Study of the reactions of pyridinium poly(hydrogen fluoride) with some ternary oxides

The products of the reaction of pyridinium poly(hydrogen fluoride), PPHF, with KIO3, Na2SnO3, NaBiO3, K2CrO4, Na2MoO4 and Na2WO4 were KIO2F2; Na2SnF6; NaHF2, BiF3; K3CrF6, KHF2, (PyH)(3)CrF6; NaHF2, (PyH)(2)MoO2F4.2NaHF(2); and (PyH)(2)WO2F4.2NaHF(2), respectively, while KClO3, KBrO3 and KlO(4) react with complete decomposition to form KHF2 as the fluorinated product. This differential reactivity and mode of reaction has been discussed in terms of the oxidation state of the central atom, the nature and strength of the bonds and the complex behaviour of the formed intermediate or fluorinated products that undergo complexation or solvation with pyridine and/or hydrogen fluoride.

Synthesis and studies on pyridinium chlorofluoro complexes of indium and bismuth

Pyridinium trichlorotrifluoroindate, (C5H5NH)(3)InCl3F3, and pyridinium trichlorofluorobismuthate, C5H5NHBiCl3F, have been synthesised by the reaction of pyridinium poly(hydrogen fluoride), PPHF, with InCI3 and BiCl3, respectively. These new complexes have been characterised by chemical and thermal analysis, NMR (H-1 and F-19) and infrared spectroscopy, and powder X-ray diffraction methods

Unsteady laminar compressible swirling flow with massive blowing

THE study of swirling boundary layers is of considerable importance in many rotodynamic machines such as rockets, jet engines, swirl generators, swirl atomizers, arc heaters, etc. For example, the introduction of swirl in a flow acceleration device such as a nozzle in a rocket engine promises efficient mass flow control. In nuclear rockets, swirl is used to retain the uranium atoms in the rocket chamber. With these applications in mind, Back1 and Muthanna and Nath2 have obtained the similarity solutions for a low-speed three-dimensional steady laminar compressible boundary layer with swirl inside an axisymmetric surface of variable cross section. The aim of the present analysis is to study the effect of massive blowing rates on the unsteady laminar swirling compressible boundary-layer flow of an axisymmetric body of arbitrary cross section when the freestream velocity and blowing rate vary with time. The type of swirl considered here is that of a free vortex superimposed on the longitudinal flow of a compressible fluid with variable properties. The analysis is applicable to external flow over a body as well as internal flow along a surface. For the case of external flow, strong blowing can have significant use in cooling the surface of hypervelocity vehicles, particularly when ablation occurs under large aerodynamic or radiative heating, but there may not be such an important application of strong blowing in the case of internal flow. The governing partial differential equations have been solved numerically using an implicit finite difference scheme with a quasilinearization technique.3 High temperature gas effects, such as radiation, dissociation, and ionization, etc., are not investigated. The nomenclature is usually that of Ref. 4 and is listed in the full paper.

Model studies directed towards the synthesis of functionalised chiral A-ring derivatives of taxanes

Model studies, starting from the monoterpene R-carvone, directed towards the synthesis of chiral A-ring derivatives of taxanes with oxygen functionalities at C-2, 9 and 13 carbon atoms as in taxol is described.

Quantum Dots and Nanoroads of Graphene Embedded in Hexagonal Boron Nitride

The quest for novel two-dimensional materials has led to the discovery of hybrids where graphene and hexagonal boron nitride (h-BN) occur as phase-separated domains. Using first-principles calculations, we study the energetics and electronic and magnetic properties of such hybrids in detail. The formation energy of quantum dot inclusions (consisting of n carbon atoms) varies as 1/root n, owing to the interface. The electronic gap between the occupied and unoccupied energy levels of quantum dots is also inversely proportional to the length scale, 1/root n-a feature of confined Dirac fermions. For zigzag nanoroads, a combination of the intrinsic electric field caused by the polarity of the h-BN matrix and spin polarization at the edges results in half-metallicity; a band gap opens up under the externally applied ``compensating'' electric field. For armchair nanoroads, the electron confinement opens the gap, different among three subfamilies due to different bond length relaxations at the interfaces, and decreasing with the width.

Ultrasonic wave characteristics of a monolayer graphene on silicon substrate

The present work deals with an ultrasonic type of wave propagation characteristics of monolayer graphene on silicon (Si) substrate. An atomistic model of a hybrid lattice involving a hexagonal lattice of graphene and surface atoms of diamond lattice of Si is developed to identify the carbon-silicon bond stiffness. Properties of this hybrid lattice model is then mapped into a nonlocal continuum framework. Equivalent force constant due to Si substrate is obtained by minimizing the total potential energy of the system. For this equilibrium configuration, the nonlocal governing equations are derived to analyze the ultrasonic wave dispersion based on spectral analysis. From the present analysis we show that the silicon substrate affects only the flexural wave mode. The frequency band gap of flexural mode is also significantly affected by this substrate. The results also show that, the silicon substrate adds cushioning effect to the graphene and it makes the graphene more stable. The analysis also show that the frequency bang gap relations of in-plane (longitudinal and lateral) and out-of-plane (flexural) wave modes depends not only on the y-direction wavenumber but also on nonlocal scaling parameter. In the nonlocal analysis, at higher values of the y-directional wavenumber, a decrease in the frequency band gap is observed for all the three fundamental wave modes in the graphene-silicon system. The atoms movement in the graphene due to the wave propagation are also captured for all the tree fundamental wave modes. The results presented in this work are qualitatively different from those obtained based on the local analysis and thus, are important for the development of graphene based nanodevices such as strain sensor, mass and pressure sensors, atomic dust detectors and enhancer of surface image resolution that make use of the ultrasonic wave dispersion properties of graphene. (C) 2011 Elsevier Ltd. All rights reserved.

