Predicted hot superconductivity in LaSc2H24 under pressure.

The recent theory-driven discovery of a class of clathrate hydrides (e.g., CaH6, YH6, YH9, and LaH10) with superconducting critical temperatures (Tc) well above 200 K has opened the prospects for "hot" superconductivity above room temperature under pressure. Recent efforts focus on the search for superconductors among ternary hydrides that accommodate more diverse material types and configurations compared to binary hydrides. Through extensive computational searches, we report the prediction of a unique class of thermodynamically stable clathrate hydrides structures consisting of two previously unreported H24 and H30 hydrogen clathrate cages at megabar pressures. Among these phases, LaSc2H24 shows potential hot superconductivity at the thermodynamically stable pressure range of 167 to 300 GPa, with calculated Tcs up to 331 K at 250 GPa and 316 K at 167 GPa when the important effects of anharmonicity are included. The very high critical temperatures are attributed to an unusually large hydrogen-derived density of states at the Fermi level arising from the newly reported peculiar H30 as well as H24 cages in the structure. Our predicted introduction of Sc in the La-H system is expected to facilitate future design and realization of hot superconductors in ternary clathrate superhydrides.

Chemical interactions that govern the structures of metals.

Most metals adopt simple structures such as body-centered cubic (BCC), face-centered cubic (FCC), and hexagonal close-packed (HCP) structures in specific groupings across the periodic table, and many undergo transitions to surprisingly complex structures on compression, not expected from conventional free-electron-based theories of metals. First-principles calculations have been able to reproduce many observed structures and transitions, but a unified, predictive theory that underlies this behavior is not yet in hand. Discovered by analyzing the electronic properties of metals in various lattices over a broad range of sizes and geometries, a remarkably simple theory shows that the stability of metal structures is governed by electrons occupying local interstitial orbitals and their strong chemical interactions. The theory provides a basis for understanding and predicting structures in solid compounds and alloys over a broad range of conditions.

Stress-induced high-Tc superconductivity in solid molecular hydrogen.

Solid molecular hydrogen has been predicted to be metallic and high-temperature superconducting at ultrahigh hydrostatic pressures that push current experimental limits. Meanwhile, little is known about the influence of nonhydrostatic conditions on its electronic properties at extreme pressures where anisotropic stresses are inevitably present and may also be intentionally introduced. Here we show by first-principles calculations that solid molecular hydrogen compressed to multimegabar pressures can sustain large anisotropic compressive or shear stresses that, in turn, cause major crystal symmetry reduction and charge redistribution that accelerate bandgap closure and promote superconductivity relative to pure hydrostatic compression. Our findings highlight a hitherto largely unexplored mechanism for creating superconducting dense hydrogen, with implications for exploring similar phenomena in hydrogen-rich compounds and other molecular crystals.

Coexistence of vitreous and crystalline phases of H2O at ambient temperature.

Formation of vitreous ice during rapid compression of water at room temperature is important for biology and the study of biological systems. Here, we show that Raman spectra of rapidly compressed water at greater than 1 GPa at room temperature exhibits the signature of high-density amorphous ice, whereas the X-ray diffraction (XRD) pattern is dominated by crystalline ice VI. To resolve this apparent contradiction, we used molecular dynamics simulations to calculate full vibrational spectra and diffraction patterns of mixtures of vitreous ice and ice VI, including embedded interfaces between the two phases. We show quantitatively that Raman spectra, which probe the local polarizability with respect to atomic displacements, are dominated by the vitreous phase, whereas a small amount of the crystalline component is readily apparent by XRD. The results of our combined experimental and theoretical studies have implications for detecting vitreous phases of water, survival of biological systems under extreme conditions, and biological imaging. The results provide additional insight into the stable and metastable phases of H2O as a function of pressure and temperature, as well as of other materials undergoing pressure-induced amorphization and other metastable transitions.

Thermal conductivity of Fe-Si alloys and thermal stratification in Earth's core.

