Semiconductor-metal transition in selenium under shock compression

Phase transitions in selenium are studied by time-resolved measurements of the electrical conductivity under shock compression at a pressure of up to 32 GPa. The pressure dependence of the electrical conductivity (σ(P)) has two portions: a sharp increase at P < 21 GPa and a plateau at P > 21 GPa. The experimental data and the temperature estimates indicate that, at P < 21 GPa, selenium is in the semiconductor state. The energy gap of semiconducting selenium decreases substantially under compression. At P > 21 GPa, the electrical conductivity saturates at ～10⁴ Ω^?1 cm^?1. Such a high value of the electrical conductivity shows the effective semiconductor-metal transition taking place in shock-compressed selenium. Experiments with samples having different initial densities demonstrate the effect of temperature on the phase transition. For example, powdered selenium experiences the transition at a lower shock pressure than solid selenium. Comparison of the temperature estimates with the phase diagram of selenium shows that powdered selenium metallizes in a shock wave as a result of melting. The most plausible mechanism behind the shock-induced semiconductor-metal transition in solid selenium is melting or the transition in the solid phase. Under shock compression, the metallic phase arises without a noticeable time delay. After relief, the metallic phase persists for a time, delaying the reverse transition.     

Electrical resistivity of fluid methane multiply shock compressed to 147 GPa

Shock wave experiments were carried out to measure the electrical resistivity of fluid methane. The pressure range of 89–147?GPa and the temperature range from 1800 to 2600?K were achieved with a two-stage light-gas gun. We obtained a minimum electrical resistivity value of 4.5?×?10^?2?Ω?cm at pressure and temperature of 147?GPa and 2600?K, which is two orders of magnitude higher than that of hydrogen under similar conditions. The data are interpreted in terms of a continuous transition from insulator to semiconductor state. One possibility reason is chemical decomposition of methane in the shock compression process. Along density and temperature increase with Hugoniot pressure, dissociation of fluid methane increases continuously to form a H₂-rich fluid.     

Metallic liquid hydrogen and likely Al<Subscript>2</Subscript>O<Subscript>3</Subscript> metallic glass

Dynamic compression has been used to synthesize liquid metallic hydrogen at 140 GPa (1.4 million bar) and experimental data and theory predict Al₂O₃ might be a metallic glass at ∼ 300 GPa. The mechanism of metallization in both cases is probably a Mott-like transition. The strength of sapphire causes shock dissipation to be split differently in the strong solid and soft fluid. Once the 4.5-eV H-H and Al-O bonds are broken at sufficiently high pressures in liquid H₂ and in sapphire (single-crystal Al₂O₃), electrons are delocalized, which leads to formation of energy bands in fluid H and probably in amorphous Al₂O₃. The high strength of sapphire causes shock dissipation to be absorbed primarily in entropy up to ∼400 GPa, which also causes the 300-K isotherm and Hugoniot to be virtually coincident in this pressure range. Above ∼400 GPa shock dissipation must go primarily into temperature, which is observed experimentally as a rapid increase in shock pressure above ∼400 GPa. The metallization of glassy Al₂O₃, if verified, is expected to be general in strong oxide insulators. Implications for Super Earths are discussed.     

Is superdense fluid hydrogen a molecular metal?

Recent experiments on the compression of liquid hydrogen in reverberating shock waves, which indicate the transition into a metallic state at about nine times the liquid H₂ density [S. T. Weir, A. C. Mitchell, and W. J. Nellis, Phys. Rev. Lett. 76, 1860 (1996)], have been interpreted by a microscopic percolation in a virtual molecular structure with a continuous spectrum of the electron excitations. The scaling dependence of the electron mobility on the energy above the percolation threshold has been used to qualitatively describe the electrical conductivity of fluid molecular hydrogen in the vicinity of the insulator-metal transition point. Zh. éksp. Teor. Fiz. 113, 1094–1100 (March 1998) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

A new global hydrogen equation of state model

Abstract

Simple statistical mechanics models have been assembled into a wide-range equation of state for the hydrogen isotopes. The solid is represented by an Einstein-Grüneisen model delimited by a Lindemann melting curve. The fluid is represented by an ideal gas plus a soft-sphere fluid configurational term. Dissociation and ionization are approximated by modifying the ideal gas chemical-equilibrium formulation. The T = 0 isotherm and dissociation models have been fitted to a new diamond-anvil isotherm and to laser-generated shock data. The main limitation of the model is in ionization at high compression.     

