A short, formal synthesis of (+/-)-2-pupukeanone

A short approach to (+/-)-2-pupukeanone, starting from 2,6-dimethylcyclohexenone employing a combination of Michael-Michael reaction and an intramolecular rhodium carbenoid C-H insertion as key reactions, is described.

Topological phases, Majorana modes and quench dynamics in a spin ladder system

We explore the salient features of the `Kitaev ladder', a two-legged ladder version of the spin-1/2 Kitaev model on a honeycomb lattice, by mapping it to a one-dimensional fermionic p-wave superconducting system. We examine the connections between spin phases and topologically non-trivial phases of non-interacting fermionic systems, demonstrating the equivalence between the spontaneous breaking of global Z(2) symmetry in spin systems and the existence of isolated Majorana modes. In the Kitaev ladder, we investigate topological properties of the system in different sectors characterized by the presence or absence of a vortex in each plaquette of the ladder. We show that vortex patterns can yield a rich parameter space for tuning into topologically non-trivial phases. We introduce and employ a new topological invariant for explicitly determining the presence of zero energy Majorana modes at the boundaries of such phases. Finally, we discuss dynamic quenching between topologically non-trivial phases in the Kitaev ladder and, in particular, the post-quench dynamics governed by tuning through a quantum critical point.

Growth mechanism of phases by interdiffusion and atomic mechanism of diffusion in the molybdenum-silicon system

Tracer diffusion coefficients are calculated in different phases in the Mo-Si system from diffusion couple experiments using the data available on thermodynamic parameters. Following, possible atomic diffusion mechanism of the species is discussed based on the crystal structure. Unusual diffusion behaviour is found in the Mo(5)Si(3) and Mo(3)Si phases, which indicate the nature of defects present on different sublattices. Further the growth mechanism of the phases is discussed and morphological evolution during interdiffusion is explained. (C) 2011 Elsevier Ltd. All rights reserved.

Icosahedral quasicrystalline and hexagonal approximant phases in the Al-Mn-Be alloy system

We report the formation of a primitive icosahedral quasicrystal with increased stability in Al Mn-Be alloys close to the compound Al15Mn13Be2, by melt spinning and injection casting. The crystal structure of this compound was unknown. We show that in as-cast as well as heat treated condition the intermetallic phase H1 has a hexagonal structure with lattice parameters a = 1.2295 run and c = 2.4634 nm. The space group is P6(3)/mmc In the injection-cast samples, the quasicrystal coexists with another closely related hexagonal phase H2 with a = 1.2295 nm and c = 1.2317 nm with a possible space group of P6/mmm. This phase exhibits specific orientation relationships with the icosahedral quasicrystal given by [0001](hex)//2f(QC) and [01 (1) over bar0](hex)//5f(QC) where 2f(QC) and 5f(QC) represent twofold and fivefold axes respectively. Electron diffraction patterns from both phases exhibit a close resemblance to the quasicrystalline phase. It is shown that the H1 phase is closely related to mu-Al4Mn with the same e parameter while the a parameter is reduced by tau. Following Kreiner and Franzen, it is postulated that both structures (H1 and H2) can be understood by a simple hexagonal packing of I13 clusters.

Investigation of short-time isomerization dynamics in p-nitroazobenzene from resonance Raman intensity analysis

Resonance Raman (RR) spectra are presented for p-nitroazobenzene dissolved in chloroform using 18 excitation Wavelengths, covering the region of (1)(n --> pi*) electronic transition. Raman intensities are observed for various totally symmetric fundamentals, namely, C-C, C-N, N=N, and N-O stretching vibrations, indicating that upon photoexcitation the excited-state evolution occurs along all of these vibrational coordinates. For a few fundamentals, interestingly, in p-nitroazobenzene, it is observed that the RR intensities decrease near the maxima of the resonant electronic (1)(n --> pi*) transition. This is attributed to the interference from preresonant scattering due to the strongly allowed (1)(pi --> pi*) electronic transition. The electronic absorption spectrum and the absolute Raman cross section for the nine Franck-Condon active fundamentals of p-nitroazobenzene have been successfully modeled using Heller's time-dependent formalism for Raman scattering. This employs harmonic description of the lowest energy (1)(n --> pi*) potential energy surface. The short-time isomerization dynamics is then examined from a priori knowledge of the ground-state normal mode descriptions of p-nitroazobenzene to convert the wave packet motion in dimensionless normal coordinates to internal coordinates. It is observed that within 20 fs after photoexcitation in p-nitroazobenzene, the N=N and C-N stretching vibrations undergo significant changes and the unsubstituted phenyl ring and the nitro stretching vibrations are also distorted considerably.