Light elements in Earth's core play a key role in driving convection and influencing geodynamics, both of which are crucial to the geodynamo. However, the thermal transport properties of iron alloys at high-pressure and -temperature conditions remain uncertain. Here we investigate the transport properties of solid hexagonal close-packed and liquid Fe-Si alloys with 4.3 and 9.0 wt % Si at high pressure and temperature using laser-heated diamond anvil cell experiments and first-principles molecular dynamics and dynamical mean field theory calculations. In contrast to the case of Fe, Si impurity scattering gradually dominates the total scattering in Fe-Si alloys with increasing Si concentration, leading to temperature independence of the resistivity and less electron-electron contribution to the conductivity in Fe-9Si. Our results show a thermal conductivity of ∼100 to 110 W⋅m-1⋅K-1 for liquid Fe-9Si near the topmost outer core. If Earth's core consists of a large amount of silicon (e.g., > 4.3 wt %) with such a high thermal conductivity, a subadiabatic heat flow across the core-mantle boundary is likely, leaving a 400- to 500-km-deep thermally stratified layer below the core-mantle boundary, and challenges proposed thermal convection in Fe-Si liquid outer core.

Combining pressure and electrochemistry to synthesize superhydrides.

Recently, superhydrides have been computationally identified and subsequently synthesized with a variety of metals at very high pressures. In this work, we evaluate the possibility of synthesizing superhydrides by uniquely combining electrochemistry and applied pressure. We perform computational searches using density functional theory and particle swarm optimization calculations over a broad range of pressures and electrode potentials. Using a thermodynamic analysis, we construct pressure-potential phase diagrams and provide an alternate synthesis concept, pressure-potential ([Formula: see text]), to access phases having high hydrogen content. Palladium-hydrogen is a widely studied material system with the highest hydride phase being Pd3H4 Most strikingly for this system, at potentials above hydrogen evolution and ∼ 300 MPa pressure, we find the possibility to make palladium superhydrides (e.g., PdH10). We predict the generalizability of this approach for La-H, Y-H, and Mg-H with 10- to 100-fold reduction in required pressure for stabilizing phases. In addition, the [Formula: see text] strategy allows stabilizing additional phases that cannot be done purely by either pressure or potential and is a general approach that is likely to work for synthesizing other hydrides at modest pressures.

P-V-T equation of state of boron carbide.

We report the P-V-T equation of state measurements of B4C to 50 GPa and approximately 2500 K in laser-heated diamond anvil cells. We obtain an ambient temperature, third-order Birch-Murnaghan fit to the P-V data that yields a bulk modulus K0 of 221(2) GPa and derivative, (dK/dP)0 of 3.3(1). These were used in fits with both a Mie-Grüneisen-Debye model and a temperature-dependent, Birch-Murnaghan equation of state that includes thermal pressure estimated by thermal expansion (α) and a temperature-dependent bulk modulus (dK0/dT). The ambient pressure thermal expansion coefficient (α0 + α1T), Grüneisen γ(V) = γ0(V/V0)q and volume-dependent Debye temperature, were used as input parameters for these fits and found to be sufficient to describe the data in the whole P-T range of this study. This article is part of the theme issue 'Exploring the length scales, timescales and chemistry of challenging materials (Part 1)'.

Acoustic properties, elasticity, and equation of state of glycerol under pressure.

We employed high-pressure Brillouin scattering to study the pressure dependencies of acoustic modes of glycerol up to 14 GPa at 300 K. We observed longitudinal acoustic velocities and transverse acoustic velocities for the first time from 5 to 14 GPa. The results allow the determination of a complete set of elastic properties and an accurate determination of the pressure-volume (P-V) equation of state (EOS). EOS parameters, K0 = 14.9 ± 1.8 GPa and K'0 = 5.6 ± 0.5, were determined from fits to the data from ambient pressure to 14 GPa. Direct volume measurements of the P-V EOS are consistent with those determined by Brillouin scattering. A deviation from a Cauchy-like relationship for elastic properties was observed, and the pressure dependencies of the photoelastic constants and relaxation times were documented from 5 to 14 GPa. These results have broad implications for glass-forming liquids, viscoelastic theory, and mode coupling theory.

Evidence for complex iron oxides in the deep mantle from FeNi(Cu) inclusions in superdeep diamond.

