Low-temperature and high-pressure Raman and x-ray studies of pyrochlore Tb2Ti2O7: Phonon anomalies and possible phase transition

We have carried out temperature- and pressure-dependent Raman and x-ray measurements on single crystals of Tb2Ti2O7. We attribute the observed anomalous temperature dependence of phonons to phonon-phonon anharmonic interactions. The quasiharmonic and anharmonic contributions to the temperature-dependent changes in phonon frequencies are estimated quantitatively using mode Grüneisen parameters derived from pressure-dependent Raman experiments and bulk modulus from high-pressure x-ray measurements. Further, our Raman and x-ray data suggest a subtle structural deformation of the pyrochlore lattice at ~9 GPa. We discuss possible implications of our results on the spin-liquid behavior of Tb2Ti2O7.

Theoretical description of time-resolved pump/probe photoemission in TaS2: a single-band DFT+DMFT(NRG) study within the quasiequilibrium approximation

In this work, we theoretically examine recent pump/probe photoemission experiments on the strongly correlated charge-density-wave insulator TaS2.We describe the general nonequilibrium many-body formulation of time-resolved photoemission in the sudden approximation, and then solve the problem using dynamical mean-field theory with the numerical renormalization group and a bare density of states calculated from density functional theory including the charge-density-wave distortion of the ion cores and spin-orbit coupling. We find a number of interesting results: (i) the bare band structure actually has more dispersion in the perpendicular direction than in the two-dimensional planes; (ii) the DMFT approach can produce upper and lower Hubbard bands that resemble those in the experiment, but the upper bands will overlap in energy with other higher energy bands; (iii) the effect of the finite width of the probe pulse is minimal on the shape of the photoemission spectra; and (iv) the quasiequilibrium approximation does not fully describe the behavior in this system.

NMR relaxation study of disorder in the mixed system BP x GPI(1-x) and the low temperature transition from classical to quantum rotation

1H NMR spin-lattice relaxation time (T1) studies have been carried out in the temperature range 100 K to 4 K, at two Larmor frequencies 11.4 and 23.3 MHz, in the mixed system of betaine phosphate and glycine phosphite (BPxGPI(1-x)), to study the effects of disorder on the proton group dynamics. Analysis of T1 data indicates the presence of a number of inequivalent methyl groups and a gradual transition from classical reorientations to quantum tunneling rotations. At lower temperatures, microstructural disorder in the local environments of the methyl groups, result in a distribution in the activation energy (Ea) and the torsional energy gap (E01). For certain values of x, the magnetisation recovery shows biexponential behaviour at lower temperatures.

Characterization of alinite cements through X-ray diffraction and mas 29Si NMR studies

Alinite cements have been synthesized using mining and steel plant wastes and pulverized fuel ash (fly ash) as raw materials and a clinkering temperature of 1150°C. The cements possess hydration characteristics comparable to those of portland cements. X-ray diffraction studies on these samples confirm the presence of alinite as the predominant phase. MAS 29Si NMR spectra have been used to distinguish alinite and alite cements. While both show resonances characteristic of Q° type silicate species, the portland cements exhibit three distinct peaks corresponding to three inequivalent SiO4 units present, while alinite shows a single sharp peak corresponding to the unique Si position.

X-ray absorption spectra of niobium dichalcogenides and their first-row transition-metal intercalates

X-ra!. K-absorption spectra of niobium in niobium dichalcogenides. namely NbS, and NbSe, and their first-row transition-metal intercalates Mi P 3N bSz (M = Cr. Mn. Fe. Co. Ni) and Ml#,NbSe2 (M = Fe. CO). have been measured together with those in niobium metal. The spectra of these materials are \er? similar to one another. They reflect the transitions to the partially filled niobium d band with some p character. A bariety of x-ray absorption nearedge structures (XASES) associated with the K edges of intercalated atoms are also presented and discussed.