Synthesis of LiCo1-xNixO2 from a low temperature solution combustion route and characterization

Nickel substituted lithium-cobalt oxides, LiCo1-xNixO2 (0 < x < 0.4), have been synthesized in a very short time by a solution combustion method at 350 degreesC using diformyl hydrazine as a fuel. Pure phases with hexagonal lattice structure have been obtained. These compounds facilitate reversible insertion/extraction of Li+ ions with good discharge capacity between 3.0 and 4.4 V versus Li/Li+. Results of the studies by powder X-ray diffraction, scanning electron microscopy, cyclic voltammetry, galvanostatic charge-discharge cycling and ac impedance measurements are presented. (C) 2002 Elsevier Science B.V. All rights reserved.

Vertical thermal structure of the atmosphere during active and weak phases of convection over the north Bay of Bengal: Observation and model results

Owing to the lack of atmospheric vertical profile data with sufficient accuracy and vertical resolution, the response of the deep atmosphere to passage of monsoon systems over the Bay of Bengal. had not been satisfactorily elucidated. Under the Indian Climate Research Programme, a special observational programme called 'Bay of Bengal Monsoon Experiment' (BOBMEX), was conducted during July-August 1999. The present study is based on the high-resolution radiosondes launched during BOBMEX in the north Bay. Clear changes in the vertical thermal structure of the atmosphere between active and weak phases of convection have been observed. The atmosphere cooled below 6 km height and became warmer between 6 and 13 km height. The warmest layer was located between 8 and 10 km height, and the coldest layer was found just below 5 km height. The largest fluctuations in the humidity field occurred in the mid-troposphere. The observed changes between active and weak phases of convection are compared with the results from an atmospheric general circulation model, which is similar to that used at the National Centre for Medium Range Weather Forecasting, New Delhi. The model is not able to capture realistically some important features of the temperature and humidity profiles in the lower troposphere and in the boundary layer during the active and weak spells.

Calcium ruthenates: Determination of Gibbs energies of formation using electrochemical cells

Metallic Ru has been found to coexist separately with CaO, RuO2, and the interoxide phases, Ca2RuO4, Ca3Ru2O7, and CaRuO3, present along the pseudobinary system CaO-RuO2. The standard Gibbs energies of formation (Df((ox))G(o)) of the three calcium ruthenates from their component oxides have been measured in the temperature range 925-1350 K using solid-state cells with yttria-stabilized zirconia as the electrolyte and Ru+RuO2 as the reference electrode. The standard Gibbs energies of formation (Deltaf((ox))G(o)) of the compounds can be represented by Ca2RuO4:Deltaf((ox))G(o)/J mol(-1)=-38,340-6.611 T (+/-120), Ca3Ru2O7 : Df((ox))G(o)/J mol(-1)=-75,910-11.26 T (+/-180), and CaRuO3 : Deltaf((ox))G(o)/J mol(-1)=-35,480-3.844 T(+/-70). The data for Ca2RuO4 corresponds to the stoichiometric composition, which has an orthorhombic structure, space group Pbca, with short c axis ("S'' form). The structural features of the ternary oxides responsible for their mild entropy stabilization are discussed. A three-dimensional oxygen potential diagram for the system Ca-Ru-O is developed as a function of composition and temperature from the results obtained. Using the Neumann-Kopp rule to estimate the heat capacity of the ternary oxides relative to their constituent binary oxides, the standard enthalpies of formation of the three calcium ruthenates from the elements and their standard entropies at 298.15 K are evaluated. (C) 2003 The Electrochemical Society.

Evolution of metastable phases during crystallization of pulsed laser deposited amorphous Al–Fe films

Amorphous thin films of different Al–Fe compositions were produced by plasma/vapor quenching during pulsed laser deposition. The chosen compositions Al72Fe28, Al40Fe60, and Al18Fe82 correspond to Al5Fe2 and B2-ordered AlFe intermetallic compounds and α–Fe solid solution, respectively. The films contained fine clusters that increased with iron content. The sequences of phase evolution observed in the heating stage transmission electron microscopy studies of the pulsed laser ablation deposited films of Al72Fe28, Al40Fe60, and Al18Fe82 compositions showed evidence of composition partitioning during crystallization for films of all three compositions. This composition partitioning, in turn, resulted in the evolution of phases of compositions richer in Fe, as well as richer in Al, compared to the overall film composition in each case. The evidence of Fe-rich phases was the B2 phase in Al72Fe28 film, the L12- and DO3-ordered phases in Al40Fe60 film, and the hexagonal ε–Fe in the case of the Al18Fe82 film. On the other hand, the Al-rich phases were Al13Fe4 for both Al72Fe28 and Al40Fe60 films and DO3 and Al5Fe2 phases in the case of Al18Fe82 film. We believe that this tendency of composition partitioning during crystallization from amorphous phase is a consequence of the tendency of clustering of the Fe atoms in the amorphous phase during nucleation. The body-centered cubic phase has a nucleation advantage over other metastable phases for all three compositions. The amorphization of Al18Fe82 composition and the evolution of L12 and ε–Fe phases in the Al–Fe system were new observations of this work.

