First-principles electronic structure of the delafossites ABO(2) (A=Cu, Ag, Au; B=Al, Ga, Sc, In, Y): evolution of d(10)-d(10) interactions

While bonding between d(10) atoms and ions in molecular systems has been well studied, less attention has been paid to interactions between such seemingly closed shell species in extended inorganic solids. In this contribution, we present visualizations of the electronic structures of the delafossites ABO(2) (A = Cu, Ag, Au) with particular emphasis on the nature of d(10)-d(10) interactions in the close packed plane of the coinage metal ion. We find that on going from Cu to Ag to Au, the extent of bonding between A and A increases. However, the structures (in terms of distances) of these compounds are largely determined by the strongly ionic 13,11 0 interaction and for the larger B ions Sc, In and Y, the A atoms are sufficiently well-separated that A-A bonding is almost negligible. We also analyze some interesting differences between Ag and Au, including the larger A-O covalency of the Au. The trends in electronic structure suggest that the Ag and Au compounds are not good candidate transparent conducting oxides. (C) 2002 Editions scientifiques et medicales Elsevier SAS. All rights reserved.

Correlation of Oxygen Storage Capacity and Structural Distortion in Transition-Metal-, Noble-Metal-, and Rare-Earth-Ion-Substituted CeO2 from First Principles Calculation

Oxygen storage/release (OSC) capacity is an important feature common to all three-way catalysts to combat harmful exhaust emissions. To understand the mechanism of improved OSC for doped CeO2, we undertook the structural investigation by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H-2-TPR (temperature-programmed hydrogen reduction) and density functional theoretical (DFT) calculations of transition-metal-, noble-metal-, and rare-earth (RE)-ion-substituted ceria. In this report, we present the relationship between the OSC and structural changes induced by the dopant ion in CeO2. Transition metal and noble metal ion substitution in ceria greatly enhances the reducibility of Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu, Pd, Pt, Ru), whereas rare-earth-ion-substituted Ce(1-x)A(x)O(2-delta) (A = La, Y) have very little effect in improving the OSC. Our simulated optimized structure shows deviation in cation oxygen bond length from ideal bond length of 2.34 angstrom (for CeO2). For example, our theoretical calculation for Ce28Mn4O62 structure shows that Mn-O bonds are in 4 + 2 coordination with average bond lengths of 2.0 and 3.06 angstrom respectively. Although the four short Mn-O bond lengths spans the bond distance region of Mn2O3, the other two Mn-O bonds are moved to longer distances. The dopant transition and noble metal ions also affects Ce coordination shell and results in the formation of longer Ce-O bonds as well. Thus longer cation oxygen bonds for both dopant and host ions results in enhanced synergistic reduction of the solid solution. With Pd ion substitution in Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu) further enhancement in OSC is observed in H-2-TPR. This effect is reflected in our model calculations by the presence of still longer bonds compared to the model without Pd ion doping. The synergistic effect is therefore due to enhanced reducibility of both dopant and host ion induced due to structural distortion of fluorite lattice in presence of dopant ion. For RE ions (RE = Y, La), our calculations show very little deviation of bonds lengths from ideal fluorite structure. The absence of longer Y-O/La-O and Ce-O bonds make the structure much less susceptible to reduction.

Electric and magnetic polarizabilities of hexagonal Ln(2)CuTiO(6)(Ln = Y, Dy, Ho, Er, and Yb)

