Ternary superconducting hydrides stabilized via Th and Ce elements at mild pressures.

The discovery of covalent H3S and clathrate structure LaH10 with excellent superconducting critical temperatures at high pressures has facilitated a multitude of research on compressed hydrides. However, their superconducting pressures are too high (generally above 150 GPa), thereby hindering their application. In addition, making room-temperature superconductivity close to ambient pressure in hydrogen-based superconductors is challenging. In this work, we calculated the chemically "pre-compressed" Be-H by heavy metals Th and Ce to stabilize the superconducting phase near ambient pressure. An unprecedented ThBeH8 (CeBeH8) with a "fluorite-type" structure was predicted to be thermodynamically stable above 69 GPa (76 GPa), yielding a T c of 113 K (28 K) decompressed to 7 GPa (13 GPa) by solving the anisotropic Migdal-Eliashberg equations. Be-H vibrations play a vital role in electron-phonon coupling and structural stability of these ternary hydrides. Our results will guide further experiments toward synthesizing ternary hydride superconductors at mild pressures.

Superconducting ternary hydrides: progress and challenges.

Since the discovery of the high-temperature superconductors H3S and LaH10 under high pressure, compressed hydrides have received extensive attention as promising candidates for room-temperature superconductors. As a result of current high-pressure theoretical and experimental studies, it is now known that almost all the binary hydrides with a high superconducting transition temperature (T c) require extremely high pressure to remain stable, hindering any practical application. In order to further lower the stable pressure and improve superconductivity, researchers have started exploring ternary hydrides and had many achievements in recent years. Here, we discuss recent progress in ternary hydrides, aiming to deepen the understanding of the key factors regulating the structural stability and superconductivity of ternary hydrides, such as structural motifs, bonding features, electronic structures, electron-phonon coupling, etc. Furthermore, the current issues and challenges of superconducting ternary hydrides are presented, together with the prospects and opportunities for future research.

Strategies for improving the superconductivity of hydrides under high pressure.

The successful prediction and confirmation of unprecedentedly high-temperature superconductivity in compressed hydrogen-rich hydrides signify a remarkable advancement in the continuous quest for attaining room-temperature superconductivity. The recent studies have established a broad scope for developing binary and ternary hydrides and illustrated correlation between specific hydrogen motifs and high-Tcs under high pressures. The analysis of the microscopic mechanism of superconductivity in hydrides suggests that the high electronic density of states at the Fermi level (EF), the large phonon energy scale of the vibration modes and the resulting enhanced electron-phonon coupling are crucial contributors towards the high-Tcphonon-mediated superconductors. The aim of our efforts is to tackle forthcoming challenges associated with elevating theTcand reducing the stabilization pressures of hydrogen-based superconductors, and offer insights for the future discoveries of room-temperature superconductors. Our present Review offers an overview and analysis of the latest advancements in predicting and experimentally synthesizing various crystal structures, while also exploring strategies to enhance the superconductivity and reducing their stabilization pressures of hydrogen-rich hydrides.

Superconductivity of thulium substituted clathrate hexahydrides at moderate pressure.

Due to the BCS theory, hydrogen, the lightest element, would be the prospect of room-temperature superconductor after metallization, but because of the difficulty of the hydrogen metallization, the theory about hydrogen pre-compression was proposed that the hydrogen-rich compounds could be a great option for the high Tc superconductors. The superior properties of TmH6, YbH6 and LuH6 indicated the magnificent potential of heavy rare earth elements for low-pressure stability. Here, we designed XTmH12 (X = Y, Yb, Lu, and La) to obtain higher Tc while maintaining low pressure stability. Most prominently, YbTmH12 can stabilize at a pressure of 60 GPa. Compared with binary TmH6 hydride, its Tc was increased to 48 K. The results provide an effective method for the rational design of moderate pressure stabilized hydride superconductors.

One-Dimensional Non-coplanar Nitrogen Chains in Manganese Tetranitride under High Pressure.

Transition metal nitrides have great potential applications as incompressible and high energy density materials. Various polymeric nitrogen structures significantly affect their properties, contributing to their complex bonding modes and coordination conditions. Herein, we first report a new manganese polynitride MnN4 with bifacial trans-cis [N4]n chains by treating with high-pressure and high-temperature conditions in a diamond anvil cell. Our experiments reveal that MnN4 has a P-1 symmetry and could stabilize in the pressure range of 56-127 GPa. Detailed pressure-volume data and calculations of this phase indicate that MnN4 is a potential hard (255 GPa) and high energy density (2.97 kJ/g) material. The asymmetric interactions impel N1 and N4 atoms to hybridize to sp2-3, which causes distortions of [N4]n chains. This work discovers a new polynitride material, fills the gap for the study of manganese polynitride under high pressure, and offers some new insights into the formation of polymeric nitrogen structures.

