. [J. Phys.: Condens. Matter 14, 10675 (2002)]. The substructure as now solved is not related to any close-packed arrangement, contrary to previous proposals. Surprisingly, the arrangement of the carbon atoms is isostructural with that of α-manganese at ambient conditions.

Strength analysis and optimisation of double-toroidal anvils for high-pressure research.

We used the finite element method for stress and deformation analysis of the large sample volume double-toroidal anvil and gasket assembly used with the Paris-Edinburgh press for neutron scattering, in order to investigate the failure of this assembly observed repeatedly in experiments at a load of approximately 240 tonnes. The analysis is based on a new approach to modelling an opposed anvil device working under extreme stress conditions. The method relies on use of experimental data to validate the simulation in the absence of the material property data available for high pressure conditions. Using this method we analysed the stress distribution on the surface and in the bulk of the double-toroidal anvils, and we conclude that the failure occurs on the surface of the anvil and that it is caused by the tensile stress. We also use the model to show possible ways of optimising the anvil design in order to extend its operational pressure range.

Extraordinarily complex crystal structure with mesoscopic patterning in barium at high pressure.

Elemental barium adopts a series of high-pressure phases with such complex crystal structures that some of them have eluded structure determination for many years. Using single-crystal synchrotron X-ray diffraction and new data analysis strategies, we have now solved the most complex of these crystal structures, that of phase Ba-IVc at 19 GPa. It is a commensurate host-guest structure with 768 atoms in the representative unit, where the relative alignment of the guest-atom chains can be represented as a two-dimensional pattern with interlocking S-shaped 12-chain motifs repeating regularly in one direction and repeating with constrained disorder in the other. The existence of such patterning on the nanometre scale points at medium-range interactions that are not fully screened by the itinerant electrons in this metal. On the basis of first-principles electronic structure calculations, pseudopotential theory and an analysis of the lattice periodicities and interatomic distances, we rationalize why the Ba phases with the common densely packed crystal structures become energetically unfavourable in comparison with the complex-structured Ba-IVc phase, and what the role of the well-known pressure-induced s-d electronic transfer is.

Note: Achieving quasi-hydrostatic conditions in large-volume toroidal anvils for neutron scattering to pressures of up to 18 GPa.

We present developments that allow neutron-scattering experiments to be performed, with both single-crystal and powder samples, under quasi-hydrostatic conditions to pressures beyond previous limits. Samples of sodium chloride and squaric acid (H(2)C(4)O(4)) have been loaded with argon as the pressure-transmitting medium in encapsulated gaskets redesigned for double-toroidal anvils, using a gas-loading method at ambient temperature. These samples have been compressed up to 18 GPa in a Paris-Edinburgh press, and no evidence of peak broadening in either the single-crystal or the powder experiments was observed.

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.

A rotator for single-crystal neutron diffraction at high pressure.

We present a modified Paris-Edinburgh press which allows rotation of the anvils and the sample under applied load. The device is designed to overcome the problem of having large segments of reciprocal space obscured by the tie rods of the press during single-crystal neutron-scattering experiments. The modified press features custom designed hydraulic bearings and provides controls for precision rotation and positioning. The advantages of using the device for increasing the number of measurable reflections are illustrated with the results of neutron-diffraction experiments on a single crystal of germanium rotated under a load of 70 tonnes.

Gas loading apparatus for the Paris-Edinburgh press.

We describe the design and operation of an apparatus for loading gases into the sample volume of the Paris-Edinburgh press at room temperature and high pressure. The system can be used for studies of samples loaded as pure or mixed gases as well as for loading gases as pressure-transmitting media in neutron-scattering experiments. The apparatus consists of a high-pressure vessel and an anvil holder with a clamp mechanism. The vessel, designed to operate at gas pressures of up to 150 MPa, is used for applying the load onto the anvils located inside the clamp. This initial load is sufficient for sealing the pressurized gas inside the sample containing gasket. The clamp containing the anvils and the sample is then transferred into the Paris-Edinburgh press by which further load can be applied to the sample. The clamp has apertures for scattered neutron beams and remains in the press for the duration of the experiment. The performance of the gas loading system is illustrated with the results of neutron-diffraction experiments on compressed nitrogen.

