Pressure-induced enhancement of tc above 150 k in hg-1223

The recently discovered homologous series HgBa(2)Can-1 Cun O2n+2+delta possesses remarkable properties. A superconducting transition temperature, T(c), as high as 133 kelvin has been measured in a multiphase Hg-Ba-Ca-Cu-O sample and found to be attributable to the Hg-1223 compound. Temperature-dependent electrical resistivity measurements under pressure on a (> 95%) pure Hg-1223 phase are reported. These data show that T(c) increases steadily with pressure at a rate of about 1 kelvin per gigapascal up to 15 gigapascals, then more slowly and reaches a T(c) = 150 kelvin, with the onset of the transition at 157 kelvin, for 23.5 gigapascals. This large pressure variation (as compared to the small effects observed in similar compounds with the optimal T(c)) strongly suggests that higher critical temperatures could be obtained at atmospheric pressure.     

Spontaneous Magnetic Ordering in the Fullerene Charge-Transfer Salt (TDAE)C60

The zero-field muon spin relaxation technique has been used in the direct observation of spontaneous magnetic order below a Curie temperature (T(c)) of approximately 16.1 kelvin in the fullerene charge-transfer salt (tetrakisdimethylaminoethylene)C(60) [(TDAE)C(60)]. Coherent ordering of the electronic magnetic moments leads to a local field of 68(1) gauss at the muon site at 3.2 kelvin (parentheses indicate the error in the last digit). Substantial spatially inhomogeneous effects are manifested in the distribution of the local fields, whose width amounts to 48(2) gauss at the same temperature. The temperature evolution of the internal magnetic field below the freezing temperature mirrors that of the saturation magnetization, closely following the behavior expected for collective spin wave (magnon) excitations. The transition to a ferromagnetic state with a T(c) higher than that of any other organic material is now authenticated.     

Ultrasonic shear wave velocities of MgSiO3 perovskite at 8 GPa and 800 K and lower mantle composition

Ultrasonic interferometric measurements of the shear elastic properties of MgSiO3 perovskite were conducted on three polycrystalline specimens at conditions up to pressures of 8 gigapascals and temperatures of 800 kelvin. The acoustic measurements produced the pressure (P) and temperature (T) derivatives of the shear modulus (G), namely ( partial differentialG/ partial differentialP)T = 1.8 +/- 0.4 and ( partial differentialG/ partial differentialT)P = -2.9 +/- 0.3 x 10(-2) gigapascals per kelvin. Combining these derivatives with the derivatives that were measured for the bulk modulus and thermal expansion of MgSiO3 perovskite provided data that suggest lower mantle compositions between pyrolite and C1 carbonaceous chondrite and a lower mantle potential temperature of 1500 +/- 200 kelvin.     

Organic molecular soft ferromagnetism in a fullerene c60

The properties of an organic molecular ferromagnet [C(60)TDAE(0.86); TDAE is tetrakis(dimethylamino)ethylene] with a Curie temperature ;T(c) = 16.1 kelvin are described. The ferromagnetic state shows no remanence, and the temperature dependence of the magnetization below ;T(c) does not follow the behavior expected of a conventional ferromagnet. These results are interpreted as a reflection of a three-dimensional system leading to a soft ferromagnet.     

Elasticity of single-crystal MgO to 8 gigapascals and 1600 kelvin

The cross pressure (P) and temperature (T) dependence of the elastic moduli (Cij) of single-crystal samples of periclase (MgO) from acoustic wave travel times was measured with ultrasonic interferometry: partial differential2C11/ partial differentialP partial differentialT = (-1.3 +/- 0.4) x 10(-3) per kelvin; partial differential2C110/ partial differentialP partial differentialT = (1. 7 +/- 0.7) x 10(-3) per kelvin; and partial differential2C44/ partial differentialP partial differentialT = (-0.2 +/- 0.3) x 10(-3) per kelvin. The elastic anisotropy of MgO decreases with increasing pressure at ambient temperature, but then increases as temperature is increased at high pressure. An assumption of zero cross pressure and temperature derivatives for the elastic moduli underestimates the elastic anisotropy and overestimates the acoustic velocities of MgO at the extrapolated high-pressure and high-temperature conditions of Earth's mantle.     