Chopped nonlinear magneto-optic rotation: A technique for precision measurements

We have developed a technique for precise measurement of small magnetic fields using nonlinear magneto-optic rotation (NMOR). The technique relies on the resonant laser beam being chopped. During the on time, the atoms are optically pumped into an aligned ground state (Delta m=2 coherence). During the off time, they freely precess around the magnetic field at the Larmor frequency. If the on-off modulation frequency matches (twice) the Larmor precession frequency, the rotation is resonantly enhanced in every cycle, thereby making the process like a repeated Ramsey measurement of the Larmor frequency. We study chopped-NMOR in a paraffin-coated Cs vapor cell. The out-of-phase demodulated rotation shows a Lorentzian peak of linewidth 85 mu G, corresponding to a sensitivity of 0.15nG/root Hz. We discuss the potential of this technique for the measurement of an atomic electric-dipole moment. Copyright (C) EPLA, 2011

Inverse surface melting in confined clusters: Ar-13 in zeolite L

Monte Carlo and molecular dynamics simulations on an Ar-13 cluster in zeolite L have been carried out at a series of temperatures to understand the rigid-nonrigid transition corresponding to the solid-liquid transition exhibited by the free Ar-13 cluster. The icosahedral geometry of the free cluster is no longer preferred when the cluster is confined in the zeolite. The root-mean-squared pair distance fluctuation, delta, exhibits a sharp, well-defined rigid-nonrigid transition at 17 K as compared to 27 K for the free cluster. Multiple peaks in the distribution of short-time averages of the guest-host interaction energy indicate coexistence of two phases.; It is shown that this transition is associated with the inner atoms becoming mobile at 17 K even while the outer layer atoms, which are in close proximity to the zeolitic wall, continue to be comparatively immobile. This may be contrasted with the melting of large free clusters of 40 or more atoms which exhibit surface melting. Guest-host interactions seem to play a predominant role in determining the properties of confined clusters. We demonstrate that the volume of the cluster increases rather sharply at 17 and 27 K respectively for the confined and the free cluster. Power spectra suggest that the motion of the inner atoms is generally parallel to the atoms which form the cage wall.

Mo3O5(OH)(2)(AsO4)2: A new solid with a structure related to beta VOPO4

Mo3O5(OH)(2)(AsO4)(2) was prepared at 100 degrees C from an aqueous solution of MoO3 containing arsenic and nitric acids. It crystallises in the monoclinic system, a = 13.024(1)Angstrom, b = 7.2974 (2) Angstrom, c = 13.281(1) Angstrom, beta = 121.124(8)degrees, Z = 4, space group C2/c. The structure was determined by Rietveld refinement from X-ray powder diffraction data. The three-dimensional structure is built up from MoO6 and MoO5OH octahedra and AsO4 tetrahedra sharing corners. The octahedra share two opposite vertices forming zigzag chains that run parallel to [10(1) over bar]. Each AsO4 tetrahedron is connected to four octahedra, two of which belong to the same chain, thus linking three chains. The resulting covalent framework is similar to that of beta VOPO4 in which one tetrahedral P site for every three is empty. The two protons are likely to be bonded to two (out of four) unshared oxygen atoms surrounding this empty site. All the Mo atoms are strongly off-centred in the octahedra; and the off-centring is disordered. The disorder is discussed in terms of Mo shifts perturbed by a disordered hydrogen bonding scheme.

Monte Carlo and molecular dynamics simulation of argon clusters andn-alkanes in the confined regions of zeolites

Geometry and energy of argon clusters confined in zeolite NaCaA are compared with those of free clusters. Results indicate the possible existence of magic numbers among the confined clusters. Spectra obtained from instantaneous normal mode analysis of free and confined clusters give a larger percentage of imaginary frequencies for the latter indicating that the confined cluster atoms populate the saddle points of the potential energy surface significantly. The variation of the percentage of imaginary frequencies with temperature during melting is akin to the variation of other properties. It is shown that confined clusters might exhibit inverse surface melting, unlike medium-to-large-sized free clusters that exhibit surface melting. Configurational-bias Monte Carte (CBMC) simulations of n-alkanes in zeolites Y and A are reported. CBMC method gives reliable estimates of the properties relating to the conformation of molecules. Changes in the conformational properties of n-butane and other longer n-alkanes such as n-hexane and n-heptane when they are confined in different zeolites are presented. The changes in the conformational properties of n-butane and n-hexane with temperature and concentration is discussed. In general, in zeolite Y as well as A, there is significant enhancement of the gauche population as compared to the pure unconfined fluid.