We investigated the rare-earth transition-metal oxide series, Ln(2)CuTiO(6) (Ln = Y, Dy, Ho, Er, and Yb), crystallizing in the hexagonal structure with noncentrosymmetric P6(3)cm space group for possible occurrences of multiferroic properties. Our results show that while these compounds, except Ln = Y, exhibit a low-temperature antiferromagnetic transition due to the ordering of the rare-earth moments, the expected ferroelectric transition is frustrated by the large size difference between Cu and Ti at the B site. Interestingly, this leads these compounds to attain a rare and unique combination of desirable paraelectric properties with high dielectric constants, low losses, and weak temperature and frequency dependencies. First-principles calculations establish these exceptional properties result from a combination of two effects. A significant difference in the MO5 polyhedral sizes for M = Cu and M = Ti suppress the expected cooperative tilt pattern of these polyhedra, required for the ferroelectric transition, leading to relatively large values of the dielectric constant for every compound investigated in this series. Additionally, it is shown that the majority contribution to the dielectric constant arises from intermediate-frequency polar vibrational modes, making it relatively stable against any temperature variation. Changes in the temperature stability of the dielectric constant among different members of this series are shown to arise from changes in relative contributions from soft polar modes.

Microwave ECR Plasma Assisted MOCVD of Y(2)O(3) Thin Films Using Y(tod)(3) Precursor and Their Characterization

Yttrium oxide (Y(2)O(3)) thin films were deposited by microwave electron cyclotron resonance (ECR) plasma assisted metal organic chemical vapour deposition (MOCVD) process using indigenously developed metal organic precursors Yttrium 2,7,7-trimethyl-3,5-octanedionates, commonly known as Y(tod)(3) which were synthesized by an ultrasound method. A series of thin films were deposited by varying the oxygen flow rate from 1-9 sccm, keeping all other parameters constant. The deposited coatings were characterized by X-ray photoelectron spectroscopy, glancing angle X-ray diffraction and infrared spectroscopy. Thickness and roughness for the films were measured by stylus profilometry. Optical properties of the coatings were studied by the spectroscopic ellipsometry. Hardness and elastic modulus of the films were measured by nanoindentation technique. Being that microwave ECR CVD process is operating-pressure-sensitive, optimum oxygen activity is very essential for a fixed flow rate of precursor, in order to get a single phase cubic yttrium oxide in the films. To the best of our knowledge, this is the first effort that describes the use of Y(tod)(3) precursor for deposition of Y(2)O(3) films using plasma assisted CVD process.

First-order structural transition in the magnetically ordered phase of Fe(1.13)Te

Specific heat, resistivity, magnetic susceptibility, linear thermal expansion (LTE), and high-resolution synchrotron x-ray powder diffraction investigations of single crystals Fe(1+y) Te (0.06 <= y <= 0.15) reveal a splitting of a single, first-order transition for y <= 0.11 into two transitions for y >= 0.13. Most strikingly, all measurements on identical samples Fe(1.13)Te consistently indicate that, upon cooling, the magnetic transition at T(N) precedes the first-order structural transition at a lower temperature T(s). The structural transition in turn coincides with a change in the character of the magnetic structure. The LTE measurements along the crystallographic c axis display a small distortion close to T(N) due to a lattice striction as a consequence of magnetic ordering, and a much larger change at T(s). The lattice symmetry changes, however, only below T(s) as indicated by powder x-ray diffraction. This behavior is in stark contrast to the sequence in which the phase transitions occur in Fe pnictides.

Climatic fluctuations during the LIA and post-LIA in the Kumaun Lesser Himalaya, India: Evidence from a 400 y old stalagmite record

This paper presents the first stable isotope (delta O-18 and delta C-13) data of a similar to 400 years (1590-2006 AD) long annual to decadal-resolution speleothem record collected from the Indian Lesser Himalaya. The data show a variation from -2.7 to -5.9 parts per thousand in delta O-18 and -5.3 to -8.8 parts per thousand in delta C-13. The isotopic analyses indicate that the climate during this period can be divided into two stages: a wet phase during the Little Ice Age (LIA) (1590-1850 AD) and comparatively dry phase during the post-LIA after 1850 AD. However, the record also documents the minor dry events during the LIA and a wet episode after the LIA. Within the age uncertainty, the dry spells during the LIA are linked with the historical drought events in the Indian subcontinent and similar latitudes. The isotopic record is consistent with a number of previous studies in the areas influenced by the Westerlies but appears to be conflicting to the regions, dominated by the Indian Summer Monsoon (ISM). This may be due to the possible changes in the strength of Westerlies in the study area and added by negative anomaly of North Atlantic Oscillation (NAO) during the LIA. (C) 2012 Elsevier Ltd and INQUA. All rights reserved.

