Motivated to explore the formation of novel extended carbon-nitrogen solids via well-defined molecular precursor pathways, we studied the chemical reactivity of highly pure phosphorous tricyanide, P(CN)(3), under conditions of high pressure at room temperature. Raman and infrared (IR) spectroscopic measurements reveal a series of phase transformations below 10 GPa, and several low-frequency vibrational modes are reported for the first time. Synchrotron powder X-ray diffraction measurements taken during compression show that molecular P(CN)(3) is highly compressible, with a bulk modulus of 10.0 +/- 0.3 GPa, and polymerizes into an amorphous solid above similar to 10.0 GPa. Raman and IR spectra, together with first-principles molecular-dynamics simulations, show that the amorphization transition is associated with polymerization of the cyanide groups into CN bonds with predominantly sp(2) character, similar to known carbon nitrides, resulting in a novel phosphorous carbon nitride (PCN) polymeric phase, which is recoverable to ambient pressure. (C) 2015 AIP Publishing LLC.

Aluminous bridgmanite (Al-Bm) is the dominant phase in the Earth's lower mantle. In this study, the Mossbauer spectra of an Al-Bm sample Mg0.868Fe0.087Si0.944Al0.101O2.994 were recorded from 65 to 300 K at 1 bar. The temperature dependence of the center shift was fitted by the Debye model and yielded the Debye temperatures of 305 3 K for Fe2+ and 361 22 K for Fe3+. These values are lower than those of Al-free bridgmanite by 17 and 24%, respectively, indicating that the presence of Fe and Al increases the average Fe-O bond length and weakens the bond strength. At 300 K, the calculated recoil-free fractions of Fe2+ (0.637 +/- 0.006) and Fe3+ (0.72 +/- 0.02) are similar and therefore the molar fractions of Fe2+ and Fe3+ are nearly the same as the area fractions of the corresponding Mossbauer doublets. At 900 K, the calculated recoil-free fractions of Fe3+ is 46% higher than that of Fe2+, implying that the molar fraction of Fe3+ is only 41% for a measured spectral area fraction of 50%, and that the area fractions of iron sites may change with temperature without any changes in the valence state or spin state of iron. We infer that Fe3+ accounts for 46 +/- 2% of the iron in the Al-Bm and it enters the A site along with Al3+ in the B site through the coupled-substitution mechanism. An Fe2+ component with large quadrupole splitting (similar to 4.0 mm/s) was observed at cryogenic conditions and interpreted as a high-spin distorted iron site.

We use molecular dynamics with a first-principles-based shell model potential to study the electrocaloric effect (ECE) in lithium niobate, LiNbO3, and find a giant electrocaloric effect along a line passing through the ferroelectric transition. With an applied electric field, a line of maximum ECE passes through the zero field ferroelectric transition, continuing along a Widom line at high temperatures with increasing fields, and along the instability that leads to homogeneous ferroelectric switching below T-c with an applied field antiparallel to the spontaneous polarization. This line is defined as the minimum in the inverse capacitance under an applied electric field. We investigate the effects of pressure, temperature and an applied electric field on the ECE. The behavior we observe in LiNbO3 should generally apply to ferroelectrics; we therefore suggest that the operating temperature for refrigeration and energy scavenging applications should be above the ferroelectric transition region to obtain a large electrocaloric response. The relationship between T-c, the Widom line, and homogeneous switching should be universal among ferroelectrics, relaxors, multiferroics, and the same behavior should be found under applied magnetic fields in ferromagnets.

The structure of a liquid Fe-3.5wt% C alloy is examined for up to 7.2GPa via multiangle energy-dispersive X-ray diffraction using a Paris-Edinburgh type large-volume press. X-ray diffraction data show clear changes in the pressure-dependent peak positions of structure factor and reduced pair distribution function at 5GPa. These results suggest that the liquid Fe-3.5wt% C alloys change structurally at approximately 5GPa. This finding serves as a microscopic explanation for the alloy's previously observed density change at the same pressure. The pressure dependencies of the nearest and second neighbor distances of the liquid Fe-3.5wt% C alloy are similar to those of liquid Fe which exhibits a structural change near the bcc-fcc-liquid triple point (5.2GPa and 1991K). Similarities between Fe-3.5wt% C and Fe suggest that a density change also occurs in liquid Fe and that this structural change extends to other Fe-light element alloys.

