Conventional superconductivity at 203 kelvin at high pressures in the sulfur hydride system.

A superconductor is a material that can conduct electricity without resistance below a superconducting transition temperature, Tc. The highest Tc that has been achieved to date is in the copper oxide system: 133 kelvin at ambient pressure and 164 kelvin at high pressures. As the nature of superconductivity in these materials is still not fully understood (they are not conventional superconductors), the prospects for achieving still higher transition temperatures by this route are not clear. In contrast, the Bardeen-Cooper-Schrieffer theory of conventional superconductivity gives a guide for achieving high Tc with no theoretical upper bound--all that is needed is a favourable combination of high-frequency phonons, strong electron-phonon coupling, and a high density of states. These conditions can in principle be fulfilled for metallic hydrogen and covalent compounds dominated by hydrogen, as hydrogen atoms provide the necessary high-frequency phonon modes as well as the strong electron-phonon coupling. Numerous calculations support this idea and have predicted transition temperatures in the range 50-235 kelvin for many hydrides, but only a moderate Tc of 17 kelvin has been observed experimentally. Here we investigate sulfur hydride, where a Tc of 80 kelvin has been predicted. We find that this system transforms to a metal at a pressure of approximately 90 gigapascals. On cooling, we see signatures of superconductivity: a sharp drop of the resistivity to zero and a decrease of the transition temperature with magnetic field, with magnetic susceptibility measurements confirming a Tc of 203 kelvin. Moreover, a pronounced isotope shift of Tc in sulfur deuteride is suggestive of an electron-phonon mechanism of superconductivity that is consistent with the Bardeen-Cooper-Schrieffer scenario. We argue that the phase responsible for high-Tc superconductivity in this system is likely to be H3S, formed from H2S by decomposition under pressure. These findings raise hope for the prospects for achieving room-temperature superconductivity in other hydrogen-based materials.

Lone-pair interactions and photodissociation of compressed nitrogen trifluoride.

High-pressure behavior of nitrogen trifluoride (NF3) was investigated by Raman and IR spectroscopy at pressures up to 55 GPa and room temperature, as well as by periodic calculations up to 100 GPa. Experimentally, we find three solid-solid phase transitions at 9, 18, and 39.5 GPa. Vibrational spectroscopy indicates that in all observed phases NF3 remains in the molecular form, in contrast to the behavior of compressed ammonia. This finding is confirmed by density functional theory calculations, which also indicate that the phase transitions of compressed NF3 are governed by the interplay between lone­pair interactions and efficient molecule packing. Although nitrogen trifluoride is molecular in the whole pressure range studied, we show that it can be photodissociated by mid-IR laser radiation. This finding paves the way for the use of NF3 as an oxidizing and fluorinating agent in high-pressure reactions.

Pressure induced ionic-superionic transition in silver iodide at ambient temperature.

Silver iodide (AgI-V) is an archetypical ionic compound for studying the formation mechanism of a superionic state. Previous studies have proven that superionic AgI with high ionic conductivity greater than 0.1 Ω(-1)cm(-1) could only be obtained at high temperatures. We show in this paper that high pressure could also induce the superionic state in AgI even at ambient temperature. Using electrochemical impedance spectroscopy, we investigated Ag(+) ions diffusing in rock-salt structured AgI-III and KOH-type AgI-V under high pressures and directly observed the superionic state in AgI-V. The diffusion coefficient of AgI-V is ∼3.4 × 10(-4)-8.6 × 10(-4) cm(2)/s in the investigated pressure range of 12-17 GPa, comparable with those of superionic α-AgI and AgI-III'. By analyzing the half infinite length Warburg diffusion process, two parameters α and ß, which closely relate to the disordered state of Ag(+) ions, have been determined and it was suggested that Ag(+) ions in AgI-V become disordered. The ionic conductivity of AgI-V is three orders of magnitude higher than that of AgI-III, and has reached around 0.1 Ω(-1)cm(-1). Evidence for all three, the diffusion coefficient, α and ß, and conductivity have proven that AgI-V is a superionic conductor at ambient temperature.

Conductive dense hydrogen.

Molecular hydrogen is expected to exhibit metallic properties under megabar pressures. This metal is predicted to be superconducting with a very high critical temperature, T(c), of 200-400 K, and it may acquire a new quantum state as a metallic superfluid and a superconducting superfluid. It may potentially be recovered metastably at ambient pressures. However, experiments carried out at low temperatures, T<100 K, showed that at record pressures of 300 GPa, hydrogen remains in the molecular insulating state. Here we report on the transformation of normal molecular hydrogen at room temperature (295 K) to a conductive and metallic state. At 200 GPa the Raman frequency of the molecular vibron strongly decreased and the spectral width increased, evidencing a strong interaction between molecules. Deuterium behaved similarly. Above 220 GPa, hydrogen became opaque and electrically conductive. At 260-270 GPa, hydrogen transformed into a metal as the conductance of hydrogen sharply increased and changed little on further pressurizing up to 300 GPa or cooling to at least 30 K; and the sample reflected light well. The metallic phase transformed back at 295 K into molecular hydrogen at 200 GPa. This significant hysteresis indicates that the transformation of molecular hydrogen into a metal is accompanied by a first-order structural transition presumably into a monatomic liquid state. Our findings open an avenue for detailed and comprehensive studies of metallic hydrogen.

Electronic and magnetic phase diagram of beta-Fe(1.01)Se with superconductivity at 36.7 K under pressure.

The discovery of new high-temperature superconductors based on FeAs has led to a new 'gold rush' in high-T(C) superconductivity. All of the new superconductors share the same common structural motif of FeAs layers and reach T(C) values up to 55 K (ref. 2). Recently, superconductivity has been reported in FeSe (ref. 3), which has the same iron pnictide layer structure, but without separating layers. Here, we report the magnetic and electronic phase diagram of beta-Fe(1.01)Se as a function of temperature and pressure. The superconducting transition temperature increases from 8.5 to 36.7 K under an applied pressure of 8.9 GPa. It then decreases at higher pressures. A marked change in volume is observed at the same time as T(C) rises, owing to a collapse of the separation between the Fe(2)Se(2) layers. No static magnetic ordering is observed for the whole p-T phase diagram. We also report that at higher pressures (starting around 7 GPa and completed at 38 GPa), Fe(1.01)Se transforms to a hexagonal NiAs-type structure and exhibits non-magnetic behaviour.