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Abstract Phase transitions in the mantle control its internal dynamics and structure. The post-spinel transition marks the upper–lower mantle boundary, where ringwoodite dissociates into bridgmanite plus ferropericlase, and its Clapeyron slope regulates mantle flow across it. This interaction has previously been assumed to have no lateral spatial variations, based on the assumption of a linear post-spinel boundary in pressure and temperature. Here we present laser-heated diamond anvil cell experiments with synchrotron X-ray diffraction to better constrain this boundary, especially at higher temperatures. Combining our data with results from the literature, and using a global analysis based on machine learning, we find a pronounced nonlinearity in the post-spinel boundary, with its slope ranging from –4 MPa/K at 2100 K, to –2 MPa/K at 1950 K, and to 0 MPa/K at 1600 K. Changes in temperature over time and space can therefore cause the post-spinel transition to have variable effects on mantle convection and the movement of subducting slabs and upwelling plumes.

Abstract (Mg,Fe)O ferropericlase‐magnesiowüstite has been proposed to host the majority of Earth's sodium, but the mechanism and capacity for incorporating the alkali cation remain unclear. In this work, experiments in the laser‐heated diamond anvil cell and first‐principles calculations determine the solubility of sodium and favorability of sodium incorporation in iron‐rich magnesiowüstite relative to (Mg,Fe)SiO3 bridgmanite. Reaction of Mg/(Mg + Fe) (Mg#) 55 and 28 olivine with NaCl at 33–128 GPa and 1600–3000 K produces iron‐rich magnesiowüstite containing several percent sodium, while iron‐rich bridgmanite contains little to no detectable sodium. In sodium‐saturated magnesiowüstite, sodium number [Na/(Na + Mg + Fe)] is 2–5 atomic percent at pressures below 60 GPa and drastically increases to 10–20 atomic percent at deep lower mantle pressures. For these two compositions, there is no significant dependence of the results on Mg#. Our calculations not only show consistent results with experiments but further indicate that such an increase in solubility and partitioning of Na into magnesiowüstite is driven by the spin transition in iron. These results provide fundamental constraints on the crystal chemistry of sodium at lower‐mantle conditions. If the sodium capacity of (Mg,Fe)O is not strongly dependent on Mg#, (Mg,Fe)O in the lower mantle may have the capacity to store the entire sodium budget of the Earth.

Abstract The high-pressure melting curve of FeO controls key aspects of Earth’s deep interior and the evolution of rocky planets more broadly. However, existing melting studies on wüstite were conducted across a limited pressure range and exhibit substantial disagreement. Here we use an in-situ dual-technique approach that combines a suite of >1000 x-ray diffraction and synchrotron Mössbauer measurements to report the melting curve for Fe1-x O wüstite to pressures of Earth’s lowermost mantle. We further observe features in the data suggesting an order-disorder transition in the iron defect structure several hundred kelvin below melting. This solid-solid transition, suggested by decades of ambient pressure research, is detected across the full pressure range of the study (30 to 140 GPa). At 136 GPa, our results constrain a relatively high melting temperature of 4140 ± 110 K, which falls above recent temperature estimates for Earth’s present-day core-mantle boundary and supports the viability of solid FeO-rich structures at the roots of mantle plumes. The coincidence of the defect order-disorder transition with pressure-temperature conditions of Earth’s mantle base raises broad questions about its possible influence on key physical properties of the region, including rheology and conductivity.

Abstract The allotropy of solid molecular nitrogen is the consequence of a complex interplay between fundamental intermolecular as well as intramolecular interactions. Understanding the underlying physical mechanisms hinges on knowledge of the crystal structures of these molecular phases. That is especially true for ζ-N2, key to shed light on nitrogen’s polymerization. Here, we perform single-crystal X-ray diffraction on laser-heated N2 samples at 54, 63, 70 and 86 GPa and solve and refine the hitherto unknown structure of ζ-N2. In its monoclinic unit cell (space group C2/c), 16 N2 molecules are arranged in a configuration similar to that of ε-N2. The structure model provides an explanation for the previously identified Raman and infrared lattice and vibrational modes of ζ-N2. Density functional theory calculations give an insight into the gradual delocalization of electronic density from intramolecular bonds to intermolecular space and suggest a possible pathway towards nitrogen’s polymerization.

