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Three new metal chalcogenides have been identified in MnN-1(Gd2-xInx)SN+2 with N = 3, 4, and 5 via a flux-growth synthesis. All compounds crystallize in the same space group of orthorhombic Cmcm with cell constants: Mn2GdInS5 (1), a = 3.789(1) Å, b = 12.411(1) Å, and c = 15.489(1) Å; Mn3Gd2S6 (2), a = 3.778(1) Å, b = 12.505(2) Å, and c = 19.114(2) Å; Mn4Gd2S7 (3), a = 3.769(1) Å, b = 12.466(2) Å, and c = 22.289(3) Å. Compounds 1-3 form a homologous series through the modulation of the MnS unit, whose structures represent a complete system of the corresponding lillianites (N1,N2L) of 3,3L, 4,4L and 5,5L. The gradually wider slabs formed in the series result in a monotonic increase along the c dimensions from 1 to 3. Crystal 3 is the first to achieve a predicted structure of 5,5L. Mn2GdInS5 (1) displays a weak antiferromagnetic (AFM) ordering at 10 K and the Weiss constant (θ) of -0.76 K. Mn2Gd1.5In0.5S5 (1a), an isostructure of 1, shifts the AFM transition temperature to 12 K and possesses a slightly larger θ constant of -6.06 K. Mn4Gd2S7 (3), featuring the thickest slabs in this series, shows a significant antiferromagnetic behavior beginning at a high temperature of 70 K and has a largest θ constant of -40.25 K. A small amount of impurity α-Gd2S3 with an AFM transition temperature around 4 K was characterized in sample 3, which does not interfere with the magnetic ordering of 3 at much higher temperatures. These magnetic chalcogenides display band gaps of 1.66 eV for 1, 1.75 eV for 1a, and 1.44 eV for 3.
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In the present work we use Raman microscopy to investigate the size effect of spin-phonon coupling in antiferromagnetic Cr2O3 nanoparticles. The peculiarities of the dependency of the phonon wave number on temperature (with a relatively weak peak at 293 cm(-1)) can be attributed to the spin-phonon coupling. The variation with temperature of the spin-phonon mode develops when the antiferromagnetic state is near the ordering temperature of the Cr spins. The observations can be reasonably well interpreted by describing the order parameter. A shift in frequency is caused by a strong spin-phonon interaction in Cr2O3. The obtained s-ph coefficients are found to be consistent with the strain, where raising the strain results in weakening of the s-ph coupling.
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Variations in the electronic structure and structural distortion in multiferroic DyMnO(3) were probed by synchrotron x-ray diffraction, lifetime-broadening-suppressed x-ray absorption spectroscopy (XAS), and ab initio electronic structure calculations. The refined x-ray diffraction data enabled an observation of a diminished local Jahn-Teller distortion of Mn sites within MnO(6) octahedra in DyMnO(3) on applying the hydrostatic pressure. The intensity of the white line in Mn K-edge x-ray absorption spectra of DyMnO(3) progressively increased with the increasing pressure. With the increasing hydrostatic pressure, the absorption threshold of an Mn K-edge spectra of DyMnO(3) shifted toward a greater energy, whereas the pre-edge line slightly shifted to a smaller energy. We provide the spectral evidence for the pressure-induced bandwidth broadening for manganites. The intensity enhancement of the white line in Mn K-edge spectra is attributed to a diminished Jahn-Teller distortion of MnO(6) octahedra in compressed DyMnO(3). A comparison of the pressure-dependent XAS spectra with the ab initio electronic structure calculations and full calculations of multiple scattering using the code FDMNES shows the satisfactory agreement between experimental and calculated Mn K-edge spectra.
RESUMO
In the rich phase diagram of NaxCoO2, x=0.71 enjoys special stability and is called the Curie-Weiss metal due to its anomalous properties. Similarly, x=0.84 prepared from high temperature melt is a special end point beyond which the system phase separates. Using synchrotron x-ray diffraction on single crystals, we discovered sqrt[12]a and sqrt[13]a superlattice structures which we interpret as the ordering of Na (vacancy) clusters. These results lead to a picture of coexisting local moments and itinerant carriers and form the first step towards understanding the many anomalous properties of cobaltates.
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The crystallographic and magnetic behaviors of (Tb1-xNax)MnO3-y (0
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The distribution of the bismuth atoms over the cation sites in the 2212 Bi-Sr-Ca-Cu-O superconductor has been determined by anomalous scattering synchrotron crystallography. The analysis of reflection pairs measured at wavelengths of 0.9243 and 0.9600 angstrom shows a delocalization of the bismuth atoms over the calcium and strontium sites. The "mixed" plane between the CuO(2) layers contains 6.0(1.4) percent bismuth (where the number in brackets represents the statistical standard deviation derived from the least-squares refinement of the data), and a much smaller amount of strontium than often assumed. The strontium deficiency is charge-compensated by the creation of electron holes in the CuO(2) layer. The result supports the view that neither extra oxygen nor overlap of the bismuth 6p and copper 3d bands is needed to account for the holes, which are an essential feature of the superconductivity mechanism.