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Astrophysical measurements have shown that some stars have sufficiently high carbon-to-oxygen ratios such that the planets they host would be mainly composed of carbides instead of silicates. We studied the behavior of silicon carbide in the presence of water under the high pressure-temperature conditions relevant to planetary interiors in the laser-heated diamond-anvil cell (LHDAC). When reacting with water, silicon carbide converts to silica (stishovite) and diamond at pressures up to 50 GPa and temperatures up to 2500 K: SiC + 2H$_2$O -> SiO$_2$ + C + 2H$_2$. Therefore, if water can be incorporated into carbide planets during their formation or through later delivery, they could be oxidized and have mineralogy dominated by silicates and diamond in their interiors. The reaction could produce CH$_4$ at shallower depths and H$_2$ at greater depths which could be degassed from the interior, causing the atmospheres of the converted carbon planets to be rich in reducing gases. Excess water after the reaction can be stored in dense silica polymorphs in the interiors of the converted carbon planets. Such conversion of mineralogy to diamond and silicates would decrease the density of carbon-rich planet, making the converted planets distinct from silicate planets in mass-radius relations for the 2-8 Earth mass range., Comment: 11 pages, 5 figures

Iron-bearing oxides undergo a series of pressure-induced electronic, spin and structural transitions that can cause seismic anomalies and dynamic instabilities in Earth's mantle and outer core. We employ x-ray diffraction and x-ray emission spectroscopy along with state-of-the-art density functional plus dynamical mean-field theory (DFT+DMFT) to characterize the electronic structure and spin states, and crystal-structural properties of w\"ustite (Fe$_{1-x}$O) -- a basic oxide component of Earth's interior -- at high pressure-temperature conditions up to 140 GPa and 2100 K. We find that FeO exhibits complex polymorphism under pressure, with abnormal compression behavior associated with electron-spin and crystallographic phase transitions, and resulting in a substantial change of bulk modulus. Our results reveal the existence of a high-pressure phase characterized by a metallic high-spin state of iron at about the pressure-temperature conditions of Earth's core-mantle boundary. The presence of high-spin metallic iron near the base of the mantle can significantly influence the geophysical and geochemical properties of Earth's deep interior., Comment: 5 figures, with supplementary materials

The discovery of high-temperature conventional superconductivity in H3S with a critical temperature of Tc=203 K was followed by the recent record of Tc ~250 K in the face-centered cubic (fcc) lanthanum hydride LaH10 compound. It was realized in a new class of hydrogen-dominated compounds having a clathrate-like crystal structure in which hydrogen atoms form a 3D framework and surround a host atom of rare earth elements. Yttrium hydrides are predicted to have even higher Tc exceeding room temperature. In this paper, we synthesized and refined the crystal structure of new hydrides: YH4, YH6, and YH9 at pressures up to 237 GPa finding that YH4 crystalizes in the I4/mmm lattice, YH6 in Im-3m lattice and YH9 in P63/mmc lattice in excellent agreement with the calculations. The observed very high-temperature superconductivity is comparable to that found in fcc-LaH10: the pressure dependence of Tc for YH9 also displays a "dome like shape" with the highest Tc of 243 K at 201 GPa. We also observed a Tc of 227 K at 237 GPa for the YH6 phase. However, the measured Tcs are notably lower by ~30 K than predicted. Evidence for superconductivity includes the observation of zero electrical resistance, a decrease of Tc under an external magnetic field and an isotope effect. The theoretically predicted fcc YH10 with the promising highest Tc>300 K was not stabilized in our experiments under pressures up to 237 GPa.