Synthesis, Characterization, and Photocatalytic Properties of ZrMo2O8

ZrMo2O8 was synthesized via two routes, namely, the traditional solid-state method and the solution combustion method. The compounds were characterized by powder X-ray diffraction, UV−visible spectroscopy, scanning electron microscopy, and transmission electron microscopy. The crystals belong to a trigonal crystal system, space group P 1c (No. 163) with a = 10.1391(6) Å, c = 11.7084(8) Å, and Z = 6. The band gap of the compounds was around 2.7 eV, and DFT calculations suggest the indirect nature of the band gap. The irregular MoO4 tetrahedra create a dipole and inhibit the process of electron−hole recombination, thereby making the material photoactive. The photocatalytic activity of the compounds prepared by both routes has been investigated for the degradation of various dyes under UV irradiation, and this showed the specificity of the compounds towards the degradation of non-anthraquinonic dyes.

Ultrafine powders of SrTiO3 from the hydrothermal preparation and their catalytic activity in the photolysis of water

Ultrafine powders of SrTiO3 are prepared at 100–150°C by the hydrothermal method, starting from TiO2·xH2O gel and Sr(OH)2 and H2O-isopropanol mixed solvent as the medium, The X-ray diffractograms of the powder show line broadening. The minimum crystallite size obtained ranges from 5 to 20nm with 20% H2O-80% C3H7OH as the reaction medium, as estimated from X-ray half-peak widths and TEM studies. The electron diffraction results indicate high concentration of lattice defects in these crystallites. The optical spectra of the particle suspensions in water show that the absorption around the band gap is considerably broadened, together with the appearance of maxima in the far ultraviolet. Aqueous suspensions of SrTiO3 powders, as such, do not produce H2 or O2 on UV irradiation. After coating with rhodium, H2 and O2 are evolved on illumination. However, the turn over number of O2 is lower than the stoichiometrically expected values from the corresponding values of H2. No correlation of the photocatalytic activity with surface area is observed. The activity of Rh-SrTiO3 slowly deteriorates with extended period of irradiation.

A Magnetic Susceptibility Study of Spin-state Transitions in Rare-earth TrioxocobaItates( III)

Rare-earth trioxocobaltates(lll), Ln[CoO,], with Ln = Pr, Nd, Tb, Dy. and Yb exhibit low-spin to high-spin transitions of cobalt characterised by a maximum in the Ax-l against temperature plots where Ax is the cobalt contribution to the magnetic susceptibility. The susceptibility behaviour is distinct from that of La[CoO,] which shows a plateau in the x-I-T curve accompanied by a structural transition. The temperature at which the AX- I-T curve shows a maximum increases with the decrease in the size of the rare-earth ion. The susceptibility behavior of solid solutions of La,,Nd,CoO, has been investigated to see how the behaviour characteristic of Nd[CoO,] changes to that of La[CoO,].

Synthesis, characterization and photocatalytic activity of MxCe1-xVO4 (M = Li, Ca and Fe)

Non-stoichiometric substituted cerium vanadates, MxCe1-xVO4 (M = Li, Ca and Fe), were synthesized by solid-state reactions. The crystal structure was analyzed by powder X-ray diffraction and it exhibits a tetragonal zircon Structure, crystallizing in the space group I4(1)/amd with a = 7.3733(4) and c = 6.4909(4) angstrom and Z = 4. Particle sizes were in the range of 600-800 nm, as observed by scanning electron microscopy. The thermal analysis of the compounds showed phase stability up to 1100 degrees C. The UV diffuse reflectance spectra indicated that the compounds have band gaps in the range of 2.6-2.9 eV. The photocatalytic activity of these Compounds was investigated for the first time for the degradation of different dyes, and organics, the oxidation of cyclohexane and the hydroxylation of benzene. The degradation of dyes was modeled using the Langmuir-Hinshelwood kinetics, while the oxidation of cyclohexane and hydroxylation of benzene were modeled using a free radical mechanism and a series reaction mechanism, respectively.

7Li Spin-flip satellites in the EPR sectra of NH3+ -doped LiKSO4

EPR spectra of lithium potassium sulfate doped with NH3+ have been recorded at 9.05 GHz. A pair of satellites can be seen symmetrically situated on either side of the main lines. The separation of the satellite lines from the main line corresponds to the 7Li NMR frequency. The distance of the interacting 7Li nucleus from the unpaired electron in NH3+ is estimated to be 3.29 Å.