The distorted close-packed crystal structure of methane A.

We have determined the full crystal structure of the high-pressure phase methane A. X-ray single-crystal diffraction data were used to determine the carbon-atom arrangement, and neutron powder diffraction data from a deuterated sample allowed the deuterium atoms to be located. It was then possible to refine all the hydrogen positions from the single-crystal x-ray data. The structure has 21 molecules in a rhombohedral unit cell, and is quite strongly distorted from the cubic close-packed structure of methane I, although some structural similarities remain. Full knowledge of this structure is important for modeling of methane at higher pressures, including in relation to the mineralogy of the outer solar system. We discuss interesting structural parallels with the carbon tetrahalides.

Potassium under pressure: a pseudobinary ionic compound.

Experimentally, we have found that among the "complicated" phases of potassium at intermediate pressures is one which has the same space group as the double hexagonal-close-packed structure, although its atomic coordination is completely different. Calculations on this P6(3)/mmc (hP4) structure as a function of pressure show three isostructural transitions and three distinctive types of chemical bonding: free electron, ionic, and metallic. Interestingly, relationships between localized metallic structures and ionic compounds are found.

Two million hours of science.

After over a quarter of a century, the doors of the world's first synchrotron radiation source have closed. Its contribution to materials science in the past and the future should not be underestimated.

High-pressure gas hydrates.

It has long been known that crystalline hydrates are formed by many simple gases that do not interact strongly with water, and in most cases the gas molecules or atoms occupy 'cages' formed by a framework of water molecules. The majority of these gas hydrates adopt one of two cubic cage structures and are called clathrate hydrates. Notable exceptions are hydrogen and helium which form 'exotic' hydrates with structures based on ice structures, rather than clathrate hydrates, even at low pressures. Clathrate hydrates have been extensively studied because they occur widely in nature, have important industrial applications, and provide insight into water-guest hydrophobic interactions. Until recently, the expectation-based on calculations-had been that all clathrate hydrates were dissociated into ice and gas by the application of pressures of 1 GPa or so. However, over the past five years, studies have shown that this view is incorrect. Instead, all the systems so far studied undergo structural rearrangement to other, new types of hydrate structure that remain stable to much higher pressures than had been thought possible. In this paper we review work on gas hydrates at pressures above 0.5 GPa, identify common trends in transformations and structures, and note areas of uncertainty where further work is needed.

Structure of sodium above 100 GPa by single-crystal x-ray diffraction.

At pressures above a megabar (100 GPa), sodium crystallizes in a number of complex crystal structures with unusually low melting temperatures, reaching as low as 300 K at 118 GPa. We have utilized this unique behavior at extreme pressures to grow a single crystal of sodium at 108 GPa, and have investigated the complex crystal structure at this pressure using high-intensity x-rays from the new Diamond synchrotron source, in combination with a pressure cell with wide angular apertures. We confirm that, at 108 GPa, sodium is isostructural with the cI16 phase of lithium, and we have refined the full crystal structure of this phase. The results demonstrate the extension of single-crystal structure refinement beyond 100 GPa and raise the prospect of successfully determining the structures of yet more complex phases reported in sodium and other elements at extreme pressures.

Structure of dense liquid water by neutron scattering to 6.5 GPa and 670 K.

We present a neutron diffraction study of liquid water to 6.5 GPa and 670 K. From the measured structure factors we determine radial and angular distributions. It is shown that with increasing density water approaches a local structure common to a simple liquid while distorting only a little the tetrahedral first-neighbor coordination imposed by hydrogen bonds that remain intact.

