Semimetallic molecular hydrogen at pressure above 350 GPa

According to the theoretical predictions, insulating molecular hydrogen dissociates and transforms to an atomic metal at pressures P~370-500 GPa. In another scenario, the metallization first occurs in the 250-500 GPa pressure range in molecular hydrogen through overlapping of electronic bands. The calculations are not accurate enough to predict which option is realized. Here we show that at a pressure of ~360 GPa and temperatures <200 K the hydrogen starts to conduct, and that temperature dependence of the electrical conductivity is typical of a semimetal. The conductivity, measured up to 440 GPa, increases strongly with pressure. Raman spectra, measured up to 480 GPa, indicate that hydrogen remains a molecular solid at pressures up to 440 GPa, while at higher pressures the Raman signal vanishes, likely indicating further transformation to a good molecular metal or to an atomic state

Magnetic measurements at pressures above 10 GPa in a miniature ceramic anvil cell for a superconducting quantum interference device magnetometer

A miniature ceramic anvil high pressure cell (mCAC) was earlier designed by us for magnetic measurements at pressures up to 7.6 GPa in a commercial superconducting quantum interference (SQUID) magnetometer [N. Tateiwa et al., Rev. Sci. Instrum. 82, 053906 (2011)]. Here, we describe methods to generate pressures above 10 GPa in the mCAC. The efficiency of the pressure generation is sharply improved when the Cu-Be gasket is sufficiently preindented. The maximum pressure for the 0.6 mm culet anvils is 12.6 GPa when the Cu-Be gasket is preindented from the initial thickness of 0.30 to 0.06 mm. The 0.5 mm culet anvils were also tested with a rhenium gasket. The maximum pressure attainable in the mCAC is about 13 GPa. The present cell was used to study YbCu2Si2 which shows a pressure induced transition from the non-magnetic to magnetic phases at 8 GPa. We confirm a ferromagnetic transition from the dc magnetization measurement at high pressure. The mCAC can detect the ferromagnetic ordered state whose spontaneous magnetic moment is smaller than 1 mB per unit cell. The high sensitivity for magnetic measurements in the mCAC may result from the the simplicity of cell structure. The present study shows the availability of the mCAC for precise magnetic measurements at pressures above 10 GPa

Low temperature phase diagram of hydrogen at pressures up to 380 GPa. A possible metallic phase at 360 GPa and 200 K

Two new phases of hydrogen have been discovered at room temperature in Ref.1: phase IV above 220 GPa and phase V above ~270 GPa. In the present work we have found a new phase VI at P~360 GPa and T<200 K. This phase is likely metallic as follows from the featureless Raman spectra, a strong drop in resistance, and absence of a photoconductive response. We studied hydrogen at low temperatures with the aid of Raman, infrared absorption, and electrical measurements at pressures up to 380 GPa, and have built a new phase diagram of hydrogen.Comment: 9 pages, 12 figure

Equation of state of cubic boron nitride at high pressures and temperatures

We report accurate measurements of the equation of state (EOS) of cubic boron nitride by x-ray diffraction up to 160 GPa at 295 K and 80 GPa in the range 500-900 K. Experiments were performed on single-crystals embedded in a quasi-hydrostatic pressure medium (helium or neon). Comparison between the present EOS data at 295 K and literature allows us to critically review the recent calibrations of the ruby standard. The full P-V-T data set can be represented by a Mie-Gr\"{u}neisen model, which enables us to extract all relevant thermodynamic parameters: bulk modulus and its first pressure-derivative, thermal expansion coefficient, thermal Gr\"{u}neisen parameter and its volume dependence. This equation of state is used to determine the isothermal Gr\"{u}neisen mode parameter of the Raman TO band. A new formulation of the pressure scale based on this Raman mode, using physically-constrained parameters, is deduced.Comment: 8 pages, 7 figure

Conventional superconductivity at 203 K at high pressures

A superconductor is a material that can conduct electricity with no resistance below its critical temperature (Tc). The highest Tc that has been achieved in cuprates1 is 133 K at ambient pressure2 and 164 K at high pressures3. As the nature of superconductivity in these materials has still not been explained, the prospects for a higher Tc are not clear. In contrast, the Bardeen-Cooper-Schrieffer (BCS) theory gives a guide for achieving high Tc and does not put bounds on Tc, all that is needed is a favorable combination of high frequency phonons, strong electron-phonon coupling, and a high density of states. These conditions can be fulfilled for metallic hydrogen and covalent compounds dominated by hydrogen4,5. Numerous calculations support this idea and predict Tc of 50-235 K for many hydrides6 but only moderate Tc=17 K has been observed experimentally7. Here we studied sulfur hydride8 where a Tc~80 K was predicted9. We found that it transforms to a metal at pressure ~90 GPa. With cooling superconductivity was found deduced from a sharp drop of the resistivity to zero and a decrease of Tc with magnetic field. The pronounce isotope shift of Tc in D2S is evidence of an electron-phonon mechanism of superconductivity that is consistent with the BCS scenario. The superconductivity has been confirmed by magnetic susceptibility measurements with Tc=203K. The high Tc superconductivity most likely is due to H3S which is formed from H2S under its decomposition under pressure. Even higher Tc, room temperature superconductivity, can be expected in other hydrogen-based materials since hydrogen atoms provide the high frequency phonon modes as well as the strong electron-phonon coupling

