Remarkable stability of γ - N 2 and its prevalence in the nitrogen phase diagram.

Solid nitrogen exhibits a panoply of phenomena ranging from complex molecular crystalline configurations to polymerization and closing band gap at higher densities. Among the elemental molecular solids, nitrogen stands apart for having phases, which can only be stabilized following particular pressure-temperature pathways, indicative of metastability and kinetic barriers. Here, through the combination of Raman spectroscopy and dynamic compression techniques, we find that the appearance of the whole nitrogen phase diagram is determined by the P-T paths taken below 2 GPa. We reveal the existence of the path- and phase-dependent triple point between the ß - N 2 , δ loc - N 2 and γ - or ϵ - N 2 . We further show that the ß - N 2 towards γ - N 2 path below the triple point, that evades δ ( δ loc )- N 2 , results in the formation of γ - N 2 , which in turn becomes a dominant phase. We then demonstrate, that the ß - N 2 through δ ( δ loc )- N 2 above the triple point path leads to the formation of ϵ - N 2 and the "well-established" phase diagram. An additional pathway, which by-passes the rotationally inhibited modifications δ ( δ loc )- N 2 , via rapid compression is found to produce γ - N 2 at higher temperatures. We argue that the pathway and phase sensitive triple point and the compression rate dependent phase formation challenge our understanding of this archetypal dense molecular solid.

Feasible Route to High-Temperature Ambient-Pressure Hydride Superconductivity.

A key challenge in materials discovery is to find high-temperature superconductors. Hydrogen and hydride materials have long been considered promising materials displaying conventional phonon-mediated superconductivity. However, the high pressures required to stabilize these materials have restricted their application. Here, we present results from high-throughput computation, considering a wide range of high-symmetry ternary hydrides from across the periodic table at ambient pressure. This large composition space is then reduced by considering thermodynamic, dynamic, and magnetic stability before direct estimations of the superconducting critical temperature. This approach has revealed a metastable ambient-pressure hydride superconductor, Mg_{2}IrH_{6}, with a predicted critical temperature of 160 K, comparable to the highest temperature superconducting cuprates. We propose a synthesis route via a structurally related insulator, Mg_{2}IrH_{7}, which is thermodynamically stable above 15 GPa, and discuss the potential challenges in doing so.

Universal insertion of molecules in ionic compounds under pressure.

Using first-principles calculations and crystal structure search methods, we found that many covalently bonded molecules such as H2, N2, CO2, NH3, H2O and CH4 may react with NaCl, a prototype ionic solid, and form stable compounds under pressure while retaining their molecular structure. These molecules, despite whether they are homonuclear or heteronuclear, polar or non-polar, small or large, do not show strong chemical interactions with surrounding Na and Cl ions. In contrast, the most stable molecule among all examples, N2, is found to transform into cyclo-N5- anions while reacting with NaCl under high pressures. It provides a new route to synthesize pentazolates, which are promising green energy materials with high energy density. Our work demonstrates a unique and universal hybridization propensity of covalently bonded molecules and solid compounds under pressure. This surprising miscibility suggests possible mixing regions between the molecular and rock layers in the interiors of large planets.

Microscopic theory of colour in lutetium hydride.

Nitrogen-doped lutetium hydride has recently been proposed as a near-ambient-conditions superconductor. Interestingly, the sample transforms from blue to pink to red as a function of pressure, but only the pink phase is claimed to be superconducting. Subsequent experimental studies have failed to reproduce the superconductivity, but have observed pressure-driven colour changes including blue, pink, red, violet, and orange. However, discrepancies exist among these experiments regarding the sequence and pressure at which these colour changes occur. Given the claimed relationship between colour and superconductivity, understanding colour changes in nitrogen-doped lutetium hydride may hold the key to clarifying the possible superconductivity in this compound. Here, we present a full microscopic theory of colour in lutetium hydride, revealing that hydrogen-deficient LuH2 is the only phase which exhibits colour changes under pressure consistent with experimental reports, with a sequence blue-violet-pink-red-orange. The concentration of hydrogen vacancies controls the precise sequence and pressure of colour changes, rationalising seemingly contradictory experiments. Nitrogen doping also modifies the colour of LuH2 but it plays a secondary role compared to hydrogen vacancies. Therefore, we propose hydrogen-deficient LuH2 as the key phase for exploring the superconductivity claim in the lutetium-hydrogen system. Finally, we find no phonon-mediated superconductivity near room temperature in the pink phase.