High pressure X-ray diffraction study of copper hydride at room temperature

Abstract

High pressure X-ray studies on CuH up to 23 GPa have been performed at room temperature using a gasketed diamond anvil cell. The experimental data on the molar volume of CuH as a function of pressure have been fitted to Murnaghan's equation of state giving a bulk modulus: B₀ = 72.5±2 GPa and B₀ = 2.7 ± 0.3. By comparison with the equation of state for pure copper the effective additive volume of hydrogen has been evaluated as a function of pressure. It decreases from 3.2 cm³/mol H, at ambient pressure reaching a flattening value of 1.7cm³hol H at about 60 GPa. This suggests a continuous transition of CuH from ionic or covalent character at normal pressure to metallic hydride behavior at high pressure     

Dynamic high pressure: Why it makes metallic fluid hydrogen

Metallic fluid H has been made by dynamic compression decades after Wigner and Huntington (WH) predicted its existence in 1935. The density at which it was made is within a few percent of the density predicted by WH. Metallic fluid H was achieved by multiple-shock compression of liquid H₂, which is quasi-isentropic and thermally equilibrated. That is, the compressions were isentropic but for enough temperature and entropy to drive the crossover to completion from H₂ to H at 9-fold compression. The metallic fluid is highly degenerate: T/T_F≈0.014. The basic ideas of dynamic compression, also known as supersonic, adiabatic, nonlinear hydrodynamics, were developed in the last half of the Nineteenth Century in European universities. Today dynamic compression is generally unfamiliar to the scientific community, which impedes general understanding as to why fluid H becomes metallic at a pressure observable in a laboratory. The purposes of this paper are to (i) present a brief review of dynamic compression and its affects on materials, (ii) review considerations that led to the sample holder designed specifically to make metallic fluid H, and (iii) present a brief inter-comparison of dynamic and static methods to achieve high pressure relative to their prospects for making metallic H.     

Ab initio prediction of superconductivity in molecular metallic hydrogen under high pressure

We present a first ab initio investigation of the electron-phonon coupling (EPC) of molecular metallic hydrogen with a Cmca structure based on the linear-response approach. This molecular metallic hydrogen with overlapping bands has an elastic instability at lower pressures (<300 GPa), but stabilizes dynamically under further compression as indicated by the absence of phonon softening, thus supporting the choice of Cmca structure as a good candidate for metallic hydrogen. Within the conventional BCS theory, the predicted critical temperature T_c is 107 K at 347 GPa, so indicating good candidacy for a high temperature superconductor. With increasing pressure, interestingly, the EPC parameter λ, hence, T_c increases, resulting from the increased electronic density of states at the Fermi level and EPC matrix element 〈I²〉, in spite of an enhanced average phonon frequency 〈ω²〉.     

Liquid xenon study under shock and quasi-isentropic compression

Abstract

The shock adiabat for liquid xenon in the density range of 5.2–7.9 g/cm³ and pressure range of 8–70 GPa was investigated. The brightness temperature of a shock wave front from 5000 K to ?15,000 K, as well as the electrical conductivity behind the front from 4·10³ to 1.2·10⁵ 1/Ohm m, were measured. X-ray technique was used to measure quasi-isentropic compression of liquid xenon up to ～13 g/cm³.

The equations of state for liquid and solid phases of xenon were found. Anomalous behavior of xenon at p=8.37 g/cm³ was revealed, that is due to a structural transition.     

