Vadim Ksenofontov

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.The highest critical temperature of superconductivity Tc has been achieved in cuprates: 133 K at ambient pressure and 164 K at high pressures. As the nature of superconductivity in these materials is still not disclosed, the prospects for a higher Tc are not clear. In contrast the Bardeen-Cooper-Schrieffer (BCS) theory gives a clear guide for achieving high Tc: it should be a favorable combination of high frequency phonons, strong coupling between electrons and phonons, and high density of states. These conditions can be fulfilled for metallic hydrogen and covalent hydrogen dominant compounds. Numerous followed calculations supported this idea and predicted Tc=100-235 K for many hydrides but only moderate Tc~17 K has been observed experimentally. Here we found that sulfur hydride transforms at P~90 GPa to metal and superconductor with Tc increasing with pressure to 150 K at ~200 GPa. This is in general agreement with recent calculations of Tc~80 K for H2S. Moreover we found superconductivity with Tc~190 K in a H2S sample pressurized to P>150 GPa at T>220 K. This superconductivity likely associates with the dissociation of H2S, and formation of SHn (n>2) hydrides. We proved occurrence of superconductivity by the drop of the resistivity at least 50 times lower than the copper resistivity, the decrease of Tc with magnetic field, and the strong isotope shift of Tc in D2S which evidences a major role of phonons in the superconductivity. H2S is a substance with a moderate content of hydrogen therefore high Tc can be expected in a wide range of hydrogen-contain materials. Hydrogen atoms seem to be essential to provide the high frequency modes in the phonon spectrum and the strong electron-phonon coupling.

Extreme sensitivity of superconductivity to stoichiometry in Fe1+δSe

The recently discovered iron arsenide superconductors appear to display a universal set of characteristic features, including proximity to a magnetically ordered state and robustness of the superconductivity in the presence of disorder. Here we show that superconductivity in Fe1+?Se, which can be considered the parent compound of the superconducting arsenide family, is destroyed by very small changes in stoichiometry. Further, we show that nonsuperconducting Fe1+?Se is not magnetically ordered down to 5 K. These results suggest that robust superconductivity and immediate instability against an ordered magnetic state should not be considered as intrinsic characteristics of iron-based superconducting systems.

Geometric, electronic, and magnetic structure of Co2FeSi: Curie temperature and magnetic moment measurements and calculations.

In this work a simple concept was used for a systematic search for materials with high spin polarization. It is based on two semiempirical models. First, the Slater-Pauling rule was used for estimation of the magnetic moment. This model is well supported by electronic structure calculations. The second model was found particularly for Co{sub 2} based Heusler compounds when comparing their magnetic properties. It turned out that these compounds exhibit seemingly a linear dependence of the Curie temperature as function of the magnetic moment. Stimulated by these models, Co{sub 2}FeSi was revisited. The compound was investigated in detail concerning its geometrical and magnetic structure by means of x-ray diffraction, x-ray absorption, and Moessbauer spectroscopies as well as high and low temperature magnetometry. The measurements revealed that it is, currently, the material with the highest magnetic moment (6{mu}{sub B}) and Curie temperature (1100 K) in the classes of Heusler compounds as well as half-metallic ferromagnets. The experimental findings are supported by detailed electronic structure calculations.

Electronic and magnetic phase diagram of β -Fe 1.01 Se with superconductivity at 36.7 K under pressure

In this letter, we report that the superconductivity transition temperature in beta-Fe1.01Se increases from 8.5 to 36.7 K under applied pressure of 8.9 GPa. It then decreases at higher pressure. A dramatic change in volume is observed at the same time Tc rises, due to a collapse of the separation between the Fe2Se2 layers. A clear transition to a linear resistivity normal state is seen on cooling at all pressures. No static magnetic ordering is observed for the whole p-T phase diagram. We also report that at higher pressure (starting around 7 GPa and completed at 38 GPa), Fe1.01Se transforms to a hexagonal NiAs-type structure and displays non-magnetic, insulating behavior. The inclusion of electron correlation in band structure caculations is necessary to describe this behavior, signifying that such correlations are important in this chemical system. Our results strongly support unconventional superconductivity in beta-Fe1.01Se.

