Investigations of oxide superconductors by x-ray absorption, photoemission and cognate spectroscopies

X-ray absorption spectra, X-ray photoelectron spectra and Auger spectra of cuprate superconductors are discussed. The studies establish the absence of Cu3+ for all practical purposes, but point out the importance of oxygen holes. X-ray photoelectron spectra of BaBi0.25Pb0.75O3 and related compounds are also examined.

Photoacoustic Investigation of Glass Transition in AsxTe1-x Glasses

Photoacoustic (PA) technique is used to study glass transition and temperature dependence of thermal diffusivity in AsxTe1-x glasses with 0.25 0.60. PA amplitude goes through a minimum and the phase shows a maximum at glass transition temperature Tg. The variation of thermal diffusivity with temperature shows sharp decrease near Tg. The variation of thermal diffusivity with composition shows maximum at = 0.40 for all temperatures T Tg.

Evolution of magnetic order in the system LaNi1-xMnxO3 (x < 0.10)

Magnetic susceptibility measurements on dilute solid-solutions LaNi1-xMnxO3 (x < 0.1) have been carried out. With increasing x the magnetic susceptibility behaviour changes from Pauli paramagnetic to Curie-Weiss type. The temperature coefficient of resistance (TCR) changes sign around x = 0.03 but the system seems to be metallic in terms of showing a finite extrapolated conductivity at 0 K even when x = 0.10. The x = 0.10 system shows indications of spin-glass like behaviour.

X-Ray structure of a ternary complex, copper(II)–lnosine 5-monophosphate–benzimidazole. The first example for the absence of direct metal–nucleotide interaction

The unprecedented absence of direct metal–nucleotide interaction has been observed in the X-ray structure of the ternary metal nucleotide system [Cu(bzim)(H2O)5]2+[IMP]2–·3H2O [IMP = inosine 5-monophosphate(2–), bzim = benzimidazole). The complex crystallizes in the space group P21 with a= 7.013(2), b= 13.179(9), c= 14.565(9)Å, = 94.82(4)°, and Z= 2. The structure was solved by the heavy-atom method and refined by full-matrix least squares on the basis of 1 761 observed (I? 3i) reflections to final R and R values of 0.034 and 0.036 respectively. The CuII has a distorted octahedral co-ordination with a nitrogen of the bzim ligand [Cu–N 1.947(5)Å] and three oxygens of water molecules in the basal plane [mean Cu–O 2.017(3)Å] and two more water oxygens at axial positions [Cu–O 2.194(6) and 2.732(5)Å]. The nucleotide base stacks with the bzim ligand at an average distance of 3.5 Å and an angle of 22°. In the lattice, N(7) of the base is linked to a lattice water through a hydrogen bond, while all the phosphate oxygens are involved in hydrogen bonds with co-ordinated as well as lattice water molecules. The co-ordination behaviour of IMP to CuII is compared in structures containing different -aromatic amines in order to assess the influence of the ternary ligand in complex formation. The present results indicate that, apart from the commonly observed phosphate binding, other modes of co-ordination are possible, these being influenced mainly by the -accepting properties of the ternary ligand.

Synthesis, X-ray structure and catalytic properties of a copper(II) Schiff base complex modeling the activity of the Cu-B site of dopamine beta-hydroxylase

The copper(II) complex [Cu(salgly) (bpy)] . 4H(2)O (1), where salgly is a tridentate glycinatosalicylaldimine Schiffbase Ligand, is prepared and structurally characterized. The complex is found to be catalytically active in the oxidation of ascorbic acid by dioxygen and the process is also effective in the presence of benzylamine giving benzaldehyde as a product, thus modeling the activity of the Cu-B site of dopamine beta-hydroxylase. (C) 2000 Elsevier Science S.A. All rights reserved.

Photoacoustic investigation of the optical absorption and thermal diffusivity in SixTe100−x glassesstar

The photoacoustic technique is used to determine the optical energy gap E0 of bulk SixTe100−x glasses in the glass-forming region 10 ≤ x ≤ 28. The thermal diffusivity α of these samples has also been measured. The variation of E0 and α with x is reported. It is found that E0 increases with x nearly linearly with a sharp decrease in the rate of increase beyond x = 20. The thermal diffusivity also increases with x up to x = 20 but decreases for compositions with higher values of x. The observed behaviour is explained on the basis of a chemical bond approach. It is accounted for in terms of the increase in the number of Te---Te bonds and formation of SiTe4 tetrahedra with an increase in the chalcogen content.

Nature of Pb in superconducting cuprates containing lead: A Pb L3 x‐ray absorption near‐edge spectroscopy study

X‐ray absorption near‐edge spectroscopy studies show that Pb in superconducting Tl0.5Pb0.5CaSr2Cu2O7+δ is essentially in the 4+ state while it is in the 2+ state in Pb2Sr2Ca1−xLnxCu3O8+δ.