Nitrogen backbone oligomers

In contrast to carbon, which forms long polymeric chains, all-nitrogen chains are very unstable. Here we found that nitrogen and hydrogen directly react at room temperature and pressures of about 35 GPa forming a mixture of nitrogen backbone oligomers - chains of single-bonded nitrogen atom with the rest of the bonds terminated with hydrogen atoms - as identified by IR absorption, Raman, X-ray diffraction experiments and theoretical calculations. The pressure required for the synthesis strongly decreases with temperature to about 20 GPa at 550 K. At releasing pressures below about 10 GPa, the product transforms into hydrazine. Our findings might open a way for the practical synthesis of these extremely high energetic materials as the formation of nitrogen-hydrogen compounds is favorable already at pressures above 2 GPa according to the calculations.Comment: 34 pages, 21 figure

Exotic magnetism in the alkali sesquoxides Rb4O6 and Cs4O6

Among the various alkali oxides the sesquioxides Rb4O6 and Cs4O6 are of special interest. Electronic structure calculations using the local spin-density approximation predicted that Rb4O6 should be a half-metallic ferromagnet, which was later contradicted when an experimental investigation of the temperature dependent magnetization of Rb4O6 showed a low-temperature magnetic transition and differences between zero-field-cooled (ZFC) and field-cooled (FC) measurements. Such behavior is known from spin glasses and frustrated systems. Rb4O6 and Cs4O6 comprise two different types of dioxygen anions, the hyperoxide and the peroxide anions. The nonmagnetic peroxide anions do not contain unpaired electrons while the hyperoxide anions contain unpaired electrons in antibonding pi*-orbitals. High electron localization (narrow bands) suggests that electronic correlations are of major importance in these open shell p-electron systems. Correlations and charge ordering due to the mixed valency render p-electron-based anionogenic magnetic order possible in the sesquioxides. In this work we present an experimental comparison of Rb4O6 and the related Cs4O6. The crystal structures are verified using powder x-ray diffraction. The mixed valency of both compounds is confirmed using Raman spectroscopy, and time-dependent magnetization experiments indicate that both compounds show magnetic frustration, a feature only previously known from d- and f-electron systems

Spectroscopy of H3_3S: evidence of a new energy scale for superconductivity

The discovery of a superconducting phase in sulfur hydride under high pressure with a critical temperature above 200 K has provided a new impetus to the search for even higher $T_c$. Theory predicted and experiment confirmed that the phase involved is H$_3$S with Im-3m crystal structure. The observation of a sharp drop in resistance to zero at $T_c$, its downward shift with magnetic field and a Meissner effect confirm superconductivity but the mechanism involved remains to be determined. Here, we provide a first optical spectroscopy study of this new superconductor. Experimental results for the optical reflectivity of H$_3$S, under high pressure of 150 GPa, for several temperatures and over the range 60 to 600 meV of photon energies, are compared with theoretical calculations based on Eliashberg theory using DFT results for the electron-phonon spectral density $\alpha^2$F($\Omega$). Two significant features stand out: some remarkably strong infrared active phonons at $\approx$ 160 meV and a band with a depressed reflectance in the superconducting state in the region from 450 meV to 600 meV. In this energy range, as predicted by theory, H$_3$S is found to become a better reflector with increasing temperature. This temperature evolution is traced to superconductivity originating from the electron-phonon interaction. The shape, magnitude, and energy dependence of this band at 150 K agrees with our calculations. This provides strong evidence of a conventional mechanism. However, the unusually strong optical phonon suggests a contribution of electronic degrees of freedom.Comment: 10 pages, 8 figures. Main manuscript and supplementary informatio

Pressure-induced Superconductivity in a Ferromagnet UGe2_2 -- Resistivity Measurements in Magnetic Field --

The electrical resistivity measurements in the magnetic field are carried out on the pressure-induced superconductor UGe$_2$. The superconductivity is observed from 1.06 to 1.44 GPa. The upper critical field of $H_{C2}$ is anisotropic where $H_{C2}(T)$ exhibits positive curvature for $H//b$ and $c$-axis. The characteristic enhancement of $H_{C2}$ is reconfirmed for $H//a$-axis. In the temperature and field dependence of resistivity at $P > P_{C}$ where the ferromagnetic ordering disappears, it is observed that the application of the external field along the {\it a}-axis increases the coefficient of Fermi liquid behavior $AT^{2}$ correspondingly to the metamagnetic transition.Comment: To be published in the proceeding of the International Conference on High Pressure Science and Technology(AIRAPT-18),Beijing,China,23-27 July 200