Measurement of density, temperature, and electrical conductivity of a shock-compressed nonideal nitrogen plasma in the megabar pressure range

Kinematic and thermodynamic parameters of shock-compressed liquid nitrogen are measured behind the front of a plane shock wave using plane wave and hemispherical shock wave generators. In these experiments, high values of compression parameters (shock-compressed hydrogen density? ≈ 3.25 g/cm³ and temperature T≈ 56000 K at a pressure of P ≈ 265 GPa) are attained. The density, pressure, temperature, and electrical conductivity of the nonideal plasma of shock-compressed liquid nitrogen are measured. A nearly isochoric behavior of the nitrogen shock adiabat is observed in the pressure range P = 100–300 GPa. The thermodynamics of shock-compressed nitrogen is an alyzed using the model of the equation of state in the quasi-chemical representation (SAHA code) as well as the semiempirical wide-range equation of state developed at the Institute of Experimental Physics. Experimental results are interpreted on the basis of calculations as the fixation of the boundary of transition of shock-compressed nitrogen from the polymer phase to the state of a strongly nonideal plasma at P ≈ 100 GPa, ? ≈ 3.4 g/cm³.     

冲击加载下Zr51Ti5Ni10Cu25Al9金属玻璃的塑性行为

进行了10—27 GPa应力范围内Zr₅₁Ti₅Ni₁₀Cu₂₅Al₉金属玻璃的平面冲击实验以研究其高压-高应变率加载下的塑性行为.由样品自由面粒子速度剖面的分析获得了冲击加载过程的轴向应力,并通过轴向应力与静水压线的比较获得剪应力.实验结果表明,尽管存在明显的松弛效应,但Zr基金属玻璃的Hugoniot弹性极限随着冲击应力的增加而增加.然而,塑性波阵面上的剪应力则显示先硬化而后软化现象,而且软化的幅度随冲击应力的增加而增加.冲击加载下Zr基金属玻璃的上述剪应力变化特征与分子动力学模拟结果比较一致,但与压剪实验结果和一维应力冲击实验结果明显不同.     

Gold under high pressure

Abstract

First principle predictions for the equation of state of gold using solid and liquid state theories are compared up to combined pressures and temperatures of 600 GPa and 17 000 K with static diamond anvil cell compression, ultrasonic measurements and shock Hugoniot data which include a recent laser driven shock Hugoniot points at 600 GPa. Excellent agreement between theoretical and experimental data is observed. The theoretically estimated 300 K isotherm agrees to within 2 GPa with the isotherm that has been measured to 70 GPa using the diamond anvil cell. The structural energy estimates show that the normal f.c.c. phase remains stable under pressure. The estimate of the shock Hugoniot temperature of gold at 600 GPa based on a liquid state model is consistent with the measurements of laser induced shock luminescence, which in fact provides an experimental determination of the temperature of gold above its Hugoniot melting point. The powerful means provided by theory in the prediction of material properties of gold at ultra high pressures and temperatures is significant because gold is an efficient converter of laser energy into soft X-rays and is a potential candidate as a standard for high pressure, high temperature work.     

High temperature equation of state of metallic hydrogen

The equation of state of liquid metallic hydrogen is solved numerically. Investigations are carried out at temperatures from 3000 to 20 000 K and densities from 0.2 to 3 mol/cm³, which correspond both to the experimental conditions under which metallic hydrogen is produced on earth and the conditions in the cores of giant planets of the solar system such as Jupiter and Saturn. It is assumed that hydrogen is in an atomic state and all its electrons are collectivized. Perturbation theory in the electron-proton interaction is applied to determine the thermodynamic potentials of metallic hydrogen. The electron subsystem is considered in the randomphase approximation with regard to the exchange interaction and the correlation of electrons in the local-field approximation. The proton-proton interaction is taken into account in the hard-spheres approximation. The thermodynamic characteristics of metallic hydrogen are calculated with regard to the zero-, second-, and third-order perturbation theory terms. The third-order term proves to be rather essential at moderately high temperatures and densities, although it is much smaller than the second-order term. The thermodynamic potentials of metallic hydrogen are monotonically increasing functions of density and temperature. The values of pressure for the temperatures and pressures that are characteristic of the conditions under which metallic hydrogen is produced on earth coincide with the corresponding values reported by the discoverers of metallic hydrogen to a high degree of accuracy. The temperature and density ranges are found in which there exists a liquid phase of metallic hydrogen.     

