Interatomic Auger transitions in transition-metal oxides

Interatomic L3(M)M23(M)V(O) and L3(M)V(O)V(O) Auger transitions of some transition-metal oxides are reported for the first time. The interatomic mode of decay becomes progressively more dominant (relative to the intra-atomic mode) as the metal d level gets depleted or as the oxidation state of the metal increases. The usefulness of interatomic Auger transitions in studying oxidation of metals has been examined.

A novel investigation of vapor-phase charge-transfer complexes of halogens with n-donors by electron energy loss spectroscopy

Complexes of I2 with diethyl ether and triethylamine and of Br, with diethyl ether have been investigated in the vapor phase for the first time by employing electron energy loss spectroscopy. Besides the CT bands, blue-shifted vacuum-UV bands of the halogens have been assigned; the amine-I, system appears to exhibit two CT bands,associated with two different excited states of the complex.

Structural origin of set-reset processes in Ge15Te83Si2 glass investigated using in situ Raman scattering and transmission electron microscopy

We report here that the structural origin of an easily reversible Ge15Te83Si2 glass can be a promising candidate for phase change random access memories. In situ Raman scattering studies on Ge15Te83Si2 sample, undertaken during the amorphous set and reset processes, indicate that the degree of disorder in the glass is reduced from off to set state. It is also found that the local structure of the sample under reset condition is similar to that in the amorphous off state. Electron microscopic studies on switched samples indicate the formation of nanometric sized particles of c-SiTe2 structure. ©2009 American Institute of Physics

In Situ Phase Separation Following Dehydration in Bimetallic Sulfates: A Variable-Temperature X-Ray Diffraction Study

Phase separation resulting in a single-crystal-single-crystal transition accompanied by a polycrystalline phase following the dehydration of hydrated bimetallic sulfates [Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O and K4Cd3-(SO4)(5)center dot 3H(2)O] has been investigated by in situ variable-temperature single-crystal X-ray diffraction. With two examples, we illustrate the possibility of generating structural frameworks following dehydration in bimetallic sulfates, which refer to the possible precursor phases at that temperature leading to the mineral formation. The room-temperature structure of Na2Mn1.167(SO4)(2)S0.33O1.167 center dot 2H(2)O is trigonal, space group R (3) over bar. On heating the crystal in situ on the diffractometer, the diffraction images display spherical spots and concentric rings suggesting phase separation, with the spherical spots getting indexed in a monoclinic space group, C2/c. The structure determination based on this data suggests the formation of Na2Mn(SO4)(2). However, the diffraction images from concentric rings could not be indexed. In the second example, the room-temperature structure is determined to be K4Cd3(SO4)(5)center dot 3H(2)O, crystallizing in a monoclinic space group, P2(1)/n. On heating the crystal in situ, the diffraction images collected also have both spherical spots and diffuse rings. The spherical spots could be indexed to a cubic crystal system, space group P2(1)3, and the structure is K4Cd3(SO4)(3). The possible mechanism for the phase transition in the dehydration regime resulting in this remarkable single-crystal to single-crystal transition with the appearance of a surrogate polycrystalline phase is proposed.

Phase transition in malonic acid: An infrared study

Malonic acid is shown to undergo an interesting phase transition at 360 K when the two non-equivalent cyclic hydrogen-bonded dimers present in the low-temperature phase become equivalent.

Barium hexaferrite (M-phase) exhibiting superstructure

Barium hexaferrite (M-phase) prepared by the flux method is found to exhibit \checkmark 3 \ut \times \checkmark 3 \ut superstructure similar to barium hexaaluminate.

Unusual effects of anisotropic bonding in Cu(II) and Ni(II) oxides with K2NiF4 structure