Base Triggered Enhancement of First Hyperpolarizability of a Keto-Enol Tautomer

This work describes the base triggered enhancement of first hyperpolarizability of a tautomeric organic molecule, namely, benzoylacetanilide (BA). We have used the hyper-Rayleigh scattering technique to measure the first hyperpolarizability (beta) of BA which exists in the pure keto form in water and as a keto-enol tautomer in ethanol. Its anion exists in equilibrium with the keto and enol forms at pH 11 in aqueous solution. The beta value of the anion form is 709 X 10(-30) esu, whereas that of the enol is 232 x 10(-3) esu and of the keto is 88 X 10(-30) esu. There is an enhancement of beta by similar to 8 times for the anion and similar to 3 times for the enol compared to the keto form. All these are achieved by altering the equilibrium between the three forms of BA by simple means. MP2 calculations reproduce the experimental trend, but the computed beta values are much lower than the measured values. DFT calculations with the standard B3LYP functional could not predict the right order in the beta values. The difference between experimental and calculated values is, perhaps, due to the fact that electron correlation effects are important in computing optical nonlinearities of large organic molecules and MP2 and B3LYP calculations done here for different forms of BA could not account for such effects adequately.

Sputter Deposited High Capacity Li2-xMnO3-y Films for Thin Film Battery Application

Lithium manganese oxide (Li2-xMnO3-y) thin films have been deposited from activated Li2MnO3 powder by radio frequency magnetron sputtering for the first time in the literature and subjected to electrochemical characterization. Physicochemical characterization by X-ray diffraction has revealed the formation of the thin films with crystallographic phase identical to that of the powder target made of Li2-xMnO3-y. The Li:Mn atomic ratio for the powder and film are calculated by X-ray photoelectron spectroscopy and it is found to be 1.6:1.0. From galvanostatic charge discharge studies, a specific discharge capacity of 139 mu Ah mu m(-1) cm(-2) was obtained when cycled between 2.00 and 3.50 V vs Li/Li+. Additionally the rate capability of the thin film electrodes was studied by subjecting the cells to charge-discharge cycling at different current densities in the range from 10 mu A cm(-2) to 100 mu A cm(-2). (C) 2013 The Electrochemical Society. All rights reserved.

Robust dielectric properties of B-site size-disordered hexagonal Ln(2)CuTiO(6) (Ln = Y, Dy, Ho, Er, and Yb)

Hexagonal Ln(2)CuTiO(6) (Ln = Y, Dy, Ho, Er, and Yb) exhibits a rare combination of interesting dielectric properties, in the form of relatively large dielectric constants (epsilon' > 30), low losses, and extremely small temperature and frequency dependencies, over large ranges of temperature and frequency Choudhury et al., Appl. Phys. Lett. 96, 162903 (2010) and Choudhury et al., Phys. Rev. B 82, 134203 (2010)], making these compounds promising as high-k dielectric materials. The authors present a brief review of the existing literature on this interesting class of oxides, complimenting it with spectroscopic data in conjunction with first-principles calculation results, revealing a novel mechanism underlying these robust dielectric properties. These show that the large size differences in Cu2+ and Ti4+ at the B-site, aided by an inherent random distribution of CuO5 and TiO5 polyhedral units, frustrates the ferroelectric instability, inherent to the noncentrosymmetric P6(3) cm space group of this system, and gives rise to the observed relatively large dielectric constant values. Additionally, the phononic contributions to the dielectric constant are dominated primarily by mid-frequency (>100 cm(-1)) polar modes, involving mainly Ti4+ 3d(0) ions. In contrast, the soft polar phonon modes with frequencies typically less than 100 cm(-1), usually responsible for dielectric properties of materials, are found to be associated with non-d(0) Cu2+ ions and to contribute very little, giving rise to the remarkable temperature stability of dielectric properties of these compounds. (C) 2014 American Vacuum Society.

