A Perspective on Hydrogen Near the Liquid-Liquid Phase Transition and Metallization of Fluid H.

Metallic hydrogen has been a major issue in physical chemistry since its prediction in 1935. Its predicted density implies 100 GPa (106 bar = Mbar) pressures P are needed to make metallic H with the Fermi temperature TF = 220 000 K. Temperatures T can be several 1000 K and still be "very low" with T/TF ≪ 1. In 1996, metallic fluid H was made under dynamic compression at P = 140 GPa and calculated T ≈ 3000 K generated with a two-stage light-gas gun. Those T's place metallic H in the liquid-liquid phase transition region. The purpose of this Perspective is to place the phase curve measured in laser-heated diamond anvil cells in context with those measured electrical conductivities. That phase curve is probably caused by dissociation of H2 to H starting near 90 GPa/1600 K. Metallic H then forms in a crossover as a semiconductor up to 140 GPa/3000 K. Dynamic quasi-isentropic pressure was tuned to make metallic H by design in those conductivity experiments.

Metastable ultracondensed hydrogenous materials.

The primary purpose of this paper is to stimulate theoretical predictions of how to retain metastably hydrogenous materials made at high pressure P on release to ambient. Ultracondensed metallic hydrogen has been made at high pressures in the fluid and reported made probably in the solid. Because the long quest for metallic hydrogen is likely to be concluded in the relatively near future, a logical question is whether another research direction, comparable in scale to the quest for metallic H, will arise in high pressure research. One possibility is retention of metastable solid metallic hydrogen and other hydrogenous materials on release of dynamic and static high pressures P to ambient. If hydrogenous materials could be retained metastably on release, those materials would be a new class of materials for scientific investigations and technological applications. This paper is a review of the current situation with the synthesis of metallic hydrogen, potential technological applications of metastable metallic H and other hydrogenous materials at ambient, and general background of published experimental and theoretical work on what has been accomplished with metastable phases in the past and thus what might be accomplished in the future.

Dynamic compression of dense oxide (Gd3Ga5O12) from 0.4 to 2.6 TPa: Universal Hugoniot of fluid metals.

Materials at high pressures and temperatures are of great current interest for warm dense matter physics, planetary sciences, and inertial fusion energy research. Shock-compression equation-of-state data and optical reflectivities of the fluid dense oxide, Gd3Ga5O12 (GGG), were measured at extremely high pressures up to 2.6 TPa (26 Mbar) generated by high-power laser irradiation and magnetically-driven hypervelocity impacts. Above 0.75 TPa, the GGG Hugoniot data approach/reach a universal linear line of fluid metals, and the optical reflectivity most likely reaches a constant value indicating that GGG undergoes a crossover from fluid semiconductor to poor metal with minimum metallic conductivity (MMC). These results suggest that most fluid compounds, e.g., strong planetary oxides, reach a common state on the universal Hugoniot of fluid metals (UHFM) with MMC at sufficiently extreme pressures and temperatures. The systematic behaviors of warm dense fluid would be useful benchmarks for developing theoretical equation-of-state and transport models in the warm dense matter regime in determining computational predictions.

The electrical conductivity of Al2O3 under shock-compression.

Sapphire (Al2O3) crystals are used below 100 GPa as anvils and windows in dynamic-compression experiments because of their transparency and high density. Above 100 GPa shock pressures, sapphire becomes opaque and electrically conducting because of shock-induced defects. Such effects prevent temperature and dc conductivity measurements of materials compressed quasi-isentropically. Opacities and electrical conductivities at ~100 GPa are non-equilibrium, rather than thermodynamic parameters. We have performed electronic structure calculations as a guide in predicting and interpreting shock experiments and possibly to discover a window up to ~200 GPa. Our calculations indicate shocked sapphire does not metallize by band overlap at ~300 GPa, as suggested previously by measured non-equilibrium data. Shock-compressed Al2O3 melts to a metallic liquid at ~500 GPa and 10,000 K and its conductivity increases rapidly to ~2000 Ω(-1)cm(-1) at ~900 GPa. At these high shock temperatures and pressures sapphire is in thermal equilibrium. Calculated conductivity of Al2O3 is similar to those measured for metallic fluid H, N, O, Rb, and Cs. Despite different materials, pressures and temperatures, and compression techniques, both experimental and theoretical, conductivities of all these poor metals reach a common end state typical of strong-scattering disordered materials.

Transition to a virtually incompressible oxide phase at a shock pressure of 120 GPa (1.2 Mbar): Gd3Ga5O12.

Cubic, single-crystal, transparent Gd(3)Ga(5)O(12) has a density of 7.10 g/cm(3), a Hugoniot elastic limit of 30 GPa, and undergoes a continuous phase transition from 65 GPa to a quasi-incompressible (QI) phase at 120 GPa. Only diamond has a larger Hugoniot elastic limit. The QI phase of is more incompressible than diamond from 170 to 260 GPa. Electrical conductivity measurements indicate the QI phase has a band gap of 3.1 eV. Gd(3)Ga(5)O(12) can be used to obtain substantially higher pressures and lower temperatures in metallic fluid hydrogen than was achieved previously by shock reverberation between Al(2)O(3) disks.

Metallization of fluid nitrogen and the mott transition in highly compressed low-Z fluids.