The recent discovery in high-pressure experiments of compounds stable to 24-26 GPa with Fe4O5, Fe5O6, Fe7O9, and Fe9O11 stoichiometry has raised questions about their existence within the Earth's mantle. Incorporating both ferric and ferrous iron in their structures, these oxides if present within the Earth could also provide insight into diamond-forming processes at depth in the planet. Here we report the discovery of metallic particles, dominantly of FeNi (Fe0.71Ni0.24Cu0.05), in close spatial relation with nearly pure magnetite grains from a so-called superdeep diamond from the Earth's mantle. The microstructural relation of magnetite within a ferropericlase (Mg0.60Fe0.40)O matrix suggests exsolution of the former. Taking into account the bulk chemistry reconstructed from the FeNi(Cu) alloy, we propose that it formed by decomposition of a complex metal M oxide (M4O5) with a stoichiometry of (Fe3+2.15Fe2+1.59Ni2+0.17Cu+0.04)Σ=3.95O5 We further suggest a possible link between this phase and variably oxidized ferropericlase that is commonly trapped in superdeep diamond. The observation of FeNi(Cu) metal in relation to magnetite exsolved from ferropericlase is interpreted as arising from a multistage process that starts from diamond encapsulation of ferropericlase followed by decompression and cooling under oxidized conditions, leading to the formation of complex oxides such as Fe4O5 that subsequently decompose at shallower P-T conditions.

Stability of H3O at extreme conditions and implications for the magnetic fields of Uranus and Neptune.

The anomalous nondipolar and nonaxisymmetric magnetic fields of Uranus and Neptune have long challenged conventional views of planetary dynamos. A thin-shell dynamo conjecture captures the observed phenomena but leaves unexplained the fundamental material basis and underlying mechanism. Here we report extensive quantum-mechanical calculations of polymorphism in the hydrogen-oxygen system at the pressures and temperatures of the deep interiors of these ice giant planets (to >600 GPa and 7,000 K). The results reveal the surprising stability of solid and fluid trihydrogen oxide (H3O) at these extreme conditions. Fluid H3O is metallic and calculated to be stable near the cores of Uranus and Neptune. As a convecting fluid, the material could give rise to the magnetic field consistent with the thin-shell dynamo model proposed for these planets. H3O could also be a major component in both solid and superionic forms in other (e.g., nonconvecting) layers. The results thus provide a materials basis for understanding the enigmatic magnetic-field anomalies and other aspects of the interiors of Uranus and Neptune. These findings have direct implications for the internal structure, composition, and dynamos of related exoplanets.

Inelastic neutron scattering evidence for anomalous H-H distances in metal hydrides.

Hydrogen-containing materials are of fundamental as well as technological interest. An outstanding question for both is the amount of hydrogen that can be incorporated in such materials, because that determines dramatically their physical properties such as electronic and crystalline structure. The number of hydrogen atoms in a metal is controlled by the interaction of hydrogens with the metal and by the hydrogen-hydrogen interactions. It is well established that the minimal possible hydrogen-hydrogen distances in conventional metal hydrides are around 2.1 Å under ambient conditions, although closer H-H distances are possible for materials under high pressure. We present inelastic neutron scattering measurements on hydrogen in [Formula: see text] showing nonexpected scattering at low-energy transfer. The analysis of the spectra reveals that these spectral features in part originate from hydrogen vibrations confined by neighboring hydrogen at distances as short as 1.6 Å. These distances are much smaller than those found in related hydrides, thereby violating the so-called Switendick criterion. The results have implications for the design and creation of hydrides with additional properties and applications.

Prediction of Above-Room-Temperature Superconductivity in Lanthanide/Actinide Extreme Superhydrides.

Achieving room-temperature superconductivity has been an enduring scientific pursuit driven by broad fundamental interest and enticing potential applications. The recent discovery of high-pressure clathrate superhydride LaH10 with superconducting critical temperatures (Tc) of 250-260 K made it tantalizingly close to realizing this long-sought goal. Here, we report a remarkable finding based on an advanced crystal structure search method of a new class of extremely hydrogen-rich clathrate superhydride MH18 (M: rare-earth/actinide atom) stoichiometric compounds stabilized at an experimentally accessible pressure of 350 GPa. These compounds are predicted to host Tc up to 330 K, which is well above room temperature. The bonding and electronic properties of these MH18 clathrate superhydrides closely resemble those of atomic metallic hydrogen, giving rise to the highest Tc hitherto found in a thermodynamically stable hydride compound. An in-depth study of these extreme superhydrides offers insights for elucidating phonon-mediated superconductivity above room temperature in hydrogen-rich and other low-Z materials.