Orientational and Magnetic Ordering of Buckyballs in TDAE-C60

Spin ordering in the low-temperature magnetic phase is directly linked to the orientational ordering of C(60) molecules in organically doped fullerene derivatives. Electron spin resonance and alternating current susceptometry measurements on tetrakis(dimethylamino)ethylene-C(60) (TDAE-C(60)) (Curie temperature T(c) = 16 kelvin) show a direct coupling between spin and merohedral degrees of freedom. This coupling was experimentally demonstrated by showing that ordering the spins in the magnetic phase imprints a merohedral order on the solid or, conversely, that merohedrally ordering the C(60) molecules influences the spin order at low temperature. The merohedral disorder gives rise to a distribution of pi-lectron exchange interactions between spins on neighboring C(60) molecules, suggesting a microscopic origin for the observed spinglass behavior of the magnetic state.     

C60 rotation in the solid state: dynamics of a faceted spherical top

The rotational dynamics of C(60) in the solid state have been investigated with carbon-13 nuclear magnetic resonance ((13)C NMR). The relaxation rate due to chemical shift anisotropy (1/9T1(CSA)(1)) was precisely measured from the magnetic field dependence of T(1), allowing the molecular reorientational correlation time, tau, to be determined. At 283 kelvin, tau = 9.1 picoseconds; with the assumption of diffusional reorientation this implies a rotational diffusion constant D = 1.8 x 10(10) per second. This reorientation time is only three times as long as the calculated tau for free rotation and is shorter than the value measured for C(60) in solution (15.5 picoseconds). Below 260 kelvin a second phase with a much longer reorientation time was observed, consistent with recent reports of an orientational phase transition in solid C(60). In both phases tau showed Arrhenius behavior, with apparent activation energies of 1.4 and 4.2 kilocalories per mole for the high-temperature (rotator) and low-temperature (ratchet) phases, respectively. The results parallel those found for adamantane.     

"Debye-Scherrer Ellipses" from 3D fullerene polymers: An anisotropic pressure memory signature

High-pressure studies on fullerenes have previously shown the existence of one- and two-dimensional (2D) polymerized C60 structures. Synchrotron radiation measurements, performed on C60 samples quenched from 13 gigapascals and 820 kelvin, yield unambiguous proof for the existence of a three-dimensional (3D) polymerized C60 derivative. Moreover, unusual ellipsoidal Debye-Scherrer diffraction patterns are observed, which shows that the giant anisotropic deformation induced by the nonhydrostatic compression is retained in the quenched samples. The multiple bonding possibilities of the highly symmetrical C60 allow the retention (down to ambient pressure) of the deformation, a phenomenon reported previously only under high pressure.     

Order-disorder transition in polycrystalline c60 films

High-resolution Raman spectroscopy of polycrystalline films of C(60) deposited under ultrahigh-vacuum conditions show that the spectrum below 244 +/- 3 kelvin consists of a superposition of two components whose relative contributions are temperature-dependent. The spectrum of the more intense of the two components is similar to that obtained for air- or oxygen-exposed samples of C(60) at room temperature, whereas the spectrum above 244 +/- 3 kelvin corresponds to one previously reported for oxygen-free samples of C(60). The results may indicate an order-disorder phase transition involving the percolation of a cluster of C(60) molecules engaged in coherent Raman scattering.     

Two Calorimetrically Distinct States of Liquid Water Below 150 Kelvin

Vapor-deposited amorphous solid and hyperquenched glassy water were found to irreversibly transform, on compression at 77 kelvin, to a high-density amorphous solid. On heating at atmospheric pressure, this solid became viscous water (water B), with a reversible glass-liquid transition onset at 129 +/- 2 kelvin. A different form of viscous water (water A) was formed by heating the uncompressed vapor-deposited amorphous solid and hyperquenched liquid water. On thermal cycling up to 148 kelvin, water B remained kinetically and thermodynamically distinct from water A. The occurrence of these two states, which do not interconvert, helps explain both the configurational relaxation of water and stress-induced amorphization.     