Temperature-Induced Reversible First-Order Single Crystal to Single Crystal Phase Transition in Boc-gamma(4)(R)Val-Val-OH: Interplay of Enthalpy and Entropy

Crystals of Boc-gamma y(4)(R)Val-Val-OH undergo a reversible first-order single crystal to single crystal phase transition at T-c approximate to 205 K from the orthorhombic space group P22(1)2(1) (Z' = 1) to the monoclinic space group P2(1) (Z' = 2) with a hysteresis of similar to 2.1 K. The low-temperature monoclinic form is best described as a nonmerohedral twin with similar to 50% contributions from its two components. The thermal behavior of the dipeptide crystals was characterized by differential scanning calorimetry experiments. Visual changes in birefringence of the sample during heating and cooling cycles on a hot-stage microscope with polarized light supported the phase transition. Variable-temperature unit cell check measurements from 300 to 100 K showed discontinuity in the volume and cell parameters near the transition temperature, supporting the first-order behavior. A detailed comparison of the room-temperature orthorhombic form with the low-temperature (100 K) monoclinic form revealed that the strong hydrogen-bonding motif is retained in both crystal systems, whereas the non-covalent interactions involving side chains of the dipeptide differ significantly, leading to a small change in molecular conformation in the monoclinic form as well as a small reorientation of the molecules along the ac plane. A rigid-body thermal motion analysis (translation, libration, screw; correlation of translation and libration) was performed to study the crystal entropy. The reversible nature of the phase transition is probably the result of an interplay between enthalpy and entropy: the low-temperature monoclinic form is enthalpically favored, whereas the room-temperature orthorhombic form is entropically favored.

First principles study of structural stability and site preference in Co-3 (W,X)

Since the discovery 1] of gamma' precipitate (L1(2) - Co-3 (Al, W)) in the Co-Al-W ternary system, there has been an increased interest in Co-based superalloys. Since these alloys have two phase microstructures (gamma + gamma') similar to Ni-based superalloys 2], they are viable candidates in high temperature applications, particularly in land-based turbines. The role of alloying on stability of the gamma' phase has been an active area of research. In this study, electronic structure calculations were done to probe the effect of alloying in Co3W with L1(2) structure. Compositions of type Co-3(W, X), (where X/Y = Mn, Fe, Ni, Pt, Cr, Al, Si, V, W, Ta, Ti, Nb, Hf, Zr and Mo) were studied. Effect of alloying on equilibrium lattice parameters and ground state energies was used to calculate Vegard's coefficients and site preference related data. The effect of alloying on the stability of the L1(2) structure vis a vis other geometrically close packed ordered structures was also studied for a range of Co3X compounds. Results suggest that the penchant of element for the W sublattice can be predicted by comparing heats of formation of Co3X in different structures.

First principles DFT investigation Of Yttrium-decorated Boron-Nitride Nanotube: Electronic Structure and Hydrogen Storage

The electronic structure and hydrogen storage capability of Yttrium-doped BNNTs has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom prefers the hollow site in the center of the hexagonal ring with a binding energy of 0.8048eV. Decorating by Y makes the system half-metallic and magnetic with a magnetic moment of 1.0 mu(B). Y decorated Boron-Nitride (8,0) nanotube can adsorb up to five hydrogen molecules whose average binding energy is computed as 0.5044eV. All the hydrogen molecules are adsorbed with an average desorption temperature of 644.708 K. Taking that the Y atoms can be placed only in alternate hexagons, the implied wt% comes out to be 5.31%, a relatively acceptable value for hydrogen storage materials. Thus, this system can serve as potential hydrogen storage medium.