Metastable Conducting Crystalline Hydrogen at High Pressure

The quantum molecular dynamics method within the density functional theory has been used to calculate the equation of state, pair correlation function, and static electrical conductivity of solid hydrogen in the region of formation of a conducting phase. Hysteresis has been revealed on the density dependence of the pressure at a temperature of 100 K under compression and subsequent tension. The overlapping of branches of the isotherms of the molecular and nonmolecular phases of solid hydrogen corresponds to the region of existence of metastable states. The width of this region is 275 GPa. It has been shown that conducting crystalline nonmolecular hydrogen with P2₁/c symmetry can exist at extension to a pressure of 350 GPa.

     

Evidence of maximum in the melting curve of hydrogen at megabar pressures

Hydrogen at high pressures of ∼400 GPa might be in a zero-temperature liquid ground state (N. Ashcroft, J. Phys.: Condens. Matter A 12, 129 (2000), E. G. Brovrnan et al., Sov. Phys. JETP 35, 783 (1972)). If metallic hydrogen is liquid, the melting T _melt(P) line should possess a maximum. Here we report on the experimental evaluation of the melting curve of hydrogen in the megabar pressure range. The melting curve of hydrogen has been shown to reach a maximum with T _melt = 1050 ± 60 K at P = 106 GPa and the melting temperature of hydrogen decreases at higher pressures so that T _melt = 880 ± 50 K at P = 146 GPa. The data were acquired with the aid of a laser heating technique where diamond anvils were not deteriorated by the hot hydrogen. Our experimental observations are in agreement with the theoretical prediction of unusual behavior of the melted hydrogen [S. Bonev et al., Nature 481, 669 (2004)]. The article is published in the original.     

Shock wave chemistry

Abstract

Shock wave chemistry, a new scientific trend, deals with investigations of chemical aspects of the substance state under this new type of effect. Indeed, shock wave effect is not a greater imposition than pressure and temperature actions. Characteristic features of the effect are the tremendous rates of substance loading and subsequent unloading. The effects result in a substance in a strongly non- equilibrium state. The lifetime of the state is governed by the relaxation process of those phenomena which are provoked by shock waves in the substance. For instance, in the case of substance consisting of complex molecules with a large number of internal degrees of freedom, differing strongly in excitation times, all kinetic parts of the shock energy are at first absorbed by the translational degrees of freedom inside the shock wave front. Then, the energy is redistributed to the vibrational degrees of freedom. The non-equilibrium state time is not longer than the excitation time of the most slowly excited vibrational degrees of freedom (10¹⁰-10^?9 s). The same order of magnitude is the relaxation time of liquid substance polarization caused by dipolar molecules mechanically turning under the shock discontinuity zone effect. In polymers the zone turns some separate groups of polymer molecule atoms. In such a case the relaxation period, on the contrary, may last as long as it can. As far as “hot are concerned, their lifetime is determined by thermal relaxation regularities and it depends on their size. The hot spots in solids appear during the shock compression process at the sites of an imperfect substance structure. In liquids the hot spots can orighate when a shock wave front passes through negative density fluctuations. It transforms the fluctuations of very small size and of high probability into some positive temperature regions of large size and extremely low probability at equilibrium state behind the wave front. The hot spots in perfect solids (possibly in liquids too) appear due to the effect of shear stresses in shock front. Pointed and lengthy defects of solid structure occur under the effect. The lengthy defects appear in the shock wave front due to the transition from one-dimensional to volume compression. The transition takes place if the wave intensity is larger than the dynamic elastic limit of the solid under investigation. In brittle materials the transition results in their grinding into fragments and in the relative displacement of the fragments. Some liquid melted layers of substance appear between the fragments in the process of displacement. Their lifetime is also determined by the thermal relaxation regularities and probably is small. Nevertheless, the layers obviously govern the spall strength of brittle solids and promote solid-phase shock reactions. The defects created in solids by the shock effect can exist for a very long time if the solid substance residual temperature is lower than its recrystallization temperature. Therefore, solid substance treatment by shocks of proper intensity can increase their chemical reactivity.     