Molecularly adsorbed oxygen on metals: electron spectroscopic studies

Oxygen is shown to adsorb molecularly on gold as well as on Ag and Pt. UV and X-ray photoelectron spectroscopy and Auger electron spectroscopy have been employed to investigate electron states of molecularly adsorbed oxygen.

Hole Pairing In Antiferromagnetically Correlated Layered Oxides

We have considered a two-band Hubbard model having interlaced Cu-3d(x2−y2) and O-2p(x, y) orbitals representing the CuO2 square planes. Simple CuO2 -cluster calculation suggests that the additional holes created by doping stay mainly on oxygen. Motion of an oxygen hole interlacing with the antiferromagnetically correlated background of copper spins, creates a string of high energy spin configuration of finite length giving mass renormalization. Another hole of opposite spin can now anneal this string tension providing a triangular pairing potential for large pair momentum. The latter implies unusual Bose condensation of the wake-bound compact Bose-like pairs on a non-zero momentum shell. Effect of disorder favouring condensation at the mobility edge is pointed out.

Highly Enhanced Thermopower in Two-Dimensional Electron Systems at Millikelvin Temperatures

We report experimental observation of an unexpectedly large thermopower in mesoscopic two-dimensional (2D) electron systems in GaAs/AlGaA heterostructures at sub-Kelvin temperatures and zero magnetic field. Unlike conventional nonmagnetic high-mobility 2D systems, the thermopower in our devices increases with decreasing temperature below 0.3 K, reaching values in excess of 100 mu V/K, thus exceeding the free electron estimate by more than 2 orders of magnitude. With support from a parallel study of the local density of states, we suggest such a phenomenon to be linked to intrinsic localized states and many-body spin correlations in the system.

Electron-electron interactions in polyacetylene

Experimental evidence for strong electron-electron interactions in polyacetylene is presented. These include (i) observation of a dipole forbidden state below the optical gap, (ii) observation of negative spin densities at sites at which noninteracting models predict zero spin density (iii) vanishing optical gap, in the infinite chain limit, in the closely related symmetrical linear cyanine dyes. To correctly explain these features it is necessary to solve correlated model Hamiltonians. Using diagrammatic valence bond method model exact solutions of correlated models of finite-size systems can be obtained and various physical properties of the low-lying states can be computed. These properties, when extrapolated to the infinite chain limit explain many of the experimental features observed in polyacetylene.

Ce1-xRuxO2-delta (x=0.05, 0.10): A New High Oxygen Storage Material and Pt, Pd-Free Three-Way Catalyst

Nanocrystalline Ce1-xRuxO2-delta (x = 0.05 and 0.10) of 8-10 nm sizes have been synthesized by hydrothermal method using melamine as complexing agent. Compounds have been characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and energy-dispersive X-ray analysis (EDX) and their structures have been refined by the Rietveld method.The compounds crystallize in fluorite structure and the composition is Ce1-xRuxO2-x/2 where Ru is in +4 state and Ce is in mixed-valence (+3, +4) state. Substitution of Ru4+ ion in CeO2 activated the lattice oxygen. Ce1-xRuxO2-x/2 reversibly releases 0.22[O] and 0.42[O] for x = 0.05 and 0.10, respectively, which is higher than the maximumpossible OSC of 0.22 [O] observed for Ce0.50Zr0.50O2. Utilization of Higher OSC of Ce1-xRuxO2-delta (x = 0.05 and 0.10) is also reflected in terms of low-temperature CO oxidation with these catalysts, both in the presence and absence of feed oxygen. The Ru4+ ion acts as an active center for reducing molecules (CO, hydrocarbon ``HC'') and oxide ion vacancy acts as an active center for O-2 and NO, leading to low-temperature NO conversion to N-2. Thus due to Ru4+ ion, Ce1-xRuxO2-delta is not just a high oxygen storage material but also shows high activity toward CO, hydrocarbon ``HC'' oxidation, and NO reduction by CO at low temperature with high N-2 selectivity for three-way catalysis.