An experimental platform for dynamic diamond anvil cell (dDAC) research has been developed at the High Energy Density (HED) Instrument at the European X-ray Free Electron Laser (European XFEL). Advantage was taken of the high repetition rate of the European XFEL (up to 4.5 MHz) to collect pulse-resolved MHz X-ray diffraction data from samples as they are dynamically compressed at intermediate strain rates (≤103 s−1), where up to 352 diffraction images can be collected from a single pulse train. The set-up employs piezo-driven dDACs capable of compressing samples in ≥340 µs, compatible with the maximum length of the pulse train (550 µs). Results from rapid compression experiments on a wide range of sample systems with different X-ray scattering powers are presented. A maximum compression rate of 87 TPa s−1 was observed during the fast compression of Au, while a strain rate of ∼1100 s−1 was achieved during the rapid compression of N2 at 23 TPa s−1.

The physics of NiO under applied pressure has long been debated and the material has been a key contributor to our understanding of Mott insulators and strongly correlated materials more generally. Here, the authors perform high-pressure X-ray diffraction measurements reporting a pressure-induced structural phase transition for NiO, which they suggest is linked with the metal-insulator transition of this system.

We report successful coupling of dynamic loading in a diamond anvil cell and stable laser heating, which enables compression rates up to 500 GPa/s along high-temperature isotherms. Dynamic loading in a diamond-anvil cell allows exploration of a wider range of pathways in the pressure-temperature space compared to conventional dynamic compression techniques. By in situ x-ray diffraction, we are able to characterize and monitor the structural transitions with the appropriate time resolution i.e., millisecond timescales. Using this method, we investigate the γ-ε phase transition of iron under dynamic compression, reaching compression rates of hundreds of GPa/s and temperatures of 2000 K. Our results demonstrate a distinct response of the γ-ε and α-ε transitions to the high compression rates achieved, possibly due to the different transition mechanisms. These findings open up new avenues to study tailored dynamic compression pathways in the pressure-temperature space and highlight the potential of this platform to capture kinetic effects (over ms time scales) in a diamond anvil cell.

Water is an essential chemical compound for living organisms, and twenty of its different crystal solid forms (ices) are known. Still, there are many fundamental problems with these structures such as establishing the correct positions and thermal motions of hydrogen atoms. The list of ice structures is not yet complete as DFT calculations have suggested the existence of additional and – to date – unknown phases. In many ice structures, neither neutron diffraction nor DFT calculations nor X-ray diffraction methods can easily solve the problem of hydrogen atom disorder or accurately determine their anisotropic displacement parameters (ADPs). Here, accurate crystal structures of H2O, D2O and mixed (50%H2O/50%D2O) ice VI obtained by Hirshfeld atom refinement (HAR) of high-pressure single-crystal synchrotron and laboratory X-ray diffraction data are presented. It was possible to obtain O—H/D bond lengths and ADPs for disordered hydrogen atoms which are in good agreement with the corresponding single-crystal neutron diffraction data. These results show that HAR combined with X-ray diffraction can compete with neutron diffraction in detailed studies of polymorphic forms of ice and crystals of other hydrogen-rich compounds. As neutron diffraction is relatively expensive, requires larger crystals which can be difficult to obtain and access to neutron facilities is restricted, cheaper and more accessible X-ray measurements combined with HAR can facilitate the verification of the existing ice polymorphs and the quest for new ones.

A series of in situ synchrotron X-ray diffraction (XRD) measurements were carried out, combined with first-principles calculations, to study structural phase transitions of selenium at high pressures and room temperature. Several phase transitions were observed, among which an isostructural phase transition was found at around 120 GPa for the first time. Evolved from the rhombohedral (space group R3m) structure (Se-V), the new phase (Se-V′) exhibited an interesting increase of lattice parameter a at pressures from 120 to 148 GPa, known as negative linear compressibility (NLC). The discovery of NLC behavior observed in this work is mainly attributed to the accuracy and fine steps controlled by the membrane system for in situ XRD data collected with an exposure time of 0.5 s. After 140 GPa, a body-centered cubic (b.c.c.) structure Se-VI (space group Im3m) was formed, which remains stable up to 210 GPa, the highest pressure achieved in this study. The bulk moduli of phases Se-V, Se-V′ and Se-VI were estimated to be 83 ± 2, 321 ± 2 and 266 ± 7 GPa, respectively, according to the P–V curve fit by the third-order Birch–Murnaghan equation of state. The Se-V′ phase shows a bulk modulus almost 4 times larger than that of the Se-V phase, which is mainly due to the effect of its NLC. NLC in a higher pressure range is always more significant in terms of fundamental mechanism and new materials discovery, yet it has barely been reported at pressures above 100 GPa. This will hopefully inspire future studies on potential NLC behaviors in other materials at ultra-high pressure.