Hydrogen and Deuterium Analysis Using Laser‐Induced Plasma Spectroscopy

Abstract

Hydrogen emission in laser plasma has been studied by focusing a TEA CO₂ laser and Nd‐YAG lasers on various types of samples, such as glass, quartz, and zircaloy pipes doped with hydrogen. It was found that H_α emission with a narrow spectral width occurs with high efficiency when the laser plasma is produced in low‐pressure host gas. In contrast, the conventional well‐known laser‐induced breakdown spectroscopy (LIBS), which operates at atmospheric air pressure, cannot be applied for the analysis of hydrogen as impurity. The specific characteristic of hydrogen emission in low‐pressure plasma is interpreted on the basis of our shock wave model, taking account of the fact that the hydrogen mass is extremely light compared to that of the host target. Another experimental study on gas analysis was conducted using an Nd‐YAG laser and helium host gas at atmospheric pressure on a sample of mixed water (H₂O) and heavy water (D₂O) in vapor form. It was shown that completely resolved hydrogen (H_α) and deuterium (D_α) emission lines that are separated by only 0.179 nm could be obtained at a properly delayed detection time when the charged particles responsible for the strong Stark broadening effect in the plasma have mostly disappeared. It is argued that a helium metastable excited state plays the important role in the hydrogen excitation process.     

Anomalously high metallization pressure of solid neon

The equation of state of solid fcc neon at T = 0 K is calculated by the local density functional theory in the muffin-tin approximation. The calculated equation of state is in good agreement with Hawke et al.'s experimental value at about 6 Mbar by magnetic flux compression and also agrees remarkably well with that by the quantum statistical model in the region of extremely high pressures. If no structural phase transition occurs up to metallization, solid neon becomes metallic at a molar volume of 0.256 cm³/mole or at a pressure of 1.58 × 10³ Mbar. This is the highest metallization pressure ever reported.     

Melting and thermal expansion of iron in uniformly laser-heated diamond anvil cells

Abstract

A technique is described to laser heat samples uniformly under hydrostatic pressure conditions to over 2500 K and 400 kbar with very high accuracy in P and T. I re-measured the melting curve of iron by this technique and obtained excellent agreement with my earlier work using resistive wire heating (Boehler 1986). P-V-T measurements on γ-iron to 200 kbar and 2000 K using synchrotron radiation leads to a strong decrease of the thermal expansion coefficient with pressure, (?lnα/?lnV)_T = 6.5. The zero pressure bulk modulus K₀ decreases with temperature by 0.33 kbar deg^?1. This Yields densities of iron at conditions in the Earth's core which are consistent with shock compression measurements. The potiential of studying mineralogical phase transitions by this method is described.     

Dynamic compression: what it is,making metallic H and magnetic fields of Uranus and Neptune

ABSTRACT

Static compression is a well-known method to achieve very high pressures in ‘cold’ (degenerate) condensed matter. Because dynamic compression is adiabatic, it achieves both high pressures and temperatures, which are tunable by choice of pressure-pulse shape. Dynamic compression uses supersonic hydrodynamic variables, which are straight forward to measure, to achieve a wide range of extreme thermodynamic states in degenerate condensed matter. Because dynamic compression developed primarily in national laboratories, it is relatively unknown to a significant portion of the high pressure community. This paper is a brief review of (i) dynamic compression itself, (ii) its application to making metallic fluid H (MFH) and (iii) implications of data generated at extreme conditions with dynamic compression for understanding the unusual magnetic fields of Uranus and Neptune, which are made primarily by convection of semiconducting and MFH. Metallic hydrogen made under dynamic and static compression is compared.