The discovery of superconductivity at 203 K in H3S brought attention back to conventional superconductors whose properties can be described by the Bardeen-Cooper-Schrieffer (BCS) and the Migdal-Eliashberg theories. These theories predict that high, and even room temperature superconductivity (RTSC) is possible in metals possessing certain favorable parameters such as lattice vibrations at high frequencies. However, these general theories do not suffice to predict real superconductors. New superconducting materials can be predicted now with the aid of first principles calculations based on Density Functional Theory (DFT). In particular, the calculations suggested a new family of hydrides possessing a clathrate structure, where the host atom (Ca, Y, La) is at the center of the cage formed by hydrogen atoms. For LaH10 and YH10 superconductivity, with critical temperatures Tc ranging between 240 and 320 K is predicted at megabar pressures. Here, we report superconductivity with a record Tc ~ 250 K within the Fm-3m structure of LaH10 at a pressure P ~ 170 GPa. We proved the existence of superconductivity at 250 K through the observation of zero-resistance, isotope effect, and the decrease of Tc under an external magnetic field, which suggests an upper critical magnetic field of 120 T at zero-temperature. The pressure dependence of the transition temperatures Tc (P) has a maximum of 250-252 K at the pressure of about 170 GPa. This leap, by ~ 50 K, from the previous Tc record of 203 K indicates the real possibility of achieving RTSC (that is at 273 K) in the near future at high pressures and the perspective of conventional superconductivity at ambient pressure.

X-ray diffraction pressure studies at room temperature demonstrate that the spinel FeAl$_{2}$O$_{4}$ transforms to a tetragonal phase at ~18 GPa. This tetragonal phase has a highly irregular unit-cell volume versus pressure dependence up to ~45 GPa, after which a transformation to a Cmcm post-spinel phase is onset. This is attributable to pressure driven Fe-Al site inversion at room temperature, corroborated by signatures in the 57Fe M\"ossbauer spectroscopy pressure data. At the tetragonal to post-spinel transition, onset in the range 45-50 GPa, there is a concurrent emergence of a non-magnetic spectral component in the M\"ossbauer data at variable cryogenic temperatures. This is interpreted as spin crossover at sixfold coordinated Fe locations emanated from site inversion. Spin crossover commences at the end of the pressure range of the tetragonal phase and progresses in the post-spinel structure. There is also a much steeper volume change dV/V ~ 10% in the range 45-50 GPa compared to the preceding pressure regime, from the combined effects of the structural transition and spin crossover electronic change. At the highest pressure attained, ~106 GPa, the M\"ossbauer data evidences a diamagnetic Fe low-spin abundance of ~50%. The rest of the high-spin Fe in eightfold coordinated sites continue to experience a relatively small internal magnetic field of ~33 T. This is indicative of a magnetic ground state associated with strong covalency, as well as substantive disorder from site inversion and the mixed spin-state configuration. Intriguingly magnetism survives in such a spin-diluted post-spinel lattice at high densities. The R(300 K) data decreases by only two orders of magnitude from ambient pressure to the vicinity of ~100 GPa. Despite a ~26% unit-cell volume densification from the lattice compressibility, structural transitions and spin crossover., Comment: 27 Pages and 5 Figuers

X-ray diffraction studies to ~90 GPa at room temperature show that Fe$_{2}$TiO$_{4}$ ferrous inverse spinel undergoes the following sequence of structural transitions : cubic (Fd3m) to tetragonal (I41/amd)to orthorhombic(Cmcm) to orthorhombic(Pmma),at the indicated onset transition pressures. Within the Cmcm phase, site-specific spin crossover is initiated and involves only highly distorted octahedral sites constituting ~25% of all Fe locations. This is manifest as a steeper volume decrease of dV/V0 ~ 3.5% beyond ~40 GPa and an emergent diamagnetic component discerned in 57Fe M\"ossbauer spectroscopy at variable cryogenic temperatures. A subsequent Cmcm to Pmma Fe/Ti disorder-order reconfiguration is facilitated at 6-fold coordinated (octahedral) sites. The rest of the high-spin Fe in 6-fold and 8-fold coordinated sites (~75% abundance) in the Pmma phase exhibit average saturation internal magnetic fields of H$_{hf}$ ~ 42 T to ~90 GPa, typical of spin-only (orbitally quenched) Fermi-contact values. By contrast average H$_{hf}$ ~ 20 T values, signifying unquenched orbital moments, occur below the 40-45 GPa spin-crossover initiation regime in the Cmcm phase. Therefore site-specific spin crossover invokes a cooperative lattice response and polyhedral distortions at the rest of the high-spin Fe sites, translating to 3d level (sub-band) changes and consequential orbital moment quenching. Near ~90 GPa Fe$_{2}$TiO$_{4}$ is a partially spin-converted chemically ordered Pmma post-spinel structure having a persistent charge gap of ~100 meV. Despite structural symmetry changes, partial spin crossover and lattice compressibility resulting in a ~33% total reduction in unit-cell volume and corresponding 3d bandwidth broadening, strong electron correlations persist at high densification., Comment: 35 Pages and 7 Figures