Observation of a wurtzite form of gallium arsenide.

After a pressure decrease to ambient, the high-pressure SC16 phase of GaAs is found to transform to the hexagonal wurtzite structure. This has been suggested for GaAs in calculations but never previously observed experimentally. Wurtzite-GaAs is found to be stable at ambient pressures at temperatures up to 473 K, with a structure that is only slightly distorted from ideal. On recompression, the ratio is constant with pressure and wurtzite-GaAs transforms to the orthorhombic phase at 18.7(9) GPa.

Nature of the polyamorphic transition in ice under pressure.

We present a neutron diffraction study of the transition between low-density and high-density amorphous ice (LDA and HDA, respectively) under pressure at approximately 0.3 GPa, at 130 K. All the intermediate diffraction patterns can be accurately decomposed into a linear combination of the patterns of pure LDA and HDA. This progressive transformation of one distinct phase to another, with phase coexistence at constant pressure and temperature, gives direct evidence of a classical first-order transition. In situ Raman measurements and visual observation of the reverse transition strongly support these conclusions, which have implications for models of water and the proposed second critical point in the undercooled region of liquid water.

Structural complexity in gallium under high pressure: relation to alkali elements.

Ga-II, the stable phase of Ga between 2 and 10 GPa at room temperature, is shown to have a complex 104-atom orthorhombic structure. A new phase, Ga-V, is found between 10 and 14 GPa, with a rhombohedral hR6 structure. Ga-II has a modulated layer structure like those recently reported for Rb-III and Cs-III, with similar 8- and 10-atom a-b layers stacked along the c axis in the sequence 8-10-8-8-10-8-8-10-8-8-10-8. The cI16 structure of Li and Na can be understood as a stacking of very similar 8-atom layers. It is suggested that a Hume-Rothery mechanism contributes to the occurrence of these complex structures in such different metals.

Chain "melting" in the composite Rb-IV structure.

The Bragg peaks from the structure formed by the guest chains in the incommensurate composite structure of Rb-IV are all found to broaden strongly at pressures below 16.7(1) GPa. This signals a loss of the interchain correlation. At the lowest reachable pressure before the transition to Rb-III, 16.2 GPa, the correlation length is only approximately 30 A, or 4 times the interchain distance. There is also evidence of a loss of long-range order within each chain. The chains thus exhibit the onset of the characteristics of an ordered 1D liquid.

Structure of Rb-III: novel modulated stacking structures in alkali metals.

The crystal structure of Rb-III, stable between 13 and 17 GPa, has been determined from quasi-single-crystal x-ray diffraction data. It is orthorhombic, space group C222(1), with 52 atoms in the unit cell, and has an 8-10-8-8-10-8 stacking of 8- and 10-atom layers. The recently reported 84-atom structure of Cs-III can be understood as an 8-8-10-8-8-8-8-10-8-8 stacking of the same layers. These represent a new class of modulated elemental structures.

Structure of high-density amorphous ice under pressure.

We report in situ neutron diffraction studies of high-density amorphous ice (HDA) at 100 K at pressures up to 2.2 GPa. We find that the compression is achieved by a strong contraction ( approximately 20%) of the second neighbor coordination shell, so that at 2.2 GPa it closely approaches the first coordination shell, which itself remains intact in both structure and size. The hydrogen bond orientations suggest an absence of hydrogen bonding between first and second shells and that HDA has increasingly interpenetrating hydrogen bond networks under pressure.

Transition from cage clathrate to filled ice: the structure of methane hydrate III.

The structure of a new methane hydrate has been solved at 3 GPa from neutron and x-ray powder diffraction data. It is a dihydrate in which a 3D H-bonded network of water molecules forms channels surrounding the methane molecules. The network is closely related to that of ice-Ih and the methane-water system appears to be the first in which a cage clathrate hydrate is transformed into an ice-related hydrate (a "filled ice").