Spin Crossover in a Supramolecular Fe4II [2×2] Grid Triggered by Temperature, Pressure, and Light

A multiplex electronic switch on the molecular level has been realized by using a tetranuclear FeII complex of the [2×2] grid type. The four metal ions can be switched stepwise between their high-spin and low-spin states by temperature, pressure, and light, thus representing a triple level, triple switch system as illustrated in the picture.

Investigation of Co2FeSi: The Heusler compound with highest Curie temperature and magnetic moment

This work reports on structural and magnetic investigations of the Heusler compound Co2FeSi. X-ray diffraction and Mosbauer spectrometry indicate an ordered L21 structure. Magnetic measurements by means of x-ray magnetic circular dichroism and magnetometry revealed that this compound is, currently, the material with the highest magnetic moment (6μB) and Curie temperature (1100K) in the classes of Heusler compounds as well as half-metallic ferromagnets.

Tetragonal-to-Orthorhombic Structural Phase Transition at 90 K in the Superconductor Fe1.01Se

In this letter we show that superconducting Fe1.01Se undergoes a structural transition at 90 K from a tetragonal to an orthorhombic phase but that non-superconducting Fe1.03Se does not. Further, high resolution electron microscopy study at low temperatures reveals an unexpected additional modulation of the crystal structure of the superconducting phase involving displacements of the Fe atoms, and that the non-superconducting material shows a distinct, complex nanometer-scale structural modulation. Finally, we show that magnetism is not the driving force for the phase transition in the superconducting phase.

Half-metallic ferromagnetism with high magnetic moment and high Curie temperature in Co2FeSi

Co2FeSi crystallizes in the ordered L21 structure as proven by x-ray diffraction and Moβbauer spectroscopy. The magnetic moment of Co2FeSi was measured to be about 6μB at 5 K. Magnetic circular dichroism spectra excited by soft x-rays were taken to determine the element-specific magnetic moments of Co and Fe. The Curie temperature was measured with different methods to be (1100±20)K. Co2FeSi was found to be the Heusler compound as well as the half-metallic ferromagnet with the highest magnetic moment and Curie temperature.

Does the solid-liquid crystal phase transition provoke the spin-state change in spin-crossover metallomesogens?