Effect of spinel second phase on high temperature deformation in alumina

Constant stress compression creep experiments were carried out on high purity alumina composites with spinel contents of 8 and 30%, corresponding to a situation with isolated and interconnected second phases. The creep experiments were conducted over a stress and temperature range of 10 to 150 MPa and 1623 to 1723 K, respectively. Analysis of the experimental data indicated that the variation in spinel content did not have any influence on high temperature deformation in the composite. The spinel phase retards grain growth, and this may enhance superplasticity in alumina-spinel composites.

Studies on n=2 Aurivillius phases: structure of the series Bi3-xLaxTiNbO9 (0 <= x <= 1)

The crystal structures of the solid solutions of Bi3-xLaxTiNbO9 (0 less than or equal to x less than or equal to 1) have been analyzed by powder X-ray diffraction with supporting evidence from selected area electron diffraction (SAD). The structure of the starting member (x = 0) is verified to be in the orthorhombic space group A2(1) am while the end member (x = 1) is determined to crystallize in the centrosymmetric orthorhombic space group Pmcb. The structure of x = 1 phase is solved by ab initio powder diffraction. The intermediate compositions belong to the space group A2(1) am as confirmed by Rietveld refinements. Rietveld refinements on all the compositions reveal that the La3+ ion is disordered only in the A site and not in the [Bi2O2](2+) layer. The tilt in the Ti/NbO6 octahedra decreases with increasing x. (C) 2003 Elsevier B.V. All rights reserved.

A Note On The Effect Of Short And Long Laminar Separation-Bubbles On Desinent Cavitation

Earlier desinent cavitation studies on a 1/8 caliber ogive by one of the authors (J. W. H.) showed a sudden change in the magnitude of the desinent cavitation number at a critical velocity. In the present work it is shown by means of oil-film flow visualization that below the critical velocity a long laminar separation bubble exists whereas above the critical velocity the laminar separation bubble is short. Thus the desinent cavitation characteristics of a 1/8 caliber ogive are governed by the nature of the viscous flow around the body.

An Investigation into the Dependence of the Arc Voltage on the Parameters of the Short-Circuit Current and the Design of the Vacuum Interrupter

The vacuum interrupter is extensively employed in the medium voltage switchgear for the interruption of the short-circuit current. The voltage across the arc during current interruption is termed as the arc voltage. The nature and magnitude of this arc voltage is indicative of the performance of the contacts and the vacuum interrupter as a whole. Also, the arc voltage depends on the parameters like the magnitude of short-circuit current, the arcing time, the point of opening of the contacts, the geometry and area of the contacts and the type of magnetic field. This paper investigates the dependency of the arc voltage on some of these parameters. The paper also discusses the usefulness of the arc voltage in diagnosing the performance of the contacts.

Synthesis of new (Bi, La)(3)MSb(2)O(11) phases (M = Cr, Mn, Fe) with KSbO(3)-type structure and their magnetic and photocatalytic properties

Synthesis and structure of new (Bi, La)(3)MSb(2)O(11) phases (M = Cr, Mn, Fe) are reported in conjunction with their magnetic and photocatalytic properties. XRD refinements reflect that Bi(3)CrSb(2)O(11), Bi(2)LaCrSb(2)O(11), Bi(2)LaMnSb(2)O(11) and Bi(2)LaFeSb(2)O(11) adopt KSbO(3)-type structure (space group, Pn (3) over bar). The structure can be described through three interpenetrating networks where the first is the (M/Sb)O(6) octahedral network and other two are the identical networks having Bi(6)O(4) composition. The magnetic measurements on Bi(2)LaCrSb(2)O(11) and Bi(2)LaMnSb(2)O(11) show paramagnetic behaviour with magnetic moments close to the expected spin only magnetic moments of Cr(+3) and Mn(+3). The UV-Visible diffuse reflectance spectra are broad and indicate that these materials possess a bandgap of similar to 2 eV. The photocatalytic activity of these materials has been investigated by degrading Malachite Green (MG) under exposure to UV light.