Low-Pressure Electrochemical Synthesis of Complex High-Pressure Superconducting Superhydrides.

There is great current interest in multicomponent superhydrides due to their unique quantum properties under pressure. A remarkable example is the ternary superhydride Li_{2}MgH_{16} computationally identified to have an unprecedented high superconducting critical temperature T_{c} of ∼470 K at 250 GPa. However, the very high synthesis pressures required remains a significant hurdle for detailed study and potential applications. In this Letter, we evaluate the feasibility of synthesizing ternary Li-Mg superhydrides by the recently proposed pressure-potential (P^{2}) method that uniquely combines electrochemistry and applied pressure to control synthesis and stability. The results indicate that it is possible to synthesize Li-Mg superhydrides at modest pressures by applying suitable electrode potentials. Using pressure alone, no Li-Mg ternary hydrides are predicted to be thermodynamically stable, but in the presence of electrode potentials, both Li_{2}MgH_{16} and Li_{4}MgH_{24} can be stabilized at modest pressures. Three polymorphs are predicted as ground states of Li_{2}MgH_{16} below 300 GPa, with transitions at 33 and 160 GPa. The highest pressure phase is superconducting, while the two at lower pressures are not. Our findings point out the potentially important role of the P^{2} method in controlling phase stability of complex multicomponent superhydrides.

Quantum and Classical Proton Diffusion in Superconducting Clathrate Hydrides.

The discovery of near room temperature superconductivity in clathrate hydrides has ignited the search for both higher temperature superconductors and deeper understanding of the underlying physical phenomena. In a conventional electron-phonon mediated picture for the superconductivity for these materials, the high critical temperatures predicted and observed can be ascribed to the low mass of the protons, but this also poses nontrivial questions associated with how the proton dynamics affect the superconductivity. Using clathrate superhydride Li_{2}MgH_{16} as an example, we show through ab initio path integral simulations that proton diffusion in this system is remarkably high, with a diffusion coefficient, for example, reaching 6×10^{-6} cm^{2}/s at 300 K and 250 GPa. The diffusion is achieved primarily through proton transfer among interstitial voids within the otherwise rigid Li_{2}Mg sublattice at these conditions. The findings indicate the coexistence of proton quantum diffusion together with hydrogen-induced superconductivity, with implications for other very-high-temperature superconducting hydrides.

The Li-F-H ternary system at high pressures.

Evolutionary crystal structure prediction searches have been employed to explore the ternary Li-F-H system at 300 GPa. Metastable phases were uncovered within the static lattice approximation, with LiF3H2, LiF2H, Li3F4H, LiF4H4, Li2F3H, and LiF3H lying within 50 meV/atom of the 0 K convex hull. All of these phases contain HnFn+1 - (n = 1, 2) anions and Li+ cations. Other structural motifs such as LiF slabs, H3 + molecules, and Fδ- ions are present in some of the low enthalpy Li-F-H structures. The bonding within the HnFn+1 - molecules, which may be bent or linear, symmetric or asymmetric, is analyzed. The five phases closest to the hull are insulators, while LiF3H is metallic and predicted to have a vanishingly small superconducting critical temperature. Li3F4H is predicted to be stable at zero pressure. This study lays the foundation for future investigations of the role of temperature and anharmonicity on the stability and properties of compounds and alloys in the Li-F-H ternary system.

X-ray diffraction and equation of state of the C-S-H room-temperature superconductor.

X-ray diffraction indicates that the structure of the recently discovered carbonaceous sulfur hydride (C-S-H) room-temperature superconductor is derived from previously established van der Waals compounds found in the H2S-H2 and CH4-H2 systems. Crystals of the superconducting phase were produced by a photochemical synthesis technique, leading to the superconducting critical temperature Tc of 288 K at 267 GPa. X-ray diffraction patterns measured from 124 to 178 GPa, within the pressure range of the superconducting phase, are consistent with an orthorhombic structure derived from the Al2Cu-type determined for (H2S)2H2 and (CH4)2H2 that differs from those predicted and observed for the S-H system at these pressures. The formation and stability of the C-S-H compound can be understood in terms of the close similarity in effective volumes of the H2S and CH4 components, and denser carbon-bearing S-H phases may form at higher pressures. The results are crucial for understanding the very high superconducting Tc found in the C-S-H system at megabar pressures.