Temperatures in Earth's Core Based on Melting and Phase Transformation Experiments on Iron

Experiments on melting and phase transformations on iron in a laser-heated, diamond-anvil cell to a pressure of 150 gigapascals (approximately 1.5 million atmospheres) show that iron melts at the central core pressure of 363.85 gigapascals at 6350 +/- 350 kelvin. The central core temperature corresponding to the upper temperature of iron melting is 6150 kelvin. The pressure dependence of iron melting temperature is such that a simple model can be used to explain the inner solid core and the outer liquid core. The inner core is nearly isothermal (6150 kelvin at the center to 6130 kelvin at the inner core-outer core boundary), is made of hexagonal closest-packed iron, and is about 1 percent solid (MgSiO(3) + MgO). By the inclusion of less than 2 percent of solid impurities with iron, the outer core densities along a thermal gradient (6130 kelvin at the base of the outer core and 4000 kelvin at the top) can be matched with the average seismic densities of the core.     

Order and Disorder in C60 and KxC60 Multilayers: Direct Imaging with Scanning Tunneling Microscopy

Monolayer and multilayer structures of C(60), a high temperature van der Waals solid, have been studied with scanning tunneling microscopy. Structures grown on GaAs(110) at 300 kelvin and at elevated temperatures show significantly different morphologies because of balances between thermodynamics and kinetics. Condensation onto stepped surfaces demonstrates preferred bonding and nucleation at step edges. Detailed studies of potassium incorporation in crystalline C(60) show highly ordered structures in the K(3)C(60) metallic state but disordered non-metallic structures for high potassium concentrations.     

The structure of the c60 molecule: x-ray crystal structure determination of a twin at 110 k

Single-crystal x-ray diffraction methods were used to determine the crystal and molecular structure of C(60) buckminsterfullerene. At 110 kelvin C(60) is cubic, apparent Laue symmetry m3m, but it exhibits noncrystallographic systematic extinctions indicative of a twin in which I(hkl) and I(khl) are superimposed. In fact, C(60) crystallizes with four molecules in space group [See equation in the PDF file] of the cubic system (Laue symmetry m3) with lattice constant a = 14.052(5) angstroms (A) at 110 kelvin. The twin components are equal. A given component, which has crystallographically imposed symmetry [See equation in the PDF file] displays an ordered structure of a truncated icosahedron. The five independent C=C bonds that join C(6) rings average 1.355(9) A; the ten independent C-C bonds that join C(6) and C(5) rings average 1.467(21) A. The mean atom-to-atom diameter of the C(60) molecule is 7.065(3) A. The molecules are very tightly packed in the crystal structure, with intermolecular C...C distances as short as 3.131(7) A.     

Tunneling Spectroscopy of M3C60 Superconductors: The Energy Gap, Strong Coupling, and Superconductivity

Tunneling spectroscopy has been used to characterize the magnitude and temperature dependence of the superconducting energy gap (triangle up) for K(3)C(60) and Rb(3)C(60). At low temperature the reduced energy gap, 2triangle upkappaT(c) (where T(c) is the transition temperature) has a value of 5.3 +/- 0.2 and 5.2 +/- 0.3 for K(3)C(60) and Rb(3)C(60), respectively. The magnitude of the reduced gap for these materials is significantly larger than the value of 3.53 predicted by Bardeen-Cooper-Schrieffer theory. Hence, these results show that the pair-coupling interaction is strong in the M(3)C(60) superconductors. In addition, measurements of triangle up(T) for both K(3)C(60) and Rb(3)C(60) exhibit a similar mean-field temperature dependence. The characterization of triangle up and triangle up(T) for K(3)C(60) and Rb(3)C(60) provides essential constraints for theories evolving to describe superconductivity in the M(3)C(60) materials.     