Oxygen and iron are the most abundant elements on Earth, and their compounds are key planet-forming components. While oxygen is pervasive in the mantle, its presence in the solid inner core is still debatable. Yet, this issue is critical to understanding the co-evolution and the geomagnetic field generation. Thus far, iron monoxide (FeO) is the only known stoichiometric compound in the Fe–FeO system, and the existence of iron-rich FenO compounds has long been speculated. Here, we report that iron reacts with FeO and Fe2O3 at 220–260 GPa and 3000–3500 K in laser-heated diamond anvil cells. Ab initio structure searches using the adaptive genetic algorithm indicate that a series of stable stoichiometric FenO compounds (with n > 1) can be formed. Like ε–Fe and B8–FeO, FenO compounds have close-packed layered structures featuring oxygen-only single layers separated by iron-only layers. Two solid-solution models with compositions close to Fe2O, the most stable Fe-rich phase identified, explain the X-ray diffraction patterns of the experimental reaction products quenched to room temperature. These results suggest that Fe-rich FenO compounds with close-packed layered motifs might be stable under inner core conditions. Future studies of the elastic, rheological, and thermal transport properties of these more anisotropic FenO solids should provide new insights into the seismic features of the inner core, inner core formation process and composition, and the thermal evolution of the planet.

The experimental studies to understand the superconductivity of superhydrides remain scarce. Here, the authors report pressure and magnetic field dependence of superconductivity in LaH10, and indicate lattice vibrations strongly affect superconducting coupling.

The discovery of high temperature superconductivity in hydrogen-rich compounds stimulates further extensive studies. Here, the authors report superconductivity in pressurized yttrium-hydrogen system with highest predicted T c among binary compounds.

The study of water at high pressure and temperature is essential for understanding planetary interiors but is hampered by the high reactivity of water at extreme conditions. Here, indirect X-ray laser heating of water in a diamond anvil cell is realized via a gold absorber, showing no evidence of reactivity.

Along the cold subduction geotherm, glaucophane remains stable down to pressure and temperature (P–T) conditions of ca. 240 km depth, whereas under the warm subduction geotherm, it dehydrates and breaks down into pyroxenes and silica between ca. 50 and 100 km depths.

CaCO3 is more stable than MgCO3 under conditions of Earth’s lowermost mantle, with implications for deep mantle chemistry.

Abstract Single‐crystal X‐ray diffraction and Brillouin spectroscopy experiments were performed on a natural Cr‐pyrope (Prp71.0Alm12.6Sps0.7Grs3.5Uvr12.2) at high pressure and high temperature up to 11.0 GPa and 800 K. Fitting the collected data to the third‐order finite strain equation yields bulk modulus (KS0), shear modulus (G0), their pressure ((∂KS/∂P)T and (∂G/∂P)T) and temperature ((∂KS/∂T)P and (∂G/∂T)P) derivatives, KS0 = 167.7(8) GPa, G0 = 91.5(5) GPa, (∂KS/∂P)T = 4.3(1), (∂G/∂P)T = 1.4(1), (∂KS/∂T)P = −0.0175(1) GPa/K and (∂G/∂T)P = −0.0073(1) GPa/K. Using the obtained results, we examined whether the elastic properties of the Cr‐pyrope can be accurately calculated from those of endmembers including pyrope, almandine, grossular, and uvarovite assuming a linear relationship between elastic properties and composition (end‐member model). The results indicate that the end‐member model provides a sufficient approximation for the elastic properties of Cr‐pyrope in calculating the density and velocity of the subcontinental lithospheric mantle (SCLM). We modeled the densities and velocities of three typical types of SCLM (Archon, Proton, and Tecton) in order to investigate how the variation of chemical composition influences the SCLM. We obtained that the compositional change from the Archon to the Tecton increases the density of the SCLM significantly, which can be an important prerequisite for SCLM delamination. However, the compositional variation only slightly changes the velocity of the SCLM and the change is within the uncertainty of the calculation. Moreover, in comparison to the velocity, ρ/VP and ρ/VS are much more sensitive to the compositional change of the SCLM.