Geometric constraints present in A2BO4 compounds with the tetragonal-T structure of K2NiF4 impose a strong pressure on the B---OII---B bonds and a stretching of the A---OI---A bonds in the basal planes if the tolerance factor is t congruent with RAO/√2 RBO < 1, where RAO and RBO are the sums of the A---O and B---O ionic radii. The tetragonal-T phase of La2NiO4 becomes monoclinic for Pr2NiO4, orthorhombic for La2CuO4, and tetragonal-T′ for Pr2CuO4. The atomic displacements in these distorted phases are discussed and rationalized in terms of the chemistry of the various compounds. The strong pressure on the B---OII---B bonds produces itinerant σ*x2−y2 bands and a relative stabilization of localized dz2 orbitals. Magnetic susceptibility and transport data reveal an intersection of the Fermi energy with the d2z2 levels for half the copper ions in La2CuO4; this intersection is responsible for an intrinsic localized moment associated with a configuration fluctuation; below 200 K the localized moment smoothly vanishes with decreasing temperature as the d2z2 level becomes filled. In La2NiO4, the localized moments for half-filled dz2 orbitals induce strong correlations among the σ*x2−y2 electrons above Td reverse similar, equals 200 K; at lower temperatures the σ*x2−y2 electrons appear to contribute nothing to the magnetic susceptibility, which obeys a Curie-Weiss law giving a μeff corresponding to S = 1/2, but shows no magnetic order to lowest temperatures. These surprising results are verified by comparison with the mixed systems La2Ni1−xCuxO4 and La2−2xSr2xNi1−xTixO4. The onset of a charge-density wave below 200 K is proposed for both La2CuO4 and La2NiO4, but the atomic displacements would be short-range cooperative in mixed systems. The semiconductor-metallic transitions observed in several systems are found in many cases to obey the relation Ea reverse similar, equals kTmin, where varrho = varrho0exp(−Ea/kT) and Tmin is the temperature of minimum resistivity varrho. This relation is interpreted in terms of a diffusive charge-carrier mobility with Ea reverse similar, equals ΔHm reverse similar, equals kT at T = Tmin.

Thermal expansion and a new phase transition in pyroelectric LiKSO4

Single crystal macroscopic thermal expansion coefficient measurements have been made on uniaxial lithium potassium sulphate crystal both along and normal to the six fold axis, employing Fizeau’s interferometer method. Measurements were made in the range of −120°C to 500°C. The results show that lithium potassium sulphate exhibits two major anomalies in its expansion coefficients around −95°C and 422°C respectively, the one at −95°C has been observed for the first time. The nature of dimensional changes of the crystal at the upper and lower transition points are opposite in nature. The crystal shows considerable lattice anisotropy. Megaw’s tilt concept has been invoked to explain the relative magnitudes of expansion coefficients alonga andc directions. Structural features responsible for the absence of ferroelectricity in this crystal have been pointed out.

Synthesis, Structural Characterization and Formation Mechanism of Ferroelectric Bismuth Vanadate Nanotubes

We report the synthesis and structural characterization of ferroelectric bismuth vanadate (Bi2VO5.5) (BVO) nanotubes within the nanoporous anodic aluminum oxide (AAO) templates via sol-gel method. The as-prepared BVO nanotubes were characterized by X-ray powder diffraction (XRD), Scanning Electron Microscope (SEM), High-Resolution Transmission Electron Microscope (HRTEM) and the stoichiometry of the nanotubes was established by energy-dispersive X-ray spectroscopy (EDX). Postannealed (675 degrees C for 1 h), BVO nanotubes were a polycrystalline and the XRD studies confirmed the crystal structure to be orthorhombic. The uniformity in diameter and length of the nanotubes as reveled by the TEM and SEM suggested that these were influenced to a guest extent by the thickness and pore diameter of the nanoporous AAO template. EDX analysis demonstrated the formation of stoichiometric Bi2VO5.5 phase. HRTEM confirmed that the obtained BVO nanotubes were made up of nanoparticles of 5-9 nm range. The possible formation mechanism of nanotubes was elucidated.

High Lithium Storage in Mixed Crystallographic Phase Nanotubes of Titania and Carbon-Titania

Morphology and electrochemical performance of mixed crystallographic phase titania nanotubes for prospective application as anode in rechargeable lithium ion batteries are discussed. Hydrothermally grown nanotubes of titania (TiO2) and carbon-titania (C-TiO2) comprise a mixture of both anatase and TiO2 (B) crystallographic phases. The first cycle capacity (at Current rate = 10 mAg(-1)) for bare TiO2 nanotubes was 355 mAhg(-1) (approximately 1.06 Li), which is higher than both the theoretical capacity (335 mAhg(-1)) and the reported values for pure anatase and TiO2 (B) nanotubes. Higher capacity is attributed to it combination of the presence of mixed crystallographic phases of titania and trivial size effects. The surface area of bare TiO2 nanotubes was very high at 340 m(2) g(-1). C-TiO2 nanotubes showed a slightly lower first-cycle specific capacity of 307 mAhg(-1), but the irreversible capacity loss in the first cycle decreased by half compared to bare TiO2 nanotubes. The C-TiO2 nanotubes also showed a better rate capability, that is, higher capacities compared to bare TiO2 nanotubes in the Current range 0.1-2 Ag-1. Enhanced rate capability in the case of C-TiO2 is attributed to the efficient percolation of electrons as well its to the decrease in the anatase phase.

