Structure and bandgap closure in dense hydrogen

The possibility that steadily compressed hydrogen might undergo a transition from a proton-paired insulator to a monatomic metal was first suggested in 1935. But experimental realization of metallic hydrogen in solid form has remained elusive, despite studies at pressures as high as 342 GPa. The pairing structure is known to be robust (from the persistence of its associated vibron mode), leading to the suggestion of an alternative route to the metallic state, involving a band-overlap transition in which the pairing is preserved. Here we report density functional calculations within the local density approximation that predict a range of densities for hydrogen where a paired or molecular metallic state may be energetically preferred. The transition to this metallic state is naturally associated with the closing of an overall bandgap; but the pressures required to effect the transition are shown to change significantly when the gaps are corrected by approximate inclusion of many-electron effects. The implication is that a complete resolution of the structural and phase problem in dense hydrogen may require methods beyond the local density approximation.     

A quantum fluid of metallic hydrogen suggested by first-principles calculations

It is generally assumed that solid hydrogen will transform into a metallic alkali-like crystal at sufficiently high pressure. However, some theoretical models have also suggested that compressed hydrogen may form an unusual two-component (protons and electrons) metallic fluid at low temperature, or possibly even a zero-temperature liquid ground state. The existence of these new states of matter is conditional on the presence of a maximum in the melting temperature versus pressure curve (the 'melt line'). Previous measurements of the hydrogen melt line up to pressures of 44 GPa have led to controversial conclusions regarding the existence of this maximum. Here we report ab initio calculations that establish the melt line up to 200 GPa. We predict that subtle changes in the intermolecular interactions lead to a decline of the melt line above 90 GPa. The implication is that as solid molecular hydrogen is compressed, it transforms into a low-temperature quantum fluid before becoming a monatomic crystal. The emerging low-temperature phase diagram of hydrogen and its isotopes bears analogies with the familiar phases of 3He and 4He (the only known zero-temperature liquids), but the long-range Coulomb interactions and the large component mass ratio present in hydrogen would result in dramatically different properties.     

Superconductivity in compressed lithium at 20 K

Superconductivity at high temperatures is expected in elements with low atomic numbers, based in part on conventional BCS (Bardeen-Cooper-Schrieffer) theory. For example, it has been predicted that when hydrogen is compressed to its dense metallic phase (at pressures exceeding 400 GPa), it will become superconducting with a transition temperature above room temperature. Such pressures are difficult to produce in a laboratory setting, so the predictions are not easily confirmed. Under normal conditions lithium is the lightest metal of all the elements, and may become superconducting at lower pressures; a tentative observation of a superconducting transition in Li has been previously reported. Here we show that Li becomes superconducting at pressures greater than 30 GPa, with a pressure-dependent transition temperature (T(c)) of 20 K at 48 GPa. This is the highest observed T(c) of any element; it confirms the expectation that elements with low atomic numbers will have high transition temperatures, and suggests that metallic hydrogen will have a very high T(c). Our results confirm that the earlier tentative claim of superconductivity in Li was correct.     

Electronic and structural transitions in dense liquid sodium

At ambient conditions, the light alkali metals are free-electron-like crystals with a highly symmetric structure. However, they were found recently to exhibit unexpected complexity under pressure. It was predicted from theory--and later confirmed by experiment--that lithium and sodium undergo a sequence of symmetry-breaking transitions, driven by a Peierls mechanism, at high pressures. Measurements of the sodium melting curve have subsequently revealed an unprecedented (and still unexplained) pressure-induced drop in melting temperature from 1,000 K at 30 GPa down to room temperature at 120 GPa. Here we report results from ab initio calculations that explain the unusual melting behaviour in dense sodium. We show that molten sodium undergoes a series of pressure-induced structural and electronic transitions, analogous to those observed in solid sodium but commencing at much lower pressure in the presence of liquid disorder. As pressure is increased, liquid sodium initially evolves by assuming a more compact local structure. However, a transition to a lower-coordinated liquid takes place at a pressure of around 65 GPa, accompanied by a threefold drop in electrical conductivity. This transition is driven by the opening of a pseudogap, at the Fermi level, in the electronic density of states--an effect that has not hitherto been observed in a liquid metal. The lower-coordinated liquid emerges at high temperatures and above the stability region of a close-packed free-electron-like metal. We predict that similar exotic behaviour is possible in other materials as well.     