Metallization of pure hydrogen via overlapping of electronic bands requires high pressure above 3 Mbar. Here the authors study the Ba-H system and discover a unique superhydride BaH12 that contains molecular hydrogen, which demonstrates metallic properties and superconductivity below 1.5 Mbar.

The crystal structure of MgCO3-II has long been discussed in the literature where DFT-based model calculations predict a pressure-induced transition of the carbon atom from the sp2 to the sp3 type of bonding. We have now determined the crystal structure of iron-bearing MgCO3-II based on single-crystal X-ray diffraction measurements using synchrotron radiation. We laser-heated a synthetic (Mg0.85Fe0.15)CO3 single crystal at 2500 K and 98 GPa and observed the formation of a monoclinic phase with composition (Mg2.53Fe0.47)C3O9 in the space group C2/m that contains tetrahedrally coordinated carbon, where CO44− tetrahedra are linked by corner-sharing oxygen atoms to form three-membered C3O96− ring anions. The crystal structure of (Mg0.85Fe0.15)CO3 (magnesium iron carbonate) at 98 GPa and 300 K is reported here as well. In comparison with previous structure-prediction calculations and powder X-ray diffraction data, our structural data provide reliable information from experiments regarding atomic positions, bond lengths, and bond angles.

The pyrope (Prp)–almandine (Alm) solid solutions are the most fundamental garnet components on the Earth, and both the quartz inclusions in garnet (QuiG) barometry and the garnet inclusions in diamond barometry need to be constrained by the thermoelastic parameters of Prp-Alm solid solution garnets. Here, we report the thermoelastic properties of a series of synthetic Prp-Alm solid solutions based on the high-pressure and high-temperature (HP–HT) in situ synchrotron single-crystal x-ray diffraction (SCXRD) experiments up to ∼20 GPa and 700 K, using diamond anvil cell (DAC). Fitting the SCXRD data by the Birch-Murnaghan equation of state (BM-EoS) and the thermal-pressure EoS, we obtain the thermoelastic parameters of Prp-Alm solid solution garnets, including bulk modulus (K0), its pressure derivative (K′0), and the thermal expansion coefficient (α0). The K0 along the Prp-Alm solid solution changes linearly with Prp content within their uncertainties and can be expressed by K0 (GPa) = 181.0(8) – 0.11(1) Xprp (R2 = 0.91, Xprp is the Prp mole fraction and K′0 fixed at 4). Our result indicates that the compressibility of the Prp-Alm solid solution increases with the increasing Prp content. However, the thermal expansion coefficient of Prp-Alm solid solution at ambient pressure shows a non-linear trend with Prp content and can be expressed by α0 (10−5 K−1) = 2.7 (1) + 3.0 (5) XPrp− 3.2 (4) X2Prp (R2 = 0.985). It shows that the Prp-Alm solid solution with intermediate composition has a larger thermal expansion coefficient than those close to the endmembers at ambient conditions. Furthermore, we also evaluated the influence of thermoelastic properties of the Prp-Alm solid solution on the entrapment pressure (Pe) estimation for two types of elastic geobarometers. Our results indicate that the garnet component may significantly influence entrapment pressure, and among the thermoelastic parameters of garnet, the thermal expansion coefficient has the main effect on the estimation of Pe.

We predict superconductivity for the carbon–boron clathrate SrB_{3}C_{3} with T_{c}=27–43K for Coulomb pseudopotential (μ^{*}) values between 0.17 and 0.10 using first-principles calculations with conventional electron–phonon coupling. Electrical transport measurements, facilitated by an in situ experimental design compatible with extreme synthesis conditions (>3000K at 50 GPa), show nonhysteretic resistivity drops that track the calculated magnitude and pressure dependence of superconductivity for μ^{*}≈0.15, and transport measurements collected under applied magnetic fields indicate superconductivity with an onset T_{c} of approximately 20 K at 40 GPa. Carbon-based clathrates thus represent a class of superconductors similar to other covalent metals like MgB_{2} and doped fullerenes. Carbon clathrates share structures similar to superconducting superhydrides with wide potential for tunable properties, and covalent C–B bonds allow metastable persistence at ambient conditions.

