In situ Raman spectroscopy of cubic boron nitride to 90GPa and 800K

AbstractThe temperature and pressure dependences of the Raman spectrum of the transverse-optical mode of cubic boron nitride were calibrated for applications to a Raman spectroscopy pressure sensor in optical cells to about 800K and 90GPa. A significant deviation from linearity of the pressure dependence is confirmed at pressures above 20GPa. At ambient temperature, dv/dP slopes are 3.41(7) and 2.04(7) cm−1/GPa at 0 and 90GPa, respectively. A polynomial expression is used to fit the pressure–temperature dependence of the Raman line. The pressure dependence does not significantly change with temperature, as determined from experiments conducted up to 800K. At 0GPa, the dv/dP slope is 3.46(7)cm−1/GPa at 800K. At pressures above 90GPa, the Raman spectrum of the transverse-optical mode cannot be observed because of an overlap of the signals of cubic boron nitride and diamond used as the anvils in the high-pressure cell

Crystal Structure of 200 K-Superconducting Phase of Sulfur Hydride System

This article reports the experimentally clarified crystal structure of a recently discovered sulfur hydride in high temperature superconducting phase which has the highest critical temperature Tc over 200 K which has been ever reported. For understanding the mechanism of the high superconductivity, the information of its crystal structure is very essential. Herein we have carried out the simultaneous measurements electrical resistance and synchrotron x-ray diffraction under high pressure, and clearly revealed that the hydrogen sulfide, H2S, decomposes to H3S and its crystal structure has body-centered cubic symmetry in the superconducting phase.Comment: 8 pages, 3 figure

Compression experiments to 126 GPa and 2500 K and thermal equation of state of Fe3S: Implications for sulphur in the Earth’s core

Pressure-volume-temperature (P-V-T) experiments on tetragonal Fe3S were conducted to 126 GPa and 2500 K in laser-heated diamond anvil cells (DAC) with in-situ X-ray diffraction (XRD). Seventy nine high-T data as well as four 300-K data were collected, based on which new thermal equations of state (EoS) for Fe3S were established. The room-T data together with existing data were fitted to the third order Birch-Murnaghan EoS, which yielded, GPa and with fixed at 377.0 Å3. A constant term in the thermal pressure equation, Pth = , fitted the high-T data well to the highest temperature, which implies that the contributions from the anharmonic and electronic terms should be minor in the thermal pressure term. The high-T data were also fitted to the Mie-Grüneisen-Debye model; with and q fixed at 417 K and 1 respectively. Calculations from the EoS show that crystalline Fe3S at 4000-5500 K is denser than the Earth's outer core and less dense than the inner core. Assuming a density reduction due to melting, liquid Fe3S would meet the outer core density profile, which however suggests that no less than 16 wt%S is needed to reconcile the observed outer core density deficit. The S-rich B2 phase, which was suggested to be a potential liquidus phase of an Fe3S-outer core above 250 GPa, namely the main constituent of its solid inner core, would likely be less dense than the Earth's inner core. As such, while the outer core density requires as much sulphur as 16 wt%, the resulting liquidus phase cannot meet the density of the inner core. Any sulphur-rich composition should therefore be rejected for the Earth's core

High-pressure melting experiments of Fe3S and a thermodynamic model of the Fe-S liquids for the Earth’s core

Melting experiments on Fe3S were conducted to 75 GPa and 2800 K in laser-heated and internally resistive-heated diamond anvil cells with in-situ x-ray diffraction and/or post-mortem textural observation. From the constrained melting curve, we assessed the thermal equation of state for Fe3S liquid. Then we constructed a thermodynamic model of melting of the system Fe–Fe3S including the eutectic relation under high pressures based on our new experimental data. The mixing properties of Fe–S liquids under high pressures were evaluated in order to account for existing experimental data on eutectic temperature. The results demonstrate that the mixing of Fe and S liquids are nonideal at any core pressure. The calculated sulphur content in eutectic point decreases with increasing pressure to 120 GPa and is fairly constant of 8 wt% at greater pressures. From the Gibbs free energy, we derived the parameters to calculate the crystallising point of an Fe–S core and its isentrope, and then we calculated the density and the longitudinal seismic wave velocity (Vp) of these liquids along each isentrope. While Fe3S liquid can account for the seismologically constrained density and Vp profiles over the outer core, the density of the precipitating phase is too low for the inner core. On the other hand, a hypothetical Fe–S liquid core with a bulk composition on the Fe-rich side of the eutectic point cannot represent the density and Vp profiles of the Earth's outer core. Therefore, Earth's core cannot be approximated by the system Fe–S and it should include another light element

Optimized unconventional superconductivity in a molecular Jahn-Teller metal

Understanding the relationship between the superconducting, the neighboring insulating, and the normal metallic state above Tc is a major challenge for all unconventional superconductors. The molecular A3C60 fulleride superconductors have a parent antiferromagnetic insulator in common with the atom-based cuprates, but here, the C603– electronic structure controls the geometry and spin state of the structural building unit via the on-molecule Jahn-Teller effect. We identify the Jahn-Teller metal as a fluctuating microscopically heterogeneous coexistence of both localized Jahn-Teller–active and itinerant electrons that connects the insulating and superconducting states of fullerides. The balance between these molecular and extended lattice features of the electrons at the Fermi level gives a dome-shaped variation of Tc with interfulleride separation, demonstrating molecular electronic structure control of superconductivity

Thermal Equation of State of Fe3C to 327 GPa and Carbon in the Core

The density and sound velocity structure of the Earth’s interior is modeled on seismological observations and is known as the preliminary reference Earth model (PREM). The density of the core is lower than that of pure Fe, which suggests that the Earth’s core contains light elements. Carbon is one plausible light element that may exist in the core. We determined the equation of state (EOS) of Fe3C based on in situ high-pressure and high-temperature X-ray diffraction experiments using a diamond anvil cell. We obtained the P–V data of Fe3C up to 327 GPa at 300 K and 70–180 GPa up to around 2300 K. The EOS of nonmagnetic (NM) Fe3C was expressed by two models using two different pressure scales and the third-order Birch–Murnaghan EOS at 300 K with the Mie–Grüneisen–Debye EOS under high-temperature conditions. The EOS can be expressed with parameters of V0 = 148.8(±1.0) Å3, K0 = 311.1(±17.1) GPa, K0′ = 3.40(±0.1), γ0 = 1.06(±0.42), and q = 1.92(±1.73), with a fixed value of θ0 = 314 K using the KBr pressure scale (Model 1), and V0 = 147.3(±1.0) Å3, K0 = 323.0(±16.6) GPa, K0′ = 3.43(±0.09), γ0 = 1.37(±0.33), and q = 0.98(±1.01), with a fixed value of θ0 = 314 K using the MgO pressure scale (Model 2). The density of Fe3C under inner core conditions (assuming P = 329 GPa and T = 5000 K) calculated from the EOS is compatible with the PREM inner core