Intermediate-depth earthquake faulting by dehydration embrittlement with negative volume change

Earthquakes are observed to occur in subduction zones to depths of approximately 680 km, even though unassisted brittle failure is inhibited at depths greater than about 50 km, owing to the high pressures and temperatures. It is thought that such earthquakes (particularly those at intermediate depths of 50-300 km) may instead be triggered by embrittlement accompanying dehydration of hydrous minerals, principally serpentine. A problem with failure by serpentine dehydration is that the volume change accompanying dehydration becomes negative at pressures of 2-4 GPa (60-120 km depth), above which brittle fracture mechanics predicts that the instability should be quenched. Here we show that dehydration of antigorite serpentinite under stress results in faults delineated by ultrafine-grained solid reaction products formed during dehydration. This phenomenon was observed under all conditions tested (pressures of 1-6 GPa; temperatures of 650-820 degrees C), independent of the sign of the volume change of reaction. Although this result contradicts expectations from fracture mechanics, it can be explained by separation of fluid from solid residue before and during faulting, a hypothesis supported by our observations. These observations confirm that dehydration embrittlement is a viable mechanism for nucleating earthquakes independent of depth, as long as there are hydrous minerals breaking down under a differential stress.     

高压下GaN的光学特性

根据密度泛函理论,采用平面波赝势和广义梯度方法,研究了闪锌矿结构的GaN晶体在不同压强下的光学性质。结果表明,随着压强的增大,直接带隙和间接带隙都逐渐增大;在外界压强为125 GPa时,GaN从直接带隙半导体变成间接带隙半导体,吸收波段出现了蓝移的现象。     

Semiconducting non-molecular nitrogen up to 240 GPa and its low-pressure stability

The triple bond of diatomic nitrogen has among the greatest binding energies of any molecule. At low temperatures and pressures, nitrogen forms a molecular crystal in which these strong bonds co-exist with weak van der Waals interactions between molecules, producing an insulator with a large band gap. As the pressure is raised on molecular crystals, intermolecular interactions increase and the molecules eventually dissociate to form monoatomic metallic solids, as was first predicted for hydrogen. Theory predicts that, in a pressure range between 50 and 94 GPa, diatomic nitrogen can be transformed into a non-molecular framework or polymeric structure with potential use as a high-energy-density material. Here we show that the non-molecular phase of nitrogen is semiconducting up to at least 240 GPa, at which pressure the energy gap has decreased to 0.4 eV. At 300 K, this transition from insulating to semiconducting behaviour starts at a pressure of approximately 140 GPa, but shifts to much higher pressure with decreasing temperature. The transition also exhibits remarkably large hysteresis with an equilibrium transition estimated to be near 100 GPa. Moreover, we have succeeded in recovering the non-molecular phase of nitrogen at ambient pressure (at temperatures below 100 K), which could be of importance for practical use.     

Quantum distribution of protons in solid molecular hydrogen at megabar pressures

Solid hydrogen, a simple system consisting only of protons and electrons, exhibits a variety of structural phase transitions at high pressures. Experimental studies based on static compression up to about 230 GPa revealed three relevant phases of solid molecular hydrogen: phase I (high-temperature, low-pressure phase), phase II (low-temperature phase) and phase III (high-pressure phase). Spectroscopic data suggest that symmetry breaking, possibly related to orientational ordering, accompanies the transition into phases II and III. The boundaries dividing the three phases exhibit a strong isotope effect, indicating that the quantum-mechanical properties of hydrogen nuclei are important. Here we report the quantum distributions of protons in the three phases of solid hydrogen, obtained by a first-principles path-integral molecular dynamics method. We show that quantum fluctuations of protons effectively hinder molecular rotation--that is, a quantum localization occurs. The obtained crystal structures have entirely different symmetries from those predicted by the conventional simulations which treat protons classically.     