Origin of carrier-type reversal in Pb-Ge-Se glasses: A detailed thermal, electrical, and structural study

A long-standing and important problem in glass science has been carrier-type reversal (CTR) in semiconducting glasses. This phenomenon is exhibited by Pb-Ge-Se glasses also. It has been addressed here by carrying out detailed electrical, thermal, and spectroscopic investigations. PbxGe42-xSe58 (x = 0-20) glasses were prepared by a two stage melt-quenching process and characterized using x-ray diffraction, high-resolution electron microscropy, and energy dispersive analysis of x-rays. Thermoelectric power and high-pressure electrical resistivity have been measured. IR, Raman, and X-ray adsorption near edge structure spectroscopies have been used for examining the glass structures as well as differential scanning calorimetry (DSC) for studying the thermal properties. A structural model based on the chemical nature of the constituents has been proposed to account for the observed properties of these glasses. Effect of Pb incorporation on local structures and qualitative consequences on the energy band structures of Ge-Se glasses has been considered. The p -->n transition has been attributed to the energetic disposition of the sp(3)d(2) band of Pb atoms, which is located closely above the lone pair band of selenium. This feature makes Pb unique in the context of p -->n transition of chalcogenide glasses. The model can be extended successfully to account for the CTR behavior observed in Bi containing chalcogenide glasses also.

Reactivation kinetics of boron acceptors in hydrogenated silicon during zero bias anneal

The reactivation kinetics of passivated boron accepters in hydrogenated silicon during zero bias annealing in the temperature range of 65-130 degrees C are reported, For large annealing times and high annealing temperatures, the reactivation process follows second-order kinetics and is rate limited by a thermally activated <(H)over tilde (2)> complex formation process, For short annealing times and low annealing temperatures, the reactivation rate is found to be larger than that due to <(H)over tilde (2)> complex formation alone. We conclude that the faster reactivation is caused by the diffusion of the liberated hydrogen atoms into the bulk as well as <(H)over tilde (2)> complex formation. The effective diffusion coefficient of hydrogen is measured and found to obey the Arrhenius relation with an activation energy (1.41 +/- 0.1) eV. (C) 1997 American Institute of Physics.

First-principle description of magnonic PdnFem multilayers

Ab-initio calculations are used to determine the parameters that determine magnonic band structure of PdnFem multilayers (n = 2, m <= 8). We obtain the layer-resolved magnetization, the exchange coupling, and the magnetic anisotropy of the Pd-Fe structures. The Fe moment is 3.0 mu(B) close to the Pd layers and 2.2 mu(B) in the middle of the Fe layers. An intriguing but not usually considered aspect is that the elemental Pd is nonmagnetic, similar to Cu spacer layers in other multilayer systems. This leads to a pre-asymptotic ferromagnetic coupling through the Pd (about 40 mJ/m(2)). Furthermore, the Pd acquires a small moment due to spin polarization by neighboring Fe atoms, which translates into magnetic anisotropy. The anisotropies are large, in the range typical for L1(0) structures, which is beneficial for high-frequency applications. (C) 2011 American Institute of Physics. doi:10.1063/1.3556763]

Synthesis of Co(II), Ni(II) and Cu(II) Complexes from Schiff base Ligand and Reactivity Studies with Thermosetting Epoxy Resin

A hybrid thermosetting maleimido epoxy compound 4-(N-maleimidophenyl) glycidylether (N-MPGE) containing Co(II), Ni(II) and Cu(II) ions was prepared by curing N-MPGE and tetradentate Schiff base Co(II), Ni(II) and Cu(II) complexes. The curing polymerization reaction of N-MPGE with metal complexes as curing agents was studied. The cured samples were studied for thermal stability, chemical (acid/alkali/solvent) and water absorption resistance and homogeneity of the cured systems. The tetradentate Schiff base, 3-(Z)-2-piperazin-1-yl-ethylimino]-1,3-dihydro indol-2-one was synthesized by the condensation of Isatin (Indole-2, 3-dione) with 1-(2-aminoethyl)piperazine (AEP). Its complexes with Co(II), Ni(II) and Cu(II) have been synthesized and characterized by microanalysis, conductivity, Uv-Visible, FT-IR, TGA and magnetic susceptibility measurements. The spectral data revealed that the ligand acts as a neutral tetradentate Schiff base and coordinating through the azomethine nitrogen, two piperazine nitrogen atoms and carbonyl oxygen.

Bis(acetylacetonato-kappa 2 O,O')(pyridine-kappa N)zinc(II)

In the title compound, Zn(C5H7O2)(2)(C5H5N)], the metal atom has square-pyramidal coordination geometry with the basal plane defined by the four O atoms of the chelating acetylacetonate ligands and with the axial position occupied by the pyridine N atom. The crystal packing is characterized by a C-H...O hydrogen-bonded ribbon structure approximately parallel to 10 ].