High-pressure--high-temperature polymorphism in ta: resolving an ongoing experimental controversy.

Phase diagrams of refractory metals remain essentially unknown. Moreover, there is an ongoing controversy over the high-pressure melting temperatures of these metals: results of diamond anvil cell (DAC) and shock wave experiments differ by at least a factor of 2. From an extensive ab initio study on tantalum we discovered that the body-centered cubic phase, its physical phase at ambient conditions, transforms to another solid phase, possibly hexagonal omega phase, at high temperature. Hence the sample motion observed in DAC experiments is very likely not due to melting but internal stresses accompanying a solid-solid transformation, and thermal stresses associated with laser heating.

The influence of hydrogen contamination on the structural stability of CoSn under compression.

The binary CoSn compound has a unique ground state large-void crystal structure, whose stability under pressure has recently been examined. Whereas theoretical results predicted a series of phase transformations, the room temperature experiments did not observe any structural change. We suggest that the large void of a CoSn-type structure could contain natural impurities such as hydrogen, which can influence the thermodynamic stability of a CoSn system and explain the unusual disagreement between the theoretical and experimental results. Based on first-principles calculations we reveal that the contamination of CoSn by hydrogen only results in a subtle change of structural parameters and the equation of state of CoSn, but drastically increases the stability of the CoSn-type phase in comparison with the high-pressure phases predicted earlier. We argue that the hardly detectable natural impurities of light elements in porous compounds like CoSn are able to change the phase equilibria.

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.

Molybdenum at high pressure and temperature: melting from another solid phase.

The Gibbs free energies of bcc and fcc Mo are calculated from first principles in the quasiharmonic approximation in the pressure range from 350 to 850 GPa at room temperatures up to 7500 K. It is found that Mo, stable in the bcc phase at low temperatures, has lower free energy in the fcc structure than in the bcc phase at elevated temperatures. Our density-functional-theory-based molecular dynamics simulations demonstrate that fcc melts at higher than bcc temperatures above 1.5 Mbar. Our calculated melting temperatures and bcc-fcc boundary are consistent with the Mo Hugoniot sound speed measurements. We find that melting occurs at temperatures significantly above the bcc-fcc boundary. This suggests an explanation of the recent diamond anvil cell experiments, which find a phase boundary in the vicinity of our extrapolated bcc-fcc boundary.

Pure iron compressed and heated to extreme conditions.

The results of a first-principles study supported by the temperature-quenched laser-heated diamond anvil-cell experiments on the high-pressure high-temperature structural behavior of pure iron are reported. We show that in contrast to the widely accepted picture, the face-centered cubic (fcc) phase becomes as stable as the hexagonal-close-packed (hcp) phase at pressures around 300-360 GPa and temperatures around 5000-6000 K. Our temperature-quenched experiments indicate that the fcc phase of iron can exist in the pressure-temperature region above 160 GPa and 3700 K, respectively. This, in particular, means that the actual structure of the Earth's core may be a complex phase with a large number of stacking faults.

Body-centered cubic iron-nickel alloy in Earth's core.

Cosmochemical, geochemical, and geophysical studies provide evidence that Earth's core contains iron with substantial (5 to 15%) amounts of nickel. The iron-nickel alloy Fe(0.9)Ni(0.1) has been studied in situ by means of angle-dispersive x-ray diffraction in internally heated diamond anvil cells (DACs), and its resistance has been measured as a function of pressure and temperature. At pressures above 225 gigapascals and temperatures over 3400 kelvin, Fe(0.9)Ni(0.1) adopts a body-centered cubic structure. Our experimental and theoretical results not only support the interpretation of shockwave data on pure iron as showing a solid-solid phase transition above about 200 gigapascals, but also suggest that iron alloys with geochemically reasonable compositions (that is, with substantial nickel, sulfur, or silicon content) adopt the bcc structure in Earth's inner core.

Noblest of all metals is structurally unstable at high pressure.

In a series of experiments in externally electrically heated diamond anvil cells we demonstrate that at pressures above approximately 240 GPa gold adopts a hexagonal-close-packed structure. Ab initio calculations predict that at pressures about 250 GPa different stacking sequences of close-packed atomic layers in gold become virtually degenerate in energy, strongly supporting the experimental observations.

Fluctuating lattice constants of indium under high pressure.

Recent high-pressure investigations of elemental In have yielded controversial results. We show that the observed high-pressure face-centered orthorhombic (fco) structure can be explained as an intermediate state between two body-centered tetragonal (bct) structures with different c/a ratios (c/a < square root [2] and c/a > square root [2], respectively). In a pressure range from about 50 to 200 GPa these two bct structures correspond to local minima of the total energy with respect to orthorhombic distortion of the ground-state bct In structure. The fco saddle point represents a tiny barrier and even at low temperatures rapid structural fluctuations should occur. Such a situation has not been identified in any other elemental metal.