We provide experimental and theoretical evidence for a novel type of pressure-induced insulator-metal transition characterized by site-selective delocalization of the electrons. M\"ossbauer spectroscopy, X-ray diffraction and electrical transport measurements on Fe$_2$O$_3$ to 100 GPa, along with dynamical mean-field theory (DFT+DMFT) calculations, reveal this site-selective Mott transition between 50 and 68 GPa, such that the metallization can be described by ($^\rm{VI}$Fe$^{3+\rm{HS}}$)$_2$O$_3$ [$R\bar{3}c$ structure] $\overrightarrow{\tiny\rm{50~GPa}}$ ($^\rm{VIII}$Fe$^{3+\rm{HS~VI}}$Fe$^\rm{M}$)O$_3$ [$P2_1/n$ structure] $\overrightarrow{\tiny\rm{68~GPa}}$ ($^\rm{VI}$Fe$^\rm{M}$)$_2$O$_3$ [$Aba2$ structure]. Within the $P2_1/n$ crystal structure, characterized by two distinct coordination sites (VI and VIII), we observe equal abundances of ferric ions (Fe$^{3+}$) and ions having delocalized electrons (Fe$^\rm{M}$), and only at higher pressures is a fully metallic $Aba2$ structure obtained, all at room temperature. The transition is characterized by delocalization/metallization of the $3d$ electrons on half the Fe sites, with a site-dependent collapse of local moments. Above $\sim$50 GPa, Fe$_2$O$_3$ is a strongly correlated metal with reduced electron mobility (large band renormalizations) of m*/m$\sim$4 and 6 near the Fermi level. Upon decompression, we observe a site-selective (metallic) to conventional Mott insulator phase transition ($^\rm{VIII}$Fe$^{3+\rm{HS~VI}}$Fe$^\rm{M}$)O$_3$ $\overrightarrow{\tiny\rm{50~GPa}}$ ($^\rm{VIII}$Fe$^{3+\rm{HS~VI}}$Fe$^{3+ \rm{HS}}$)O$_3$ within the same $P2_1/n$ structure, indicating a decoupling of the electronic and lattice degrees of freedom, characteristic of a true Mott transition. Our results show that the interplay of electronic correlations and lattice may result in rather complex behavior of the electronic structure and magnetic state., Comment: 18 pages, 5 figures

Here we report the discovery of superconductivity in multiple phases of the compressed GeSb2Te4 (GST) phase change memory alloy, which has attracted considerable attention for the last decade due to its unusual physical properties with many potential applications. Superconductivity is observed through electrical transport measurements, both for the amorphous (a-GST) and for the crystalline (c-GST) phases. The superconducting critical temperature, TC, continuously increases with the applied pressure reaching a maximum Tc =6K at P=20 GPa for a-GST, whereas the critical temperature of the cubic phase reaches a maximum Tc =8 K at 30 GPa. This new material system, exhibiting a superconductor-insulator quantum phase transition (SIT) has an advantage over disordered metals since it has a continuous control of the crystal structure and the electronic properties using pressure as an external stimulus, which was lacking in SIT studies until today., Comment: 10 pages (including 4 supplementary), 9 figures (including 4 supplementary)

We report high pressure powder synchrotron x-ray diffraction studies on MFe2As2 (M=Ba, Ca) over a range of temperatures and pressures up to about 56 GPa using a membrane diamond anvil cell. A phase transition to a collapsed tetragonal phase is observed in both compounds upon compression. However, at 300 (33) K in the Ba-compound the transition occurs at 26 (29) GPa, which is a much higher pressure than 1.7 (0.3) GPa at 300 (40) K in the Ca-compound, due to its larger volume. It is important to note that the transition in both compounds occurs when they are compressed to almost the same value of the unit cell volume and attain similar ct/at ratios. We also show that the FeAs4 tetrahedra are much less compressible and more distorted in the collapsed tetragonal phase than their nearly regular shape in the ambient pressure phase. We present a detailed analysis of the pressure dependence of the structures as well as equation of states in these important BaFe2As2 and CaFe2As2 compounds., Comment: 26 pages, 12 figures