Developments and further applications of ephemeral data derived potentials.

Machine-learned interatomic potentials are fast becoming an indispensable tool in computational materials science. One approach is the ephemeral data-derived potential (EDDP), which was designed to accelerate atomistic structure prediction. The EDDP is simple and cost-efficient. It relies on training data generated in small unit cells and is fit using a lightweight neural network, leading to smooth interactions which exhibit the robust transferability essential for structure prediction. Here, we present a variety of applications of EDDPs, enabled by recent developments of the open-source EDDP software. New features include interfaces to phonon and molecular dynamics codes, as well as deployment of the ensemble deviation for estimating the confidence in EDDP predictions. Through case studies ranging from elemental carbon and lead to the binary scandium hydride and the ternary zinc cyanide, we demonstrate that EDDPs can be trained to cover wide ranges of pressures and stoichiometries, and used to evaluate phonons, phase diagrams, superionicity, and thermal expansion. These developments complement continued success in accelerated structure prediction.

Search for ambient superconductivity in the Lu-N-H system.

Motivated by the recent report of room-temperature superconductivity at near-ambient pressure in N-doped lutetium hydride, we performed a comprehensive, detailed study of the phase diagram of the Lu-N-H system, looking for superconducting phases. We combined ab initio crystal structure prediction with ephemeral data-derived interatomic potentials to sample over 200,000 different structures. Out of the more than 150 structures predicted to be metastable within ~50 meV from the convex hull we identify 52 viable candidates for conventional superconductivity, for which we computed their superconducting properties from Density Functional Perturbation Theory. Although for some of these structures we do predict a finite superconducting Tc, none is even remotely compatible with room-temperature superconductivity as reported by Dasenbrock et al. Our work joins the broader community effort that has followed the report of near-ambient superconductivity, confirming beyond reasonable doubt that no conventional mechanism can explain the reported Tc in Lu-N-H.

Excitonic insulator to superconductor phase transition in ultra-compressed helium.

Helium, the second most abundant element in the universe, exhibits an extremely large electronic band gap of about 20 eV at ambient pressures. While the metallization pressure of helium has been accurately determined, thus far little attention has been paid to the specific mechanisms driving the band-gap closure and electronic properties of this quantum crystal in the terapascal regime (1 TPa = 10 Mbar). Here, we employ density functional theory and many-body perturbation calculations to fill up this knowledge gap. It is found that prior to reaching metallicity helium becomes an excitonic insulator (EI), an exotic state of matter in which electrostatically bound electron-hole pairs may form spontaneously. Furthermore, we predict metallic helium to be a superconductor with a critical temperature of ≈ 20 K just above its metallization pressure and of ≈ 70 K at 100 TPa. These unforeseen phenomena may be critical for improving our fundamental understanding and modeling of celestial bodies.

Automatic differentiation for orbital-free density functional theory.

Differentiable programming has facilitated numerous methodological advances in scientific computing. Physics engines supporting automatic differentiation have simpler code, accelerating the development process and reducing the maintenance burden. Furthermore, fully differentiable simulation tools enable direct evaluation of challenging derivatives-including those directly related to properties measurable by experiment-that are conventionally computed with finite difference methods. Here, we investigate automatic differentiation in the context of orbital-free density functional theory (OFDFT) simulations of materials, introducing PROFESS-AD. Its automatic evaluation of properties derived from first derivatives, including functional potentials, forces, and stresses, facilitates the development and testing of new density functionals, while its direct evaluation of properties requiring higher-order derivatives, such as bulk moduli, elastic constants, and force constants, offers more concise implementations than conventional finite difference methods. For these reasons, PROFESS-AD serves as an excellent prototyping tool and provides new opportunities for OFDFT.