Electrical conductivities are reported for degenerate fluid nitrogen at pressures up to 180 GPa (1.8 Mbar) and temperatures of approximately 7000 K. These extreme quasi-isentropic conditions were achieved with multiple-shock compression generated with a two-stage light-gas gun. Nitrogen undergoes a nonmetal-metal transition at 120 GPa, probably in the monatomic state. These N data and previous conductivity data for H, O, Cs, and Rb are used to develop a general picture of the systematics of the nonmetal-metal transition in these fluids. Specifically, the density dependences of electrical conductivities in the semiconducting fluid are well correlated with the radial extent of the electronic charge-density distributions of H, N, O, Cs, and Rb atoms. These new data for N scale with previous data for O, as expected from their similar charge-density distributions.

Shock compression of deuterium near 100 GPa pressures.

The shock-compression curve (Hugoniot) of D2 near 100 GPa pressures (1 Mbar) has been contro-versial because the two published measurements have limiting compressions of fourfold and sixfold. Our purpose is to examine published experimental results to decide which, if either, is probably correct. The published Hugoniot data of low-Z diatomic molecules have a universal behavior. The deuterium data of Knudson et al. (fourfold limiting compression) have this universal behavior, which suggests that Knudson et al. are correct and shows that deuterium behaves as other low-Z elements at high tem-peratures. In D2, H2, N2, CO, and O2, dissociation completes and average kinetic energy dominates average potential energy above approximately 60 GPa. Below approximately 30 GPa, D2, H2, N2, CO, and O2 are diatomic. D2 dissociation is accompanied by a temperature-driven nonmetal-metal transition at approximately 50 GPa.

High pressure insulator-metal transition in molecular fluid oxygen.

We report the first experimental evidence for a metallic phase in fluid molecular oxygen. Our electrical conductivity measurements of fluid oxygen under dynamic quasi-isentropic compression show that a nonmetal-metal transition occurs at 3.4 fold compression, 4500 K, and 1.2 Mbar. We discuss the main features of the electrical conductivity dependence on density and temperature and give an interpretation of the nature of the electrical transport mechanisms in fluid oxygen at these extreme conditions.

Metallization and electrical conductivity of hydrogen in Jupiter.

Electrical conductivities of molecular hydrogen in Jupiter were calculated by scaling electrical conductivities measured at shock pressures in the range of 10 to 180 gigapascals (0.1 to 1.8 megabars) and temperatures to 4000 kelvin, representative of conditions inside Jupiter. Jupiter's magnetic field is caused by convective dynamo motion of electrically conducting fluid hydrogen. The data imply that Jupiter should become metallic at 140 gigapascals in the fluid, and the electrical conductivity in the jovian molecular envelope at pressures up to metallization is about an order of magnitude larger than expected previously. The large magnetic field is produced in the molecular envelope closer to the surface than previously thought.

Temperature measurements of shock-compressed liquid hydrogen: implications for the interior of Jupiter.

Shock temperatures of hydrogen up to 5200 kelvin were measured optically at pressures up to 83 gigapascals (830 kilobars). At highest pressures, the measured temperatures are substantially lower than predicted. These lower temperatures are caused by a continuous dissociative phase transition above 20 gigapascals. Because hydrogen is in thermal equilibrium in shock-compression experiments, the theory derived from the shock data can be applied to Jupiter. The planet's molecular envelope is cooler and has much less temperature variation than previously believed. The continuous dissociative phase transition suggests that there is no sharp boundary between Jupiter's molecular mantle and its metallic core. A possible convectively quiescent boundary layer might induce an additional layer in the molecular region, as has been predicted.

Phase transformations in carbon fullerenes at high shock pressures.

C(60) powders were shock-compressed quasi-isentropically and quenched from pressures in the range 10 to 110 GPa (0.1 to 1.1 Mbar). Recovered specimens were analyzed by Raman spectroscopy and optical microscopy. C(60) fullerenes are stable into the 13- to 17-GPa pressure range. The onset of a fast ( approximately 0.5 micros) reconstructive transformation to graphite occurs near 17 GPa. The graphite recovered from 27 GPa and about 600 degrees C is relatively well ordered with crystal planar domain size of about 100 A. Above 50 GPa a continuous transformation to an amorphous state is observed in recovered specimens. The fast transformation to graphite is proposed to occur by pi-electron rehybridization which initiates breakup of the ball structure and formation of the graphite structure at high density.

Interior structure of neptune: comparison with uranus.

Measurements of rotation rates and gravitational harmonics of Neptune made with the Voyager 2 spacecraft allow tighter constraints on models of the planet's interior. Shock measurements of material that may match the composition of Neptune, the so-calied planetary ;;ice,'' have been carried out to pressures exceeding 200 gigapascals (2 megabars). Comparison of shock data with inferred pressure-density profiles for both Uranus and Neptune shows substantial similarity through most of the mass of both planets. Analysis of the effect of Neptune's strong differential rotation on its gravitational harmonics indicates that differential rotation involves only the outermost few percent of Neptune's mass.

The nature of the interior of uranus based on studies of planetary ices at high dynamic pressure.

Data from the Voyager II spacecraft showed that Uranus has a large magnetic field with geometry similar to an offset tilted dipole. To interpret the origin of the magnetic field, measurements were made of electrical conductivity and equation-of-state data of the planetary "ices" ammonia, methane, and "synthetic Uranus" at shock pressures and temperatures up to 75 gigapascals and 5000 K. These pressures and temperatures correspond to conditions at the depths at which the surface magnetic field is generated. Above 40 gigapascals the conductivities of synthetic Uranus, water, and ammonia plateau at about 20(ohm-cm)(-1), providing an upper limit for the electrical conductivity used in kinematic or dynamo calculations. The nature of materials at the extreme conditions in the interior is discussed.