We combine high-pressure x-ray diffraction, high-pressure Raman scattering, and optical microscopy to investigate a series of (1 - x)Pb(Mg1/3Nb2/3)O-3-xPbTiO(3) (PMN-xPT) solid solutions (x = 0.2, 0.3, 0.33, 0.35, 0.37, 0.4) in diamond anvil cells up to 20 GPa at 300 K. The Raman spectra show a peak centered at 380 cm(-1) starting above 6 GPa for all samples, in agreement with previous observations. X-ray diffraction measurements are consistent with this spectral change indicating a structural phase transition; we find that the triplet at the pseudocubic (220) Bragg peak merges into a doublet above 6 GPa. Our results indicate that the morphotropic phase boundary region (x = 0.33 - 0.37) with the presence of monoclinic symmetry persists up to 7 GPa. The pressure dependence of ferroelectric domains in PMN-0.32PT single crystals was observed using a polarizing optical microscope. The domain wall density decreases with pressure and the domains disappear at a modest pressure of 3 GPa. We propose a pressure-composition phase diagram for PMN-xPT solid solutions. DOI: 10.1103/PhysRevB.86.224111

It is well known that pressure causes profound changes in the properties of atoms and chemical bonding, leading to the formation of many unusual materials. Here we systematically explore all stable calcium carbides at pressures from ambient to 100 GPa using variable-composition evolutionary structure predictions using the USPEX code. We find that Ca5C2, Ca2C, Ca3C2, CaC, Ca2C3 and CaC2 have stability fields on the phase diagram. Among these, Ca2C and Ca2C3 are successfully synthesized for the first time via high-pressure experiments with excellent structural correspondence to theoretical predictions. Of particular significance is the base-centred monoclinic phase (space group C2/m) of Ca2C, a quasi-two-dimensional metal with layers of negatively charged calcium atoms, and the primitive monoclinic phase (space group P2(1)/c) of CaC with zigzag C-4 groups. Interestingly, strong interstitial charge localization is found in the structure of R-3m-Ca5C2 with semi-metallic behaviour.

Estimates of the primitive upper mantle (PUM) composition reveal a depletion in many of the siderophile (iron-loving) elements, thought to result from their extraction to the core during terrestrial accretion. Experiments to investigate the partitioning of these elements between metal and silicate melts suggest that the PUM composition is best matched if metal-silicate equilibrium occurred at high pressures and temperatures, in a deep magma ocean environment. The behavior of the most highly siderophile elements (HSEs) during this process however, has remained enigmatic. Silicate run-products from HSE solubility experiments are commonly contaminated by dispersed metal inclusions that hinder the measurement of element concentrations in the melt. The resulting uncertainty over the true solubility and metal-silicate partitioning of these elements has made it difficult to predict their expected depletion in PUM. Recently, several studies have employed changes to the experimental design used for high pressure and temperature solubility experiments in order to suppress the formation of metal inclusions. The addition of Au (Re, Os, Ir, Ru experiments) or elemental Si (Pt experiments) to the sample acts to alter either the geometry or rate of sample reduction respectively, in order to avoid transient metal oversaturation of the silicate melt. This contribution outlines procedures for using the pistoncylinder and multi-anvil apparatus to conduct solubility and metal-silicate partitioning experiments respectively. A protocol is also described for the synthesis of uncontaminated run-products from HSE solubility experiments in which the oxygen fugacity is similar to that during terrestrial core-formation. Time-resolved LA-ICP-MS spectra are presented as evidence for the absence of metal-inclusions in run-products from earlier studies, and also confirm that the technique may be extended to investigate Ru. Examples are also given of how these data may be applied.