Concentration-dependent NMR and conductivity studies of (PEG)(x)NH4ClO4

Films of (PEG)(x)NH4ClO4 (x = 5 to 1000) were prepared and characterized. The physical properties are observed to be a sensitive function of concentration. Hygroscopicity increases as salt content increases. Conductivity peaks (sigma = 2.7 x 10(-6) S/cm) at x = 46. The H-1 NMR line width has a minimum at x = 46, while that of Cl-35 monotonically increases with salt concentration, indicating that the complex is essentially a protonic conductor.

Evidence for correlation effects in Sr2RuO4 from resonant and x-ray photoemission spectroscopy

We study the electronic structure of Sr2RuO4, a noncuprate layered superconductor (T-c=0.93 K), using electron spectroscopy. X-ray photoemission spectroscopy shows that the single particle occupied density of states (DOS) is in fair agreement with the calculated DOS. However, resonant photoemission spectroscopy across the Ru 4p-4d threshold establishes the existence of a correlation satellite to the Ru 4d band. The results indicate substantial charge-transfer character at the Fermi level, with on-site correlations U-dd comparable in magnitude to the Ru-O hopping integral, like the cuprates.

Exceptionally long crystal formation from 4-(3-bromopropyloxy)salicylaldehyde. X-ray crystallographic investigation

Unusually long (>14 cm) crystalline needles grow from 4-(3-bromopropyloxy)salicylaldehyde 1 presumably as a consequence of Br ... Br interactions; the powdered form of 1 shows one order of magnitude greater SHG activity realtive to urea.

Low temperature synthesis and hcaracterization of Ag2S1-x Tez(O

A low-temperature route for the synthesis of Ag2S,Ag2Te and their solid solutions Ag2S1-xTex(0 less-than-or-equal-to x less-than-or-equal-to 1) is reported. Ag2S is prepared by the direct addition of silver nitrate solution to thiourea, while Ag2Te is prepared by reacting silver nitrate solution with tellurium in nitric acid and subsequently reducing it with hydrazine hydrate. The solid solutions of Ag2S and Ag2Te are obtained by the addition of nitrate solutions of silver and tellurium to thiourea followed by its reduction with hydrazine hydrate. The method enables the synthesis of low-temperature crystalline phase of Ag2S1-xTex solid solutions. The powder X-ray diffraction studies suggest that the solid solutions of compositions x < 0.3 have a phase akin to alpha-Ag2S and those with compositions x > 0.6 are similar to alpha-Ag2Te. In the intermediate range of compositions (x = 0.4 and 0.5), the solid solutions are found to be mixtures of alpha-Ag2S and alpha-Ag2Te phases which transform totally to alpha-Ag2S phase on prolonged annealing at about 473 K.

Monte Carlo simulation of low temperature phase diagrams of YBa2Cu3O6+x

We report the results of Monte Carlo simulation of oxygen ordering in the oxygen deficient portion (x<0.5) of YBa2Cu3O6+x at low temperatures. We find qualitative agreement among cluster - variation, Monte Carlo and transfer matrix methods. However, low temperature and ground state simulations clearly indicate the presence of a tetragonal phase. There is also evidence for two second order phase transition lines separating the tetragonal and the �double cell� ortho II phase. The effect of decreasing the inter-chain repulsion on oxygen ordering has also been investigated.

Giant magnetoresistance in lanthanum strontium yttrium manganese oxides (La(1-x)Sr(x-z)YuMnO(3))

Electron transport and magnetic properties of several compositions of the La1-xSx-zYzMnO3 system have been investigated in order to explore the effect of yttrium substitution on the magnetoresistance and related properties of these manganates. Yttrium substitution lowers the T-c and the insulator-metal transition temperature, while increasing the peak resistivity. A comparison of the properties of La1-xSrx-zYzMnO3 with the corresponding La1-xCax-zYzMnO3 compositions shows that the observed properties can be related to the average size of the A-site cations.

H-1 MAS NMR study of protonic conduction in layered HNbWO6 center dot xH(2)O (x=1.5, 0.5)

H-1 Magic Angle Spinning (MAS) NMR of layered HNbWO6 . xH(2)O (x = 1.5, 0.5) is carried out at room temperature and at various spinning speeds (1-12 kHz). Results on the fully hydrated sample (x = 1.5) are consistent with the model of diffusion of H3O+ ions within the layers. In the partially dehydrated sample (x = 0.5) an exchange between the distinctly present cage protons and H3O+ protons leads to protonic conduction.

Dielectric function and optical conductivity of TiOx (0.8

Reflection electron energy-loss spectra are reported for the family of compounds TiOx over the entire homogeneity range (0.8 < a: < 1.3). The spectra exhibit a plasmon feature on the low-energy side, while several interband transitions are prominent at higher energies. The real and imaginary parts of dielectric functions and optical conductivity for these compounds are determined using the Kramers-Kronig analysis. The results exhibit systematic behavior with varying oxygen stoichiometry.