First-principles study of high-pressure structural phase transition and superconductivity of YBeH8.

The theory-led prediction of LaBeH8, which has a high superconducting critical temperature (Tc) above liquid nitrogen under a pressure level below 1 Mbar, has been experimentally confirmed. YBeH8, which has a structural configuration similar to that of LaBeH8, has also been predicted to be a high-temperature superconductor at high pressure. In this study, we focus on the structural phase transition and superconductivity of YBeH8 under pressure by using first-principles calculations. Except for the known face-centered cubic phase of Fm3̄m, we found a monoclinic phase with P1̄ symmetry. Moreover, the P1̄ phase transforms to the Fm3̄m phase at ∼200 GPa with zero-point energy corrections. Interestingly, the P1̄ phase undergoes a complex electronic phase transition from semiconductor to metal and then to superconducting states with a low Tc of 40 K at 200 GPa. The Fm3̄m phase exhibits a high Tc of 201 K at 200 GPa, and its Tc does not change significantly with pressure. When we combine the method using two coupling constants, λopt and λac, with first-principles calculations, λopt is mainly supplied by the Be-H alloy backbone, which accounts for about 85% of total λ and makes the greatest contribution to the high Tc. These insights not only contribute to a deeper understanding of the superconducting behavior of this ternary hydride but may also guide the experimental synthesis of hydrogen-rich compounds.

High-temperature superconductivities and crucial factors influencing the stability of LaThH12 under moderate pressures.

The recent discovery of high-temperature superconductivity in compressed hydrides has reignited the long-standing quest for room-temperature superconductors. However, the synthesis of superconducting hydrides under moderate pressure and the identification of crucial factors that affect their stability remain challenges. Here, we predicted the ternary clathrate phases of LaThH12 with potential superconductivity under high pressures and specifically proposed a novel R3̄c-LaThH12 phase exhibiting a remarkable Tc of 54.95 K at only 30 GPa to address these confusions. Our first-principles studies show that the high-Tc value of Pm3̄m and Cmmm-LaThH12 phases was induced by the strong electron-phonon coupling driven by the synergy of the electron-phonon matrix element and phonon softening caused by Fermi surface nesting. Importantly, we demonstrate the dual effects of enhanced ionic bonding and expanded orbital hybridization between Th-6f and H-sp3 orbitals during depressurization are primary factors governing the dynamic stability of R3̄c-LaThH12 at low pressures. Our findings offer crucial insights into the underlying mechanisms governing low-pressure stability and provide guidance for experimental efforts aimed at realizing hydrogen-based superconductors with both low synthesis pressures and high-Tc.

Superconductivity of cubic MB6 (M = Na, K, Rb, Cs).

Previous studies have shown that NaB6, KB6, and RbB6 adopting Pm3̄m are superconductors with a relatively high Tc under ambient conditions. In this paper, we conducted systematic structural and related properties research on CsB6 through a genetic evolution algorithm and total energy calculations based on density functional theory between 0 and 20 GPa. Our results reveal a cubic Pm3̄m CsB6, which is dynamically stable under the pressures we studied. We systematically calculated the formation enthalpies, electronic properties, and superconducting properties of Pm3̄m MB6 (M = Na, K, Rb, Cs). They all exhibit metallic features, and boron has high contributions to band structures, density of states, and electron-phonon coupling (EPC). The calculated results about the Helmholtz free energy difference of Pm3̄m CsB6 at 0, 10, and 20 GPa indicate that it is stable upon chemical decomposition (decomposition to simple substances Cs and B) from 0 to 400 K. The phonon density of states indicates that boron atoms occupy the high frequency area. The EPC results show that Pm3̄m CsB6 is a superconductor with Tc = 11.7 K at 0 GPa, close to NaB6 (13.1 K), KB6 (11.7 K), and RbB6 (11.3 K) at 0 GPa in our work, which indicates that boron atoms play an essential role in superconductivity: vibrations of B6 regular octagons lead to the high Tc of Pm3̄m MB6. Our work about Pm3̄m hexaborides provides a supplementary study on the borides of the group IA elements (without Fr and Li) and has an important guiding significance for the experimental synthesis of CsB6.

Phase diagrams and superconductivity of ternary Ca-Al-H compounds under high pressure.