高压下WSe2的电学性质及金属化相变

利用高压原位电阻率测量技术, 观察0~48.2 GPa内WSe₂电阻率随压强的变化规律, 并测量了WSe₂电阻率在不同压强下随温度的变化关系.  结果表明: WSe₂电阻率在压力作用下的变化规律与杂质能级压致离化后的传导有关; 由于压致能隙闭合, WSe₂在38.1 GPa时发生等结构的半导体性到金属性的相转变.     

Spin crossover and iron-rich silicate melt in the Earth's deep mantle

A melt has greater volume than a silicate solid of the same composition. But this difference diminishes at high pressure, and the possibility that a melt sufficiently enriched in the heavy element iron might then become more dense than solids at the pressures in the interior of the Earth (and other terrestrial bodies) has long been a source of considerable speculation. The occurrence of such dense silicate melts in the Earth's lowermost mantle would carry important consequences for its physical and chemical evolution and could provide a unifying model for explaining a variety of observed features in the core-mantle boundary region. Recent theoretical calculations combined with estimates of iron partitioning between (Mg,Fe)SiO(3) perovskite and melt at shallower mantle conditions suggest that melt is more dense than solids at pressures in the Earth's deepest mantle, consistent with analysis of shockwave experiments. Here we extend measurements of iron partitioning over the entire mantle pressure range, and find a precipitous change at pressures greater than ～76?GPa, resulting in strong iron enrichment in melts. Additional X-ray emission spectroscopy measurements on (Mg(0.95)Fe(0.05))SiO(3) glass indicate a spin collapse around 70?GPa, suggesting that the observed change in iron partitioning could be explained by a spin crossover of iron (from high-spin to low-spin) in silicate melt. These results imply that (Mg,Fe)SiO(3) liquid becomes more dense than coexisting solid at ～1,800?km depth in the lower mantle. Soon after the Earth's formation, the heat dissipated by accretion and internal differentiation could have produced a dense melt layer up to ～1,000?km in thickness underneath the solid mantle. We also infer that (Mg,Fe)SiO(3) perovskite is on the liquidus at deep mantle conditions, and predict that fractional crystallization of dense magma would have evolved towards an iron-rich and silicon-poor composition, consistent with seismic inferences of structures in the core-mantle boundary region.     

New high-pressure phases of lithium

Lithium is considered a 'simple' metal because, under ordinary conditions of pressure and temperature, the motion of conduction electrons is only weakly perturbed by interactions with the cubic lattice of atomic cores. It was recently predicted that at pressures below 100 GPa, dense Li may undergo several structural transitions, possibly leading to a 'paired-atom' phase with low symmetry and near-insulating properties. Here we report synchrotron X-ray diffraction measurements that confirm that Li undergoes pronounced structural changes under pressure. Near 39 GPa, the element transforms from a high-pressure face-centred-cubic phase, through an intermediate rhombohedral modification, to a cubic polymorph with 16 atoms per unit cell. This cubic phase has not been observed previously in any element; unusually, its calculated electronic density of states exhibits a pronounced semimetal-like minimum near the Fermi energy. We present total-energy calculations that provide theoretical support for the observed phase transition sequence. Our calculations indicate a large stability range of the 16-atom cubic phase relative to various other crystal structures tested here.     