The structure of iron in Earth's inner core

Earth's solid inner core is mainly composed of iron (Fe). Because the relevant ultrahigh pressure and temperature conditions are difficult to produce experimentally, the preferred crystal structure of Fe at the inner core remains uncertain. Static compression experiments showed that the hexagonal close-packed (hcp) structure of Fe is stable up to 377 gigapascals and 5700 kelvin, corresponding to inner core conditions. The observed weak temperature dependence of the c/a axial ratio suggests that hcp Fe is elastically anisotropic at core temperatures. Preferred orientation of the hcp phase may explain previously observed inner core seismic anisotropy.     

(RbxK1-x)3C60 Superconductors: Formation of a Continuous Series of Solid Solutions

By means of an approach that employs alkali-metal alloys, bulk single-phase (RbxK1-x)(3)C(6O) superconductors have been prepared for all x between 0 and 1. For x = 1 it is shown that the maximum superconducting fraction, which approaches 100% in sintered pellets, occurs at a Rb to C(60) ratio of 3:1. More importantly, single-phase superconductors are formed at all intermediate values of x, and it is shown that the transition temperature (T(c)) increases linearly with x in this series of materials. The formation of a continuous range of solid solutions demonstrates that the rubidium- and potassium-doped C(60) superconducting phases must be isostructural, and furthermore, suggests that the linear increase in T(c) with x results from a chemical pressure effect.     

A superconducting field-effect switch

We report here on a novel realization of a field-effect device that allows switching between insulating and superconducting states, which is the widest possible variation of electrical properties of a material. We chose C(60) as the active material because of its low surface state density and observed superconductivity in alkali metal-doped C(60). We induced three electrons per C(60) molecule in the topmost molecular layer of a crystal with the field-effect device, creating a superconducting switch operating up to 11 kelvin. An insulator was thereby transformed into a superconductor. This technique offers new opportunities for the study of superconductivity as a function of carrier concentration.     

Compressibility of M3C60 Fullerene Superconductors: Relation Between Tc and Lattice Parameter

X-ray diffraction and diamond anvil techniques were used to measure the isothermal compressibility of K(3)C(60) and Rb(3)C(60), the superconducting, binary alkali-metal intercalation compounds of solid buckminsterfullerene. These results, combined with the pressure dependence of the superconducting onset temperature T(c) measured by other groups, establish a universal first-order relation between T(c) and the lattice parameter a over a broad range, between 13.9 and 14.5 angstroms. A small secondorder intercalate-specific effect was observed that appears to rule out the participation of intercalate-fullerene optic modes in the pairing interaction.     

High-throughput synthesis of zeolitic imidazolate frameworks and application to CO2 capture

A high-throughput protocol was developed for the synthesis of zeolitic imidazolate frameworks (ZIFs). Twenty-five different ZIF crystals were synthesized from only 9600 microreactions of either zinc(II)/cobalt(II) and imidazolate/imidazolate-type linkers. All of the ZIF structures have tetrahedral frameworks: 10 of which have two different links (heterolinks), 16 of which are previously unobserved compositions and structures, and 5 of which have topologies as yet unobserved in zeolites. Members of a selection of these ZIFs (termed ZIF-68, ZIF-69, and ZIF-70) have high thermal stability (up to 390 degrees C) and chemical stability in refluxing organic and aqueous media. Their frameworks have high porosity (with surface areas up to 1970 square meters per gram), and they exhibit unusual selectivity for CO2 capture from CO2/CO mixtures and extraordinary capacity for storing CO2: 1 liter of ZIF-69 can hold approximately 83 liters of CO2 at 273 kelvin under ambient pressure.     

Dynamical Signature of the Mott-Hubbard Transition in Ni(S,Se)2

The transition metal chalcogenide Ni(S,Se)2 is one of the few highly correlated, Mott-Hubbard systems without a strong first-order structural distortion that normally cuts off the critical behavior at the metal-insulator transition. The zero-temperature (T) transition was tuned with pressure, and significant deviations were found near the quantum critical point from the usual T1/2 behavior of the conductivity characteristic of electron-electron interactions in the presence of disorder. The transport data for pressure and temperature below 1 kelvin could be collapsed onto a universal scaling curve.