Magnetism of Ti4+ diluted manganites La1-xPbxMn1-yTiyO3 (y <= x)

The effect of nonmagnetic Ti4+ substitution for Mn4+ on magnetic ordering of La1-xPbxMn1-yTiyO3 (x = 0.15,0.26, and 0.4; 0 less than or equal to y less than or equal to x )has been studied. The ferromagnetic transition temperature and the magnetization decrease with increasing amount of titanium. Complete substitution of Mn4+ by Ti4+, for x = y, excludes the Mn3+-O-Mn4+ double exchange. However, these compounds still show ferromagnetism if the dilution of the Mn sublattice by Ti is small enough (y less than or equal to 0.2). This ferromagnetism probably originates from a ferromagnetic Mn3+-O-Mn3+ superexchange. A thorough study of magnetic properties including AC magnetic susceptibility, magnetization, temperature dependence of coercivity and relaxation of remanent magnetization has been carried out and gives evidence of cluster spin glass behaviour for La0.6Pb0.4Mn0.6Ti0.4O3. (C) 2000 Elsevier Science B.V. All rights reserved.

ESR studies of X-irradiated strontium mixed calcium tartrate crystals

The electron spin resonance spectra of X-ray irradiated single crystals of strontium doped calcium tartrate tetrahydrate (CST) with molecular formula Ca0.88Sr0.12C4H4O6.4H(2)O grown in gels has been investigated. Only one species of free radical but with two magnetically unequivalent sites was observed at room temperature. The free radical was found to be the result of the splitting of a C-II bond adjacent to both the hydroxyl and carboxyl groups. The a factor was found to be slightly anisotropic. Couplings with two H nuclei, believed to be the proton of the OH group attached directly to the unsaturated asymmetric carbon atom and the proton attached directly to the: other asymmetric carbon atom of the molecule were observed. The principal g-values were found to be 2.0030, 2.0017, 2.0027. The principal elements of the nuclear coupling are 7.45, 6.59, 4.28 and 8.56, 7.22, 18.71 G, respectively. The radical was found to be very stable. (C) 2000 Elsevier Science Ltd. All rights reserved.

Reduction in magnetic field induced broadening of the resistive transition in laser‐deposited YBa2Cu3O7−x thin films on MgO

The magnetic field induced broadening of the normal to superconducting resistive transition of YBa2Cu3O7−x thin films laser deposited on (100) MgO substrates for field oriented parallel to the c axis is found to be significantly reduced in comparison with that found previously in single crystals and in films deposited on SrTiO3. This reduction in broadening is associated with a high density of defects which, while causing a slight decrease in Tc and an increase in the zero‐field transition width, seems to provide strong vortex pinning centers that reduce flux creep

Study of magnetic field effect on the specific heat and entropy in DyBa2Cu3O7-x

The change in the specific heat by the application of magnetic field up to 161 for high temperature superconductor system for DyBa2Cu3O7-x by Revaz et al. [23] is examined through the phenomenological Ginzburg-Landau(G-L) theory of anisotropic Type-II superconductors. The observed specific heat anomaly near T-c with magnetic field is explained qualitatively through the expression <Delta C > = (B-a/T-c) t/(1 - t)(alpha Theta(gamma)lambda(2)(m)(0)), which is the anisotropic formulation of the G-L theory in the London limit developed by Kogan and coworkers; relating to the change in specific heat Delta C for the variation of applied magnetic field for different orientations with c-axis. The analysis of this equation explains satisfactorily the specific heat anomaly near T-c and determines the anisotropic ratio gamma as 5.608, which is close to the experimental value 5.3 +/- 0.5given in the paper of Revaz et al. for this system. (C) 2010 Elsevier B.V. All rights reserved.

Electronic structure of high-Tc Ba0.6K0.4BiO3 by x-ray photoelectron spectroscopy

We have investigated the electronic structure of Ba1-xKxBiO3 (0<x<0.4) by x-ray photoelectron spectroscopy. The Bi(4f) core levels show a normal valency of +3 as in Bi2O3 and we find no evidence for the disproportionation of Bi4+ to Bi3+ and Bi5+. Instead, we find that BaBiO3 has mixed valent O2- and O1- ions. As the potassium doping is increased, the binding energy of the O2- ions in the O(1s) photoelectron spectra steadily decreases from 529.7 to 528.8 eV. The effect of lowering the O(1s) binding energy is to raise the O(2p) band towards EF and at the superconducting composition a finite density of O(2p) states is observed near EF. Similarly, the Ba(5p) binding energies decrease with potassium doping, indicating increased metallicity. The behavior of the O(1s), Ba(5p), and the valence band resembles that of all the cuprate superconductors and we conclude that in all these oxide superconductors, a hole in the (filled) O(2p) band is the carrier responsible for superconductivity, which predicts hole conduction in the Ba-K-Bi-O and Ba-Pb-Bi-O systems.

Structural and magnetic properties of Sr2Fe1+xMo1-xO6 (-1 <= x <= 0.25)

We have synthesized the solid solution Sr2Fe1+xMo1-xO6 with -1 <= x <= 0.25, the composition x=0 corresponding to the well-known double-perovskite system Sr2FeMoO6. We report structural and magnetic properties of the above system, exhibiting systematic variations across the series. These results restrict the range of models that can explain magnetism in this family of compounds, providing an understanding of the magnetic structure.