Three types of interplay/synergy between spin-crossover (SCO) and liquid crystalline (LC) phase transitions can be predicted: (i) systems with coupled phase transitions, where the structural changes associated to the Cr<-->LC phase transition drives the spin-state transition, (ii) systems where both transitions coexist in the same temperature region but are not coupled, and (iii) systems with uncoupled phase transitions. Here we present a new family of Fe(II) metallomesogens based on the ligand tris[3-aza-4-((5-C(n))(6-R)(2-pyridyl))but-3-enyl]amine, with C(n) = hexyloxy, dodecyloxy, hexadecyloxy, octadecyloxy, eicosyloxy, R = hydrogen or methyl (C(n)-trenH or C(n)-trenMe), which affords examples of systems of types i, ii, and iii. Self-assembly of the ligands C(n)-trenH and C(n)-trenMe with Fe(A)2 x xH2O salts have afforded a family of complexes with general formula [Fe(C(n)-trenR)](A)2 x sH2O (s > or = 0), with A = ClO4(-), F-, Cl-, Br- and I-. Single-crystal X-ray diffraction measurements have been performed on two derivatives of this family, named as [Fe(C6-trenH)](ClO4)2 (C(6)-1) and [Fe(C6-trenMe)](ClO4)2 (C(6)-2), at 150 K for C(6)-1 and at 90 and 298 K for C(6)-2. At 150 K, C(6)-1 displays the triclinic space group P, whereas at 90 and at 298 K C(6)-2 adopts the monoclinic P2(1)/c space group. In both compounds the iron atoms adopt a pseudo-octahedral symmetry and are surrounded by six nitrogen atoms belonging to imino groups and pyridines of the ligands C(n)-trenH and C(n)-trenMe. The average Fe(II)-N bonds (1.963(2) A) at 150 K denote that C(6)-1 is in the low-spin (LS) state. For C(6)-2 the average Fe(II)-N bonds (2.007(1) A) at 90 K are characteristic of the LS state, while at 298 K they are typical for the high-spin (HS) state (2.234(3) A). Compound C(6)-1 and [Fe(C18-trenH)](ClO4)2 (C(18)-1) adopts the LS state in the temperature region between 10 and 400 K, while compound C(6)-2 and [Fe(Cn-trenMe)](ClO4)2 (n = 12 (C(12)-2), 18 (C(18)-2)) exhibit spin crossover behavior at T(1/2) centered around 140 K. The thermal spin transition is accompanied by a pronounced change of color from dark red (LS) to orange (HS). The light-induced excited spin state trapping (LIESST) effect has been investigated in compounds C(6)-2, C(12)-2 and C(18)-2. The T(1/2)LIESST is 56 K (C(6)-2), 48 K (C(16)-2), and 56 K (C(18)-2). On the basis of differential scanning calorimetry, optical polarizing microscopy, and X-ray diffraction findings for C(18)-1, C(12)-2, and C(18)-2 at high temperature a smectic mesophase SX has been identified with layered structures similar to C(6)-1 and C(6)-2. The compounds [Fe(C(n)-trenH)](Cl)2 x sH2O (n = 16 (C(16)-3, s = 3.5, C(16)-4, s = 0.5, C(16)-5, s = 0), 18 (C(18)-3, s = 3.5, C(18)-4, s = 0.5, C(18)-5, s = 0), 20 (C(20)-3, s = 3.5, C(20)-4, s = 0.5, C(20)-5, s = 0)) and [Fe(C18-tren)](F)2 x sH2O (C(18)-6, s = 3.5, C(18)-7, s = 0) show a very particular spin-state change, while [Fe(C18-tren)](Br)2 x 3H2O (C(18)-8) together with [Fe(C18-tren)](I)2 (C(18)-9) are in the LS state (10-400 K) and present mesomorphic behavior like that observed for the complexes C(18)-1, C(12)-2, and C(18)-2. In compounds C(n)-3 50% of the Fe(II) ions undergo spin-state change at T(1/2) = 375 K induced by releasing water, and in partially dehydrated compounds (s = 0.5) the Cr-->SA phase transition occurs at 287 K (C(16)-4), 301 K (C(18)-4) and 330 K (C(20)-4). For the fully dehydrated materials C(n)-5 50% of the Fe(II) ions are in the HS state and show paramagnetic behavior between 10 and 400 K. In the partially dehydrated C(n)-4 the spin transition is induced by the change of the aggregate state of matter (solid<-->liquid crystal). For compound C(18)-6 the full dehydration to C(18)-7 provokes the spin-state change of nearly 50% of the Fe(II) ions. The compounds C(n)-3 and C(18)-6 are dark purple in the LS state and become light purple-brown when 50% of the Fe(II) atoms are in the HS state.

Polymorphism and Pressure Driven Thermal Spin Crossover Phenomenon in [Fe(abpt)2(NCX)2] (X=S, and Se): Synthesis,Structure and Magnetic Properties

The monomeric compounds [Fe(abpt 2(NCX)2(X = S (1), Se (2) and abpt = 4-amino- 3,5-bis(pyridin-2-yl)-1,2,4-triazole) have been synthesized and characterized. They crystallize in the monoclinic P21/n space group with a = 11.637(2) A, b = 9.8021(14) A, c = 12.9838(12) A, β = 101.126(14)°, and Z=2 for 1, and a= 11.601(2) A, b = 9.6666(14) A, c = 12.883(2) A, β = 101.449(10)°, and Z = 2 for 2. The unit cell contains a pair mononuclear [Fe(abpt)2(NCX)21 units related by a center of symmetry. Each iron atom, located at a molecular inversion center, is in a distorted octahedral environment. Four of the six nitrogen atoms coordinated to the Fe(II) ion belong to the pyridine-N(1) and triazole-N(2) rings of two abpt ligands. The remaining trans positions are occupied by two nitrogen atoms, N(3), belonging to the two pseudo-halide ligands. The magnetic susceptibility measurements at ambient pressure have revealed that they are in the high-spin range in the 2 K300 K temperature range. The pressure study has revealed that compound 1 remains in high-spin as pressure is increased up to 4.4kbar, where an incomplete thermal spin crossover appears at around T 1/2 = 65 K.. Quenching experiments at 4.4 kbar have shown that the incomplete character of the conversion is a consequence of slow kinetics. Relatively sharp spin transition takes place at T 1/2 = 106, 152 and 179 K, as pressure attains 5.6, 8.6 and 10.5 kbar, respectively.