The elasticity of the MgSiO3 post-perovskite phase in the Earth's lowermost mantle

MgSiO3 perovskite has been assumed to be the dominant component of the Earth's lower mantle, although this phase alone cannot explain the discontinuity in seismic velocities observed 200-300 km above the core-mantle boundary (the D" discontinuity) or the polarization anisotropy observed in the lowermost mantle. Experimental and theoretical studies that have attempted to attribute these phenomena to a phase transition in the perovskite phase have tended to simply confirm the stability of the perovskite phase. However, recent in situ X-ray diffraction measurements have revealed a transition to a 'post-perovskite' phase above 125 GPa and 2,500 K--conditions close to those at the D" discontinuity. Here we show the results of first-principles calculations of the structure, stability and elasticity of both phases at zero temperature. We find that the post-perovskite phase becomes the stable phase above 98 GPa, and may be responsible for the observed seismic discontinuity and anisotropy in the lowermost mantle. Although our ground-state calculations of the unit cell do not include the effects of temperature and minor elements, they do provide a consistent explanation for a number of properties of the D" layer.     

Superconductivity in the non-magnetic state of iron under pressure.

Ferromagnetism and superconductivity are thought to compete in conventional superconductors, although in principle it is possible for any metal to become a superconductor in its non-magnetic state at a sufficiently low temperature. At pressures above 10 GPa, iron is known to transform to a non-magnetic structure and the possibility of superconductivity in this state has been predicted. Here we report that iron does indeed become superconducting at temperatures below 2 K at pressures between 15 and 30 GPa. The transition to the superconducting state is confirmed by both a drop in resistivity and observation of the Meissner effect.     

A superconductor to superfluid phase transition in liquid metallic hydrogen

Although hydrogen is the simplest of atoms, it does not form the simplest of solids or liquids. Quantum effects in these phases are considerable (a consequence of the light proton mass) and they have a demonstrable and often puzzling influence on many physical properties, including spatial order. To date, the structure of dense hydrogen remains experimentally elusive. Recent studies of the melting curve of hydrogen indicate that at high (but experimentally accessible) pressures, compressed hydrogen will adopt a liquid state, even at low temperatures. In reaching this phase, hydrogen is also projected to pass through an insulator-to-metal transition. This raises the possibility of new state of matter: a near ground-state liquid metal, and its ordered states in the quantum domain. Ordered quantum fluids are traditionally categorized as superconductors or superfluids; these respective systems feature dissipationless electrical currents or mass flow. Here we report a topological analysis of the projected phase of liquid metallic hydrogen, finding that it may represent a new type of ordered quantum fluid. Specifically, we show that liquid metallic hydrogen cannot be categorized exclusively as a superconductor or superfluid. We predict that, in the presence of a magnetic field, liquid metallic hydrogen will exhibit several phase transitions to ordered states, ranging from superconductors to superfluids.     

第一性理论研究60～160 GPa下固态氢结构稳定性

为研究固态氢结构在60~160 GPa压力范围内的结构稳定性,采用第一性原理方法,计算了在60~160 GPa压力范围内固态氢Ⅱ相P6₃/m、P2₁/c、P6₃/mmc、Pca2₁和Ⅲ相C2/c 5个结构的热力学和动力学稳定性.计算结果表明,P6₃/m、C2/c和Pca2₁为候选结构,Pca2₁、P6₃/m和C2/c结构分别在60~78、78~90 GPa和116~160 GPa的3个压力区间内稳定存在.      

Modulated structure of solid iodine during its molecular dissociation under high pressure

The application of pressure to solid iodine forces the molecules in the crystal to approach each other until intermolecular distances become comparable to the bond length of iodine; at this point, the molecules lose their identity and are essentially dissociated. According to room-temperature X-ray diffraction studies, this process involves direct dissociation of iodine molecules at about 21 GPa, whereas spectroscopic observations have identified intermediate molecular phases at pressures ranging from 15 to 30 GPa. Here we present quasi-hydrostatic powder X-ray diffraction measurements that clearly reveal an intermediate phase during the pressure-induced dissociation of solid iodine. We find that, similar to the behaviour seen in uranium, the structure of this intermediate phase is incommensurately modulated, with the nearest interatomic distances continuously distributed over the range 2.86-3.11 A. The shortest of these interatomic distances falls between the bond length of iodine in the molecular crystal (2.75 A) and the nearest interatomic distance in the fully dissociated monatomic crystal (2.89 A), implying that the intermediate phase is a transient state during molecular dissociation. We expect that further measurements at different temperatures will help to elucidate the origin and stability of the incommensurate structure, which might lead to a better understanding of the molecular-level mechanism of the pressure-induced dissociation seen here and in the molecular crystals of hydrogen, oxygen and nitrogen.     