Magnesium oxide-water compounds at megabar pressure and implications on planetary interiors.

Magnesium Oxide (MgO) and water (H2O) are abundant in the interior of planets. Their properties, and in particular their interaction, significantly affect the planet interior structure and thermal evolution. Here, using crystal structure predictions and ab initio molecular dynamics simulations, we find that MgO and H2O can react again at ultrahigh pressure, although Mg(OH)2 decomposes at low pressure. The reemergent MgO-H2O compounds are: Mg2O3H2 above 400 GPa, MgO3H4 above 600 GPa, and MgO4H6 in the pressure range of 270-600 GPa. Importantly, MgO4H6 contains 57.3 wt % of water, which is a much higher water content than any reported hydrous mineral. Our results suggest that a substantial amount of water can be stored in MgO rock in the deep interiors of Earth to Neptune mass planets. Based on molecular dynamics simulations we show that these three compounds exhibit superionic behavior at the pressure-temperature conditions as in the interiors of Uranus and Neptune. Moreover, the water-rich compound MgO4H6 could be stable inside the early Earth and therefore may serve as a possible early Earth water reservoir. Our findings, in the poorly explored megabar pressure regime, provide constraints for interior and evolution models of wet planets in our solar system and beyond.

Quantum structural fluxion in superconducting lanthanum polyhydride.

The discovery of 250-kelvin superconducting lanthanum polyhydride under high pressure marked a significant advance toward the realization of a room-temperature superconductor. X-ray diffraction (XRD) studies reveal a nonstoichiometric LaH9.6 or LaH10±Î´ polyhydride responsible for the superconductivity, which in the literature is commonly treated as LaH10 without accounting for stoichiometric defects. Here, we discover significant nuclear quantum effects (NQE) in this polyhydride, and demonstrate that a minor amount of stoichiometric defects will cause quantum proton diffusion in the otherwise rigid lanthanum lattice in the ground state. The diffusion coefficient reaches ~10-7 cm2/s in LaH9.63 at 150 gigapascals and 240 kelvin, approaching the upper bound value of interstitial hydrides at comparable temperatures. A puzzling phenomenon observed in previous experiments, the positive pressure dependence of the superconducting critical temperature Tc below 150 gigapascals, is explained by a modulation of the electronic structure due to a premature distortion of the hydrogen lattice in this quantum fluxional structure upon decompression, and resulting changes of the electron-phonon coupling. This finding suggests the coexistence of the quantum proton fluxion and hydrogen-induced superconductivity in this lanthanum polyhydride, and leads to an understanding of the structural nature and superconductivity of nonstoichiomectric hydrogen-rich materials.

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.

Revealing carbon capture chemistry with 17-oxygen NMR spectroscopy.

Carbon dioxide capture is essential to achieve net-zero emissions. A hurdle to the design of improved capture materials is the lack of adequate tools to characterise how CO2 adsorbs. Solid-state nuclear magnetic resonance (NMR) spectroscopy is a promising probe of CO2 capture, but it remains challenging to distinguish different adsorption products. Here we perform a comprehensive computational investigation of 22 amine-functionalised metal-organic frameworks and discover that 17O NMR is a powerful probe of CO2 capture chemistry that provides excellent differentiation of ammonium carbamate and carbamic acid species. The computational findings are supported by 17O NMR experiments on a series of CO2-loaded frameworks that clearly identify ammonium carbamate chain formation and provide evidence for a mixed carbamic acid - ammonium carbamate adsorption mode. We further find that carbamic acid formation is more prevalent in this materials class than previously believed. Finally, we show that our methods are readily applicable to other adsorbents, and find support for ammonium carbamate formation in amine-grafted silicas. Our work paves the way for investigations of carbon capture chemistry that can enable materials design.

Chemically Assisted Precompression of Hydrogen Molecules in Alkaline-Earth Tetrahydrides.