The search for high-temperature superconductors in hydrides under high pressure has always been a research hotspot. Hydrogen-based superconductors offer an avenue to achieve the long-sought goal of superconductivity at room temperature. Here we systematically explored the high-pressure phase diagram, electronic properties, lattice dynamics and superconductivity of the ternary Ca-Al-H system using ab initio methods. At 80 GPa, CaAlH5 transforms from Cmcm to P21/m phase. Both of Cmcm-CaAlH5 and Pnnm-CaAl2H8 are semiconductors. At 200 GPa, P4/mmm-CaAlH7 and a metastable compound Immm-Ca2AlH12 were found. Furthermore, P4/mmm-CaAlH7 shows obvious softening of the high frequency vibration modes, which improves the strength of electron-phonon coupling. Therefore, a superconducting transition temperature Tc of 71 K is generated in P4/mmm-CaAlH7 at 50 GPa. In addition, the thermodynamic metastable Immm-Ca2AlH12 exhibits a superconducting transition temperature of 118 K at 250 GPa. These results are very useful for the experimental searching of new high-Tc superconductors in ternary hydrides. Our work may provide an opportunity to search for high Tc superconductors at lower pressure.

Revealing the Mechanism of Pressure-Induced Emission in Layered Silver-Bismuth Double Perovskites.

Pressure-induced emission (PIE) associated with self-trapping excitons (STEs) in low-dimensional halide perovskites has attracted great attention for better materials-by-design. Here, using 2D layered double perovskite (C6 H5 CH2 CH2 NH3 + )4 AgBiBr8 as a model system, we advance a fundamental physicochemical mechanism of the PIE from the perspective of carrier dynamics and excited-state behaviors of local lattice distortion. We observed a pressure-driven STE transformation from dark to bright states, corresponding a strong broadband Stokes-shifted emission. Further theoretical analysis demonstrated that the suppressed lattice distortion and enhanced electronic dimensionality in the excited-state play an important role in the formation of stabilized bright STEs, which could manipulate the self-trapping energy and lattice deformation energy to form an energy barrier between the potential energy curves of ground- and excited-state, and enhance the electron-hole orbital overlap, respectively.

Pressure-induced high-temperature superconductivity in ternary Y-Zr-H compounds.

Compressed hydrogen-rich compounds have received extensive attention as appealing contenders for superconductors. Here, we found several stable hydrides YZrH6, YZrH8, YZr3H16 and YZrH18, and a series of metastable clathrate hexahydrides in the systematic investigation of Y-Zr-H ternary hydrides under pressure. Electron-phonon coupling calculations indicate that they all exhibit high temperature superconductivity and perform better than the binary Zr-H system. YZrH6 can maintain dynamic stability down to ambient pressure and keep a critical temperature (Tc) of 16 K. The stable YZrH18 and metastable Y3ZrH24 with high hydrogen content exhibit high Tc of 156 K and 185 K at 200 GPa, respectively. Further analysis shows that the phonon modes associated with H atoms contribute significantly to the electron-phonon coupling. The hydrogen content and the stoichiometric ratio of Y and Zr closely affect the density of states at the Fermi level, thereby affecting the superconductivity. Our work presents an important step toward understanding the superconductivity and stability of transition metal ternary hydrides.

Harvesting PdH Employing Pd Nano Icosahedrons via High Pressure.

Palladium hydrides (PdHx ) have important applications in hydrogen storage, catalysis, and superconductivity. Because of the unique electron subshell structure of Pd, quenching PdHx materials with more than 0.706 hydrogen stoichiometry remains challenging. Here, the 1:1 stoichiometric PdH ( F m 3 ¯ m ) $Fm\bar{3}m)$ is successfully synthesized using Pd nano icosahedrons as a starting material via high-pressure cold-forging at 0.2 GPa. The synthetic initial pressure is reduced by at least one order of magnitude relative to the bulk Pd precursors. Furthermore, PdH is quenched at ambient conditions after being laser heated ≈2000 K under ≈30 GPa. Corresponding ab initio calculations demonstrate that the high potential barrier of the facets (111) restricts hydrogen atoms' diffusion, preventing hydrogen atoms from combining to generate H2 . This study paves the way for the high-pressure synthesis of metal hydrides with promising potential applications.

First principle studies of TiO2-ZnO alloys under high pressure.

The ZnO-TiO2composite system has been applied as a photocatalyst in the treatment of organic waste and domestic wastewater due to its high separation rate of photogenerated carriers and wide light response range. Using the first-principles approach based on density functional theory, we investigated the crystal structures and the electronic properties of ZnO-TiO2alloys under high pressure and predicted three stable high-pressure phases (CmcmZnTiO3,ImmaZn2TiO4andCmZnTi3O7). Calculations of the phonon spectra and elastic constants showed that the predicted structures are dynamically and mechanically stable. In terms of electronic properties, it was found that the three crystal structures were all semiconductors. With the increase of pressure, the band gap ofCmZnTi3O7showed an increasing trend, while the band gap ofCmcmZnTiO3andImmaZn2TiO4gradually decreased. The calculated band structures showed that the band gap first increases nonlinearly and then decreases as the Zn concentration increases. Pressure can regulate the band gap of the above crystals, making them promising for applications in photocatalysis and microwave devices.