Neutron and X-ray diffraction study of the broken symmetry phase transition in solid deuterium

The solid hydrogen compounds D2, HD and H2 remain quantum molecular solids up to pressures in the 100 GPa range. A remarkable macroscopic consequence is the existence of a pressure-induced broken symmetry phase transition, in which the molecules go from a spherical rotational state to an anisotropic rotational state. Theoretical understanding of the broken symmetry phase structure remains controversial, despite numerous studies. Some open questions concern the existence of long- or short-range orientational order; whether a strong isotopic shift on the transition pressure should be assigned to the nuclear zero-point motion or to quantum localization; and whether the structures are cubic, hexagonal or orthorhombic. Here we present experimental data on the structure of the broken symmetry phase in solid D2, obtained by a combination of neutron and X-ray diffraction up to 60 GPa. Our data are incompatible with orthorhombic structures predicted by recent theoretical works. We find that the broken symmetry phase structure is incommensurate with local orientational order, being similar to that found in metastable cubic para-D2.     

A theoretical investigation on phase transition and dissociation of ammonium bromide under high pressure

Structures of ammonium bromide under high pressure were investigated through ab initio evolutionary algorithm and total-energy calculations based on density functional theory. Static enthalpy calculations indicate that the low-pressure phase V（space group P4/nmm） transforms into a monoclinic P21/m structure at 71 GPa and then an orthorhombic structure Cmma at 130 GPa, which is found to be energetically stable up to 264 GPa. Mechanism of phonon softening at the P4/nmm P21/m transformation is discussed. Ab initio calculations show that the band overlap in the molecular Cmma phase, which causes the pressure-induced insulator-to-metal transition, occurs at about 240 GPa. Enthalpy calculations show that Cmma NH4 Br becomes unstable and dissociates into NH3 and HBr above 264 GPa.     

固体氧化物电解水制氢系统效率

电解水与高效清洁一次能源耦合制氢,是理想的大规模制氢技术。该文建立了电解水制氢系统效率评估模型,并通过该模型对碱性、固体聚合物电解池(SPE)及固体氧化物电解池(SOEC)制氢系统总制氢效率进行了计算与分析。碱性制氢系统电解效率与总制氢效率均较低,分别为56%和25%;SPE制氢系统电解效率虽有提高约76%,但其总制氢效率仍较低约35%;而SOEC制氢系统电解效率可达90%以上,总制氢效率高达55%,分别是SPE与碱性制氢系统的1.5和2倍。高温气冷堆耦合的SOEC电解制氢系统是目前已知总制氢效率最高的大规模制氢系统。     

Compression behavior of Sm）2Ti2O7-pyrochlore up to 50 GPa：single-crystal X-ray diffraction and density functional theory calculations

Single-crystal X-ray diffraction at pressures up to 50 GPa has been employed to study the compression behavior of Sm2Ti2O7-pyrochlore. In contrast to earlier reports, we observed no pressure-induced amorphization or pressure-induced anion disorder up to 50 GPa. The experimental study has been complemented by density functional theory-based calculations. A combination of the theoretical and experimental data yields a bulk modulus of 185 GPa, significantly higher than a value which had been reported earlier. In comparison to earlier work, the current study provides more reliable data due to the use of neon as a pressure medium, which provides a more hydrostatic pressure than the aluminum, which had been employed as a pressure medium in the earlier studies. An analysis of the compressibility of Al2B2O7 pyrochlores shows an approximately linear dependence of the bulk modulus on the unit cell volume.