Through a series of high pressure diamond anvil experiments, we report the synthesis of alkaline earth (Ca, Sr, Ba) tetrahydrides, and investigate their properties through Raman spectroscopy, X-ray diffraction, and density functional theory calculations. The tetrahydrides incorporate both atomic and quasi-molecular hydrogen, and we find that the frequency of the intramolecular stretching mode of the H2δ- units downshifts from Ca to Sr and to Ba upon compression. The experimental results indicate that the larger the host cation, the longer the H2δ- bond. Analysis of the electron localization function (ELF) demonstrates that the lengthening of the H-H bond is caused by the charge transfer from the metal to H2δ- and by the steric effect of the metal host on the H-H bond. This effect is most prominent for BaH4, where the precompression of H2δ- units at 50 GPa results in bond lengths comparable to that of pure H2 above 275 GPa.

Metallic Aluminum Suboxides with Ultrahigh Electrical Conductivity at High Pressure.

Aluminum, as the most abundant metallic elemental content in the Earth's crust, usually exists in the form of alumina (Al2O3). However, the oxidation state of aluminum and the crystal structures of aluminum oxides in the pressure range of planetary interiors are not well established. Here, we predicted two aluminum suboxides (Al2O, AlO) and two superoxides (Al4O7, AlO3) with uncommon stoichiometries at high pressures using first-principle calculations and crystal structure prediction methods. We find that the P4/nmm Al2O becomes stable above ~765 GPa and may survive in the deep mantles or cores of giant planets such as Neptune. Interestingly, the Al2O and AlO are metallic and have electride features, in which some electrons are localized in the interstitials between atoms. We find that Al2O has an electrical conductivity one order of magnitude higher than that of iron under the same pressure-temperature conditions, which may influence the total conductivity of giant planets. Our findings enrich the high-pressure phase diagram of aluminum oxides and improve our understanding of the interior structure of giant planets.

The first-principles phase diagram of monolayer nanoconfined water.

Water in nanoscale cavities is ubiquitous and of central importance to everyday phenomena in geology and biology. However, the properties of nanoscale water can be substantially different from those of bulk water, as shown, for example, by the anomalously low dielectric constant of water in nanochannels1, near frictionless water flow2 or the possible existence of a square ice phase3. Such properties suggest that nanoconfined water could be engineered for technological applications in nanofluidics4, electrolyte materials5 and water desalination6. Unfortunately, challenges in experimentally characterizing water at the nanoscale and the high cost of first-principles simulations have prevented the molecular-level understanding required to control the behaviour of water. Here we combine a range of computational approaches to enable a first-principles-level investigation of a single layer of water within a graphene-like channel. We find that monolayer water exhibits surprisingly rich and diverse phase behaviour that is highly sensitive to temperature and the van der Waals pressure acting within the nanochannel. In addition to multiple molecular phases with melting temperatures varying non-monotonically by more than 400 kelvins with pressure, we predict a hexatic phase, which is an intermediate between a solid and a liquid, and a superionic phase with a high electrical conductivity exceeding that of battery materials. Notably, this suggests that nanoconfinement could be a promising route towards superionic behaviour under easily accessible conditions.

Structural diversity and hydrogen storage properties in the system K-Si-H.

KSiH3 exhibits 4.1 wt% experimental hydrogen storage capacity and shows reversibility under moderate conditions, which provides fresh impetus to the search for other complex hydrides in the K-Si-H system. Here, we reproduce the stable Fm3̄m phase of K2SiH6 and uncover two denser phases, space groups P3̄m1 and P63mc at ambient pressure, by means of first-principles structure searches. We note that P3̄m1-K2SiH6 has a high hydrogen content of 5.4 wt% and a volumetric density of 88.3 g L-1. Further calculations suggest a favorable dehydrogenation temperature Tdes of -20.1/55.8 °C with decomposition into KSi + K + H2. The higher hydrogen density and appropriate dehydrogenation temperature indicate that K2SiH6 is a promising hydrogen storage material, and our results provide helpful and clear guidance for further experimental studies. We found three further potential hydrogen storage materials stable at high pressure: K2SiH8, KSiH7 and KSiH8. These results suggest the need for further investigations into hydrogen storage materials among such ternary hydrides at high pressure.