Unusual structural stability and ligand induced alterations in oligomerization of a galectin

Abstract L-14, a 14-kDa S-type lectin shows the jelly roll tertiary structural fold akin to legume lectins yet, unlike them, it does not dissociate on thermal unfolding. In the absence of ligand L-14 displays denaturation transitions corresponding to tetrameric and octameric entities. The presence of complementary ligand reduces the association of L-14, which is in stark contrast with legume lectins where no alterations in quaternary structures are brought about by saccharides. From the magnitude of the increase in denaturation temperature induced by disaccharides the binding constants calculated from differential scanning calorimetry are comparable with those extrapolated from titration calorimetry indicating that L-14 interacts with ligands essentially in the folded state.

Evidence of an intermediate phase in ternary Ge7Se93-xSbx glasses

The compositional dependence of thermal properties, such as glass transition temperature (T-g), non-reversing enthalpy change (Delta H-NR) and the specific heat capacity change (Delta C-p) of melt quenched Ge7Se93-xSbx (21 a parts per thousand currency sign x a parts per thousand currency sign 31) glasses, has been studied using alternating differential scanning calorimetry (ADSC) which is analogous to modulated differential scanning calorimetry (MDSC). The glass transition temperature, T-g, which is a measure of global connectivity of the glass, has been found to increase with the addition of Sb. In addition, a change in slope has been observed in the composition dependence of T-g at an average coordination aOE (c) r > = 2.40. The experimentally observed compositional variation of glass transition temperature, has been compared with the theoretical predictions from the stochastic agglomeration theory (SAT) and has been found to be consistent. Further, a narrow thermally reversing window is seen in the compositional variation of the relaxation enthalpy (Delta H-NR), which is centered around aOE (c) r > = 2.40. The change in specific heat capacity (Delta C-p) at T-g is also found to exhibit a distinct minima at aOE (c) r > = 2.40, suggesting that the structural rearrangements for the liquid in the glass transition region are minimized around aOE (c) r > = 2.4.

Effect of oxygen partial pressure on the structural and optical properties of dc reactive magnetron sputtered molybdenum oxide films

Molybdenum oxide films (MoO3) were deposited on glass and crystalline silicon substrates by sputtering of molybdenum target under various oxygen partial pressures in the range 8 × 10−5–8 × 10−4 mbar and at a fixed substrate temperature of 473 K employing dc magnetron sputtering technique. The influence of oxygen partial pressure on the composition stoichiometry, chemical binding configuration, crystallographic structure and electrical and optical properties was systematically studied. X-ray photoelectron spectra of the films formed at 8 × 10−5 mbar showed the presence of Mo6+ and Mo5+ oxidation states of MoO3 and MoO3−x. The films deposited at oxygen partial pressure of 2 × 10−4 mbar showed Mo6+ oxidation state indicating the films were nearly stoichiometric. It was also confirmed by the Fourier transform infrared spectroscopic studies. X-ray diffraction studies revealed that the films formed at oxygen partial pressure of 2 × 10−4 mbar showed the presence of (0 k 0) reflections indicated the layered structure of α-phase MoO3. The electrical conductivity of the films decreased from 3.6 × 10−5 to 1.6 × 10−6 Ω−1 cm−1, the optical band gap of the films increased from 2.93 to 3.26 eV and the refractive index increased from 2.02 to 2.13 with the increase of oxygen partial pressure from 8 × 10−5 to 8 × 10−4 mbar, respectively.

Glass transitions in arsenic-selenium glasses

Glaiis transitions of As-Se glasses have been investigated over a wide range of compositions by using differential scanning calorimetry. The variation of Tg with composition has been interpreted on the basis of a bond-lattice model.

Quantum phase analysis of 1D superconducting quantum dot lattice using extended Bose-Hubbard model

We have obtained the quantum phase diagram of a one-dimensional superconducting quantum dot lattice using the extended Bose-Hubbard model for different commensurabilities. We describe the nature of different quantum phases at the charge degeneracy point. We find a direct phase transition from the Mott insulating phase to the superconducting phase for integer band fillings of Cooper pairs. We predict explicitly the presence of two kinds of repulsive Luttinger liquid phases, besides the charge density wave and superconducting phases for half-integer band fillings. We also predict that extended range interactions are necessary to obtain the correct phase boundary of a one-dimensional interacting Cooper system. We have used the density matrix renormalization group method and Abelian bosonization to study our system.