Undoped LaFeAsO, parent compound of the newly found high-T c superconductor, exhibits a sharp decrease in the temperature-dependent resistivity at ~160 K. The anomaly can be suppressed by F doping and the superconductivity appears correspondingly, suggesting a close associate of the anomaly with the superconductivity. We examined the crystal structures, magnetic properties and superconductivity of undoped (normal conductor) and 14 at.% F-doped LaFeAsO (T c = 20 K) by synchrotron X-ray diffraction, DC magnetic measurements, and ab initio calculations to demonstrate that the anomaly is associated with a phase transition from tetragonal (P4/nmm) to orthorhombic (Cmma) phases at ~160 K as well as an antiferromagnetic transition at ~140 K. These transitions can be explained by spin configuration-dependent potential energy surfaces derived from the ab initio calculations. The suppression of the transitions is ascribed to interrelated effects of geometric and electronic structural changes due to doping by F − ions.Parent compounds to the high-T c superconductors show a rapid decrease in their electrical resistivity (ρ), which is clearly seen on the resistivity-temperature (T) curves with a kink at ~160 K (T anom ). This anomaly has been attributed to the combined effect of a crystallographic phase transition at ~160 K, and an antiferromagnetic ordering of the Fe spins at a slightly lower temperature of ~140 K [27][28][29][30][31]. Both transitions can be simultaneously suppressed by the electron or hole doping, suggesting a close association of these phase transitions with the superconductivity observed in the doped compounds.The Fe-based and the Cu-based superconductors have a common feature in that superconductivity is attained by providing itinerant electron or hole carriers to the two-dimensional transport layers containing 3d transition metal elements. However, they differ distinctly from each other in that nine 3d electrons (one hole) are involved for Cu 2+ , which forms ionic bond with oxide ions, whereas six 3d electrons participate in a more complex interplay of Fe−Fe and Fe−As bonding.In this study, we examine the crystal structures, magnetic properties and superconductivity of undoped and 14 at.% F-doped LaFeAsO (T c = 20 K) by Rietveld refinement of synchrotron X-ray diffraction, DC magnetic measurements, and ab initio calculations. We demonstrate that the undoped LaFeAsO undergoes a phase transition from tetragonal (P4/nmm) to orthorhombic (Cmma) phases at ~160 K as well as an antiferromagnetic transition at ~140 K. These transitions can be explained by spin configuration-dependent potential energy surfaces derived from the ab initio calculations. Doping by F − ions in the LaO layers suppresses both transitions, which is ascribed to interrelated effects of geometric and electronic structural changes. Our results
We report a metallic state in a nanostructured porous crystal 12CaO x 7Al2O3 by incorporating electrons in the inherent subnanometer-sized cages, in which a three-dimensionally closely packed cage structure acts as an electronic conduction path. High-density electron doping ( approximately 2 x 10(21) cm(-3)), which was achieved by a thermal treatment in Ti metal vapor at approximately 1100 degrees C, induces homogenization of the cage geometry to a symmetric state, resulting in an insulator-metal transition with a sharp enhancement of the electron drift mobility from approximately 0.1 to 4 cm(2) V(-1) s(-1). The results provide an approach for the realization of electroactive functions in materials composed only of environmentally benign elements by utilizing the appropriate nanostructures.
A new quaternary fluoroarsenide CaFeAsF with the tetragonal ZrCuSiAs-type structure composed of alternate stacking of (FeAs)delta- and (CaF)delta+ layers was synthesized. CaFeAsF is a poor metal and shows the anomaly at approximately 120 K in temperature dependence of electrical conductivity. The electron doping by the partial replacement of the iron with cobalt suppresses the anomaly and induces the bulk superconductivity (optimal Tc = 22 K for CaFe0.9Co0.1AsF), analogous to recently discovered FeAs-based superconductors. The present results suggest that CaFeAsF is a promising candidate as a parent compound for high Tc superconductors.
Isotopic ratios of radioactive releases into the environment are useful signatures for contamination source assessment. Uranium is known to behave conservatively in sea water so that a ratio of uranium trace isotopes may serve as a superior oceanographic tracer. Here we present data on the atomic 233 U/ 236 U ratio analyzed in representative environmental samples finding ratios of (0.1-3.7)Á10 À2 . The ratios detected in compartments of the environment affected by releases of nuclear power production or by weapons fallout differ by one order of magnitude. Significant amounts of 233 U were only released in nuclear weapons fallout, either produced by fast neutron reactions or directly by 233 U-fueled devices. This makes the 233 U/ 236 U ratio a promising new fingerprint for radioactive emissions. Our findings indicate a higher release of 233 U by nuclear weapons tests before the maximum of global fallout in 1963, setting constraints on the design of the nuclear weapons employed.
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