Studies in crystal engineering: Effect of fluorine substitution in crystal packing and topological photodimerization of styryl coumarins in the solid state

Styryl coumarins generally yield centrosymmetric (alpha-mode, anti-HT) photodimers when subjected to irradiation in the solid state, However, the substitution of fluorine dramatically alters the packing mode and steers the molecules 4-(4-fluorostyryl)coumarin 1 and 4-(2-fluorostyryl)coumarin 2 to form a stereospecific photodimer, beta-mode, syn-HH across the styrenic double bond (yield 78-85%). The stereochemistry of the photodimer 2a has been established by X-ray crystallography. There is no evidence for the presence of C-H ... F interactions. The true nature of the weak atom-atom interactions called into play when fluorine is substituted is not clear, It is observed that the fluoro substituted compounds have greater crystal density than the corresponding unsubstituted ones.

Solid state amorphization in binary Ti---Ni, Ti---Cu and ternary Ti---Ni---Cu system by mechanical alloying

An amorphous phase has been synthesized by mechanical alloying in a planetary mill over a nickel content range of 10�70 at.% in the Ti---Ni system and a copper content range of 10�50 at.% in the Ti---Cu system. In the case of ternary Ti---Ni---Cu alloys the glass-forming composition range has been found to be given by x = 10�20 for Ti60Ni40 ? xCux, x = 10 � 30 for Ti50Ni50 ? xCux and x = 10 � 40 for Ti40Ni60 ? xCux alloys. The difficulty in the amorphization of copper-rich compositions is explained in the light of enthalpy composition diagrams calculated for the ternary solid solution and the amorphous phase.

Solid-state photobehaviour and crystal packing of o-chlorobenzylidene-DL-piperitone: influence of molecular topology on photobehaviour

C17H19ClO, M(r) = 274.7, triclinic, P1BAR, a = 11.154 (3), b = 12.685 (2), c = 12.713 (2) angstrom, alpha = 100.68 (1), beta = 113.58 (1), gamma = 104.50 (2)-degrees, V = 1511.1 (6) angstrom3, Z = 4, D(m) = 1.22, D(x) = 1.215 Mg m-3, Cu K-alpha, lambda = 1.5418 angstrom, mu = 2.16 mm-1, F(000) = 584, T = 293 K, R = 0.057 for 3481 observed reflections. The title compound is photostable in the crystalline state and lattice-energy calculations have been employed to rationalize the photobehaviour. The well-known beta-steering ability of the chloro group is not operative in this system as there are no Cl...Cl interactions in the crystal lattice. All five benzylidene-DL-piperitone structures so far studied are alpha-packed and the molecular topology appears to be a deciding factor even in the presence of steering groups.

Raman Spectroscopy of the Charge Transfer Complex (TTF)x C60 Br8

We report Raman studies on powder samples of the charge transfer complex (TTF)(x)C60Br8 at room temperature. The phonons show considerable softening with respect to the frequencies observed in the Raman spectrum of solid C60Br8. The strongest mode at 1464 cm(-1) in C60Br8 is red shifted to a doublet with peaks at 1414 and 1421 cm(-1), implying an average phonon softening Delta omega of -47 cm(-1). A comparison with the phonon softening of the corresponding A(g)(2) mode in alkali-doped C-60 (Delta omega similar to -36 cm(-1) for A(6)C(60), A = K, Rb or Cs) suggests that 8 electrons are transferred per C60Br8 molecule in the charge transfer complex. The mode at 503 cm(-1) in C60Br8 is shifted upwards, similar to that in A(6)C(60) compounds.

Solid-state miscibility gap and thermodynamics of the system BaO–SrO

A solid-state miscibility gap in the pseudo-binary system BaO-SrO is delineated by X-ray diffraction studies on samples equilibrated either in vacuum or under flowing inert gas at temperatures between 1073 and 1423 K. For the SrxBa1-xO solid solution an asymmetric phase boundary, characterized by a critical temperature of 1356 (+/-4) K and composition x=0.55 (+/-0.008), is obtained. Thermodynamic mixing properties of the solid solution, derived from the experimental phase boundary compositions and temperatures, can be represented by the expression: Delta G(E)=x(1-x){33 390-7.09T)x+(29 340-6.23T)(1-x)} J mol(-1)It is necessary to include excess entropy terms to obtain a good fit to the experimental data. The chemical spinodal curve is computed from the thermodynamic parameters

Structural and Dielectric-Properties Of A Novel BI2O3-(1-X)WO3-XCUO Solid-Solution

A novel solid solution in the system Bi-W-Cu-O has been synthesized and its structural and dielectric properties studied. The solid solution Bi2O3-(1-x)WO3-xCuO exists up to x = 0.7; the solid solutions up to x = 0.65 are orthorhombic but stabilize in tetragonal structure in a narrow range around x = 0.7. The solid solutions are non-centrosymmetric and exhibit ferroelectric behaviour similar to their parent phase Bi2WO6. The Curie point of the solid solution is found to decrease with increase in x.

Variation of Cu-O charge-transfer energies in YBa2Cu3O7-x thin films studied by photoemission spectroscopy

It is pointed out that the change in the oxidation state of Cu in YBa2CU3O7-x with increasing x vitiates the trend in the Cu(2p) satellite intensity and hence the Cu-O charge-transfer energy. When Y is partly replaced by Ca, however, the satellite intensity and T(c) decrease with the increase in Ca content or hole concentration, just as in other cuprates.