While metallic glasses are expected to have tunable structures, these have rarely been demonstrated. Here, the authors combine temperature and pressure to show a two-way structural tuning in rare earth-based metallic glasses beyond the nearest-neighbor atomic shells.

Hydrogen-rich superhydrides are promising high-temperature superconductors which have been observed only at pressures above 170 GPa. Here the authors show that CeH9 can be synthesized at 80-100 GPa with laser heating, and is characterized by a clathrate structure with a dense 3-dimensional atomic hydrogen sublattice.

High pressure experiments may yield materials with unusual combinations of properties, but typically in small amounts and unstable. Here the authors synthesize millimeter-sized samples of metallic, ultraincompressible and very hard rhenium nitride pernitride, recoverable at ambient conditions.

Diamond anvil cell techniques have been improved to allow access to the multimegabar ultrahigh-pressure region for exploring novel phenomena in condensed matter. However, the only way to determine crystal structures of materials above 100 GPa, namely, X-ray diffraction (XRD), especially for low Z materials, remains nontrivial in the ultrahigh-pressure region, even with the availability of brilliant synchrotron X-ray sources. In this work, we perform a systematic study, choosing hydrogen (the lowest X-ray scatterer) as the subject, to understand how to better perform XRD measurements of low Z materials at multimegabar pressures. The techniques that we have developed have been proved to be effective in measuring the crystal structure of solid hydrogen up to 254 GPa at room temperature [C. Ji et al., Nature 573, 558–562 (2019)]. We present our discoveries and experiences with regard to several aspects of this work, namely, diamond anvil selection, sample configuration for ultrahigh-pressure XRD studies, XRD diagnostics for low Z materials, and related issues in data interpretation and pressure calibration. We believe that these methods can be readily extended to other low Z materials and can pave the way for studying the crystal structure of hydrogen at higher pressures, eventually testing structural models of metallic hydrogen.

Iron oxides prevail in the deep Earth, at extreme pressures and temperatures, with different stoichiometries than in ambient conditions. Here, high-pressure synchrotron X-ray spectroscopic measurements reveal the oxidation states of Fe and O in iron superoxide, shedding light on the puzzling chemistry of iron and oxygen in the deep Earth

Carbonates are shown to exist in the lower mantle as seen in diamond inclusions, but thermodynamic constraints are poorly understood. Here, the authors synthesise two new iron carbonate compounds and find that self-oxidation-reduction reactions can preserve carbonates in the mantle.

Whether a polymorphic transition exists in high entropy alloys or not remains unclear since discovery of these alloys more than a decade ago. Here authors report an irreversible polymorphic transition fromfcc to hcp in the prototype FeCoCrMnNi high entropy alloy and provide evidence for fccphase being more stable than hcp phase only at high temperatures.

The source of the anisotropic layer (D'' layer) at the bottom of the lower mantle remains unclear. Here, using high pressure and temperature experiments, the authors find that seismic anisotropy observed at the D'' layer is caused by 50% deformation of the minerals post-perovskite and ferropericlase.

The only known compound of sodium and hydrogen is ionic NaH, but theory predicts the existence of polyhydrides at high pressure. Here, the authors report observations of the formation of polyhydrides above 40 GPa and 2000 K, supporting the idea of multicentre bonding in a material with unusual stoichiometry.

Up to 17 GPa, the crystalline phases of N2 are characterized by pronounced orientational disorder, whereas the higher-pressure phases of molecular N2 are ordered. This raises the question about long-term relaxation of orientational disorder within the low- to intermediate-pressure regime. Here, this question is addressed by comparing synthetic with natural, chemically pure, solid N2 that resides as inclusions in diamonds at 300 K for about 108 years at pressures up to 11 GPa. It is shown that disorder prevails at 8.7 GPa, 300 K, where both synthetic and natural N2 assume the same structure. However, at 10.8 GPa, natural solid N2 exhibits monoclinic distortion and partial orientational ordering of the molecules, both of which are not observed in synthetic material. This difference is interpreted as the result of long-term structural relaxation. The ordering mechanism is examined and placed into the context of the δ- to ε-N2 transition. We present explanations for the absence of complete ordering of δ-N2. [ABSTRACT FROM AUTHOR]