Pressure Induced Clathrate Hydrogen-Rich Superconductors KH20 and KH30.

Hydrogen-rich compounds have long been considered as one of the hotspot materials for achieving room-temperature superconductivity. We systematically investigate the high-pressure phase diagram of the K-H system and identified two unreported clathrate extreme superhydrides KH20 and KH30, hosting high superconducting transition temperatures (Tc) of 283 and 243 K at 500 GPa, respectively. The extremely high hydrogen content significantly increases H-derived electronic density of states at the Fermi level, constituting the main contributor to participate in electron-phonon coupling thus producing high-Tc. The large electron localizations in the interstitial region of the metal lattice under high pressure effectively assist the dissociation of hydrogen molecular units, forming unique H36 cages. These results offer key insights into the stability and potential high-Tc superconductivity of compressed extreme superhydrides and will further stimulate related research.

Room-Temperature Superconductivity in Yb/Lu Substituted Clathrate Hexahydrides under Moderate Pressure.

Room temperature superconductivity is a dream that mankind has been chasing for a century. In recent years, the synthesis of H3S, LaH10, and C-S-H compounds under high pressures has gradually made that dream become a reality. But the extreme high pressure required for stabilization of hydrogen-based superconductors limit their applications. So, the next challenge is to achieve room-temperature superconductivity at significantly low pressures, even ambient pressure. In this work, we design a series of high temperature superconductors that can be stable at moderate pressures by incorporating heavy rare earth elements Yb/Lu into sodalite-like clathrate hexahydrides. In particular, the critical temperatures (T c) of Y3LuH24, YLuH12, and YLu3H24 can reach 283 K at 120 GPa, 275 K at 140 GPa, and 288 K at 110 GPa, respectively. Their critical temperatures are close to or have reached room temperature, and minimum stable pressures are significantly lower than that of reported room temperature superconductors. Our work provides an effective method for the rational design of low-pressure stabilized hydrogen-based superconductors with room-temperature superconductivity simultaneously and will stimulate further experimental exploration.

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.

The investigation of the luminescent structure of thallium-doped cesium iodide (CsI:Tl) basing on the first-principles coupled with spectral analysis.

The luminescent structure of thallium-doped cesium iodide (CsI:Tl) and the behavior of electrons during luminescence are studied at great length based on the conventional first-principles calculation combined with ordinary spectroscopic analysis befittingly in this work. The hybrid functionals based on a screened Coulomb potential (HSE) is used to visualize the energy band structure of the experimental sample's system, and the corresponding relationship between the transition behavior of CsI:Tl energy levels and the spectrum is studied more accurately. We show the complete energy conversion process clearly, which involves the crystal beginning to receive the energy of a photon until the moment of de-excitation. All the fluorescence process is completed by Tl+ions that replace Cs+ions. Our results verify and complement the previous theories and potentially provide important references for the adjustment and design of the detectors and imaging equipment in different fields.

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.

Phase transitions and properties of lanthanum under high pressures.

Lanthanum (La), the first member of the lanthanide elements, recently aroused interests due to the discovery of high-Tcsuperconductor LaH10under high pressures and its unique superconducting properties. Here, we study the phase transitions, superconductivity and mechanical properties of metallic La under high pressures by first-principle calculations. The known face-centered cubic (fcc) phase with space groupFm3¯mstill exists above 100 GPa. And it transforms into an unprecedented body-centered tetragonal (bct) phase with space groupI4/mmmabove 180 GPa, which expands the high pressure phase transition sequence. Further calculations show that the superconducting transition temperatureTcof fcc phase decreases with increasing pressure with the rate of -0.13 K GPa-1, in good agreement with the experimental results. For the bct phase, the estimated superconducting transition temperature is very low withTcof 0.7 K at 200 GPa. The calculations of mechanical properties show that both of fcc and bct phases are compressible and brittle.

Reply to the 'Comment on "High-temperature superconductivity in transition metallic hydrides MH11 (M = Mo, W, Nb, and Ta) under high pressure"' by X. Zheng and J. Zheng, Phys. Chem. Chem. Phys., 2022, 24, DOI: 10.1039/D1CP01474A.

Our paper is concerned with the specific hydrogen compound MoH11. The authors of the Comment advocate investigating the role of umklapp processes (UP). For the hydrogen compounds, the main contribution to the strength of the pairing interaction is provided not by acoustic, but by optical phonons. This key factor leads to a diminishing role of the UP for the compound of interest.