Design Principles for High-Temperature Superconductors with a Hydrogen-Based Alloy Backbone at Moderate Pressure.

Hydrogen-based superconductors provide a route to the long-sought goal of room-temperature superconductivity, but the high pressures required to metallize these materials limit their immediate application. For example, carbonaceous sulfur hydride, the first room-temperature superconductor made in a laboratory, can reach a critical temperature (T_{c}) of 288 K only at the extreme pressure of 267 GPa. The next recognized challenge is the realization of room-temperature superconductivity at significantly lower pressures. Here, we propose a strategy for the rational design of high-temperature superconductors at low pressures by alloying small-radius elements and hydrogen to form ternary H-based superconductors with alloy backbones. We identify a "fluorite-type" backbone in compositions of the form AXH_{8}, which exhibit high-temperature superconductivity at moderate pressures compared with other reported hydrogen-based superconductors. The Fm3[over ¯]m phase of LaBeH_{8}, with a fluorite-type H-Be alloy backbone, is predicted to be thermodynamically stable above 98 GPa, and dynamically stable down to 20 GPa with a high T_{c}∼185 K. This is substantially lower than the synthesis pressure required by the geometrically similar clathrate hydride LaH_{10} (170 GPa). Our approach paves the way for finding high-T_{c} ternary H-based superconductors at conditions close to ambient pressures.

High-pressure phase behaviors of titanium dioxide revealed by a Δ-learning potential.

Titanium dioxide has been extensively studied in the rutile or anatase phase, while its high-pressure phases are less well-understood, despite that many are thought to have interesting optical, mechanical, and electrochemical properties. First-principles methods, such as density functional theory (DFT), are often used to compute the enthalpies of TiO2 phases at 0 K, but they are expensive and, thus, impractical for long time scale and large system-size simulations at finite temperatures. On the other hand, cheap empirical potentials fail to capture the relative stabilities of various polymorphs. To model the thermodynamic behaviors of ambient and high-pressure phases of TiO2, we design an empirical model as a baseline and then train a machine learning potential based on the difference between the DFT data and the empirical model. This so-called Δ-learning potential contains long-range electrostatic interactions and predicts the 0 K enthalpies of stable TiO2 phases that are in good agreement with DFT. We construct a pressure-temperature phase diagram of TiO2 in the range 0 < P < 70 GPa and 100 < T < 1500 K. We then simulate dynamic phase transition processes by compressing anatase at different temperatures. At 300 K, we predominantly observe an anatase-to-baddeleyite transformation at about 20 GPa via a martensitic two-step mechanism with a highly ordered and collective atomic motion. At 2000 K, anatase can transform into cotunnite around 45-55 GPa in a thermally activated and probabilistic manner, accompanied by diffusive movement of oxygen atoms. The pressures computed for these transitions show good agreement with experiments. Our results shed light on how to synthesize and stabilize high-pressure TiO2 phases, and our method is generally applicable to other functional materials with multiple polymorphs.

The 2021 room-temperature superconductivity roadmap.

Designing materials with advanced functionalities is the main focus of contemporary solid-state physics and chemistry. Research efforts worldwide are funneled into a few high-end goals, one of the oldest, and most fascinating of which is the search for an ambient temperature superconductor (A-SC). The reason is clear: superconductivity at ambient conditions implies being able to handle, measure and access a single, coherent, macroscopic quantum mechanical state without the limitations associated with cryogenics and pressurization. This would not only open exciting avenues for fundamental research, but also pave the road for a wide range of technological applications, affecting strategic areas such as energy conservation and climate change. In this roadmap we have collected contributions from many of the main actors working on superconductivity, and asked them to share their personal viewpoint on the field. The hope is that this article will serve not only as an instantaneous picture of the status of research, but also as a true roadmap defining the main long-term theoretical and experimental challenges that lie ahead. Interestingly, although the current research in superconductor design is dominated by conventional (phonon-mediated) superconductors, there seems to be a widespread consensus that achieving A-SC may require different pairing mechanisms.In memoriam, to Neil Ashcroft, who inspired us all.