Potential high-Tc superconducting lanthanum and yttrium hydrides at high pressure.

A systematic structure search in the La-H and Y-H systems under pressure reveals some hydrogen-rich structures with intriguing electronic properties. For example, LaH10 is found to adopt a sodalite-like face-centered cubic (fcc) structure, stable above 200 GPa, and LaH8 a C2/m space group structure. Phonon calculations indicate both are dynamically stable; electron phonon calculations coupled to Bardeen-Cooper-Schrieffer (BCS) arguments indicate they might be high-Tc superconductors. In particular, the superconducting transition temperature Tc calculated for LaH10 is 274-286 K at 210 GPa. Similar calculations for the Y-H system predict stability of the sodalite-like fcc YH10 and a Tc above room temperature, reaching 305-326 K at 250 GPa. The study suggests that dense hydrides consisting of these and related hydrogen polyhedral networks may represent new classes of potential very high-temperature superconductors.

Evidence for Superconductivity above 260 K in Lanthanum Superhydride at Megabar Pressures.

Recent predictions and experimental observations of high T_{c} superconductivity in hydrogen-rich materials at very high pressures are driving the search for superconductivity in the vicinity of room temperature. We have developed a novel preparation technique that is optimally suited for megabar pressure syntheses of superhydrides using modulated laser heating while maintaining the integrity of sample-probe contacts for electrical transport measurements to 200 GPa. We detail the synthesis and characterization of lanthanum superhydride samples, including four-probe electrical transport measurements that display significant drops in resistivity on cooling up to 260 K and 180-200 GPa, and resistivity transitions at both lower and higher temperatures in other experiments. Additional current-voltage measurements, critical current estimates, and low-temperature x-ray diffraction are also obtained. We suggest that the transitions represent signatures of superconductivity to near room temperature in phases of lanthanum superhydride, in good agreement with density functional structure search and BCS theory calculations.

Effects of Pressure and Temperature on the Atomic Fluctuations of Dihydrofolate Reductase from a Psychropiezophile and a Mesophile.

Determining the effects of extreme conditions on proteins from "extremophilic" and mesophilic microbes is important for understanding how life adapts to living at extremes as well as how extreme conditions can be used for sterilization and food preservation. Previous molecular dynamics simulations of dihydrofolate reductase (DHFR) from a psychropiezophile (cold- and pressure-loving), Moritella profunda (Mp), and a mesophile, Escherichia coli (Ec), at various pressures and temperatures indicate that atomic fluctuations, which are important for enzyme function, increase with both temperature and pressure. Here, the factors that cause increases in atomic fluctuations in the simulations are examined. The fluctuations increase with temperature not only because of greater thermal energy and thermal expansion of the protein but also because hydrogen bonds between protein atoms are weakened. However, the increase in fluctuations with pressure cannot be due to thermal energy, which remains constant, nor the compressive effects of pressure, but instead, the hydrogen bonds are also weakened. In addition, increased temperature causes larger increases in fluctuations of the loop regions of MpDHFR than EcDHFR, and increased pressure causes both increases and decreases in fluctuations of the loops, which differ between the two.

Synthesis and Stability of Lanthanum Superhydrides.

Recent theoretical calculations predict that megabar pressure stabilizes very hydrogen-rich simple compounds having new clathrate-like structures and remarkable electronic properties including room-temperature superconductivity. X-ray diffraction and optical studies demonstrate that superhydrides of lanthanum can be synthesized with La atoms in an fcc lattice at 170 GPa upon heating to about 1000 K. The results match the predicted cubic metallic phase of LaH10 having cages of thirty-two hydrogen atoms surrounding each La atom. Upon decompression, the fcc-based structure undergoes a rhombohedral distortion of the La sublattice. The superhydride phases consist of an atomic hydrogen sublattice with H-H distances of about 1.1 Å, which are close to predictions for solid atomic metallic hydrogen at these pressures. With stability below 200 GPa, the superhydride is thus the closest analogue to solid atomic metallic hydrogen yet to be synthesized and characterized.