Dynamics of H-atom exchange in stable cis-dihydrogen/hydride complexes of ruthenium( II) bearing phosphine and N-N bidentate ligands

Synthesis and characterization of cis, trans-RuH(eta(2)-H-2)(PPh3)(2)(N-N)]OTf] (N-N = 2,2'-bipyridyl (bpy) 1a, 2,2'-bipyrimidine (bpm) 2a; OTf = trifluoromethane sulfonate (CF3SO3)) complexes are reported. The cis-H-2/hydride ligands are involved in H-atom site exchange between the two moieties. This dynamics was investigated by variable temperature NMR spectral studies based on which the mechanism of the exchange process was deduced. The Delta G(#) for the exchange of H-atoms between the eta(2)-H-2 and hydride ligands was determined to be around 8 and 13 kJ mol(-1), respectively, for 1a and 2a. The H-H distances (d(HH), A) in complexes 1a and 2a have been calculated from the T-1(minimum) and (1)J(H, D) and are found to be 1.07 A (slow) and 0.95 A for 1a and 1.04 A (slow) and 0.94 A for 2a, respectively. The molecular structure of 1a was determined by X-ray crystallography.

Analytical solutions for transient temperature distribution in a geothermal reservoir due to cold water injection

An analytical solution to describe the transient temperature distribution in a geothermal reservoir in response to injection of cold water is presented. The reservoir is composed of a confined aquifer, sandwiched between rocks of different thermo-geological properties. The heat transport processes considered are advection, longitudinal conduction in the geothermal aquifer, and the conductive heat transfer to the underlying and overlying rocks of different geological properties. The one-dimensional heat transfer equation has been solved using the Laplace transform with the assumption of constant density and thermal properties of both rock and fluid. Two simple solutions are derived afterwards, first neglecting the longitudinal conductive heat transport and then heat transport to confining rocks. Results show that heat loss to the confining rock layers plays a vital role in slowing down the cooling of the reservoir. The influence of some parameters, e.g. the volumetric injection rate, the longitudinal thermal conductivity and the porosity of the porous media, on the transient heat transport phenomenon is judged by observing the variation of the transient temperature distribution with different values of the parameters. The effects of injection rate and thermal conductivity have been found to be profound on the results.

Role of different factors affecting interdiffusion in Cu(Ga) and Cu(Si) solid solutions

A detailed diffusion study was carried out on Cu(Ga) and Cu(Si) solid solutions in order to assess the role of different factors in the behaviour of the diffusing components. The faster diffusing species in the two systems, interdiffusion, intrinsic and impurity diffusion coefficients, are determined to facilitate the discussion. It was found that Cu was more mobile in the Cu-Si system, whereas Ga was the faster diffusing species in the Cu-Ga system. In both systems, the interdiffusion coefficients increased with increasing amount of solute (e.g. Si or Ga) in the matrix (Cu). Impurity diffusion coefficients for Si and Ga in Cu, found out by extrapolating interdiffusion coefficient data to zero composition of the solute, were both higher than the Cu tracer diffusion coefficient. These observed trends in diffusion behaviour could be rationalized by considering: (i) formation energies and concentration of vacancies, (ii) elastic moduli (indicating bond strengths) of the elements and (iii) the interaction parameters and the related thermodynamic factors. In summary, we have shown here that all the factors introduced in this paper should be considered simultaneously to understand interdiffusion in solid solutions. Otherwise, some of the aspects may look unusual or even impossible to explain.

Stable and low resistive zinc contacts for SnS based optoelectronic devices

The contact behavior of tin mono sulfide (SnS) nanocrystalline thin films with zinc (Zn) and silver (Ag) contacts was studied. SnS films have been deposited on glass substrates by thermal evaporation technique at a growth temperature of 300 degrees C. The as-grown SnS films composed of vertically aligned nanocrystallites with a preferential orientation along the < 010 > direction. SnS films exhibited excellent chemical stoichiometry and direct optical band gap of 1.96 eV. These films also exhibited excellent Ohmic characteristics and low electrical resistivity with Zn contacts. The observed electrical resistivity of SnS films with Zn contacts is 22 times lower than that of the resistivity with Ag contacts. The interfacing analysis reveals the formation of conductive Zn-S layer between SnS and Zn as interfacial layer. (C) 2014 Elsevier B. V. All rights reserved.

Diffraction tomography from intensity measurements: an evolutionary stochastic search to invert experimental data

We develop iterative diffraction tomography algorithms, which are similar to the distorted Born algorithms, for inverting scattered intensity data. Within the Born approximation, the unknown scattered field is expressed as a multiplicative perturbation to the incident field. With this, the forward equation becomes stable, which helps us compute nearly oscillation-free solutions that have immediate bearing on the accuracy of the Jacobian computed for use in a deterministic Gauss-Newton (GN) reconstruction. However, since the data are inherently noisy and the sensitivity of measurement to refractive index away from the detectors is poor, we report a derivative-free evolutionary stochastic scheme, providing strictly additive updates in order to bridge the measurement-prediction misfit, to arrive at the refractive index distribution from intensity transport data. The superiority of the stochastic algorithm over the GN scheme for similar settings is demonstrated by the reconstruction of the refractive index profile from simulated and experimentally acquired intensity data. (C) 2014 Optical Society of America

Do stable isotopes in carbonate cement of Mio-Pleistocene Himalayan sediments record paleoecological and paleoclimatic changes?

Non-pedogenic carbonates, such as carbonate cement and nodules in the sandstones, are quite common in the terrestrial geological record. Unlike pedogenic carbonates, their stable isotope ratios lack investigations for paleo-climatic reconstructions. The present investigation therefore, explores the possibility of use of stable isotope studies of non-pedogenic carbonates from the Mb-Pleistocene Siwalik Group of sediments exposed in the Ramnagar sub-basin of the NW Himalaya. Petrographic studies reveal the dominance of micrite fabric in carbonate nodules both of pedogenic and non-pedogenic samples irrespective of specific stratigraphic unit However, calcite as cement in the sandstones shows the dominance of micrite fabric in the younger in age sediments. Seventy-two non-pedogenic carbonate samples from the carbonate nodules and cement in the Siwalik sandstones, ranging in age between similar to 1 Ma and 12.2 Ma, were analyzed for delta C-13 and delta O-18 values. The delta C-13 values vary from -24.77 parts per thousand to -1.1 parts per thousand and delta O-18 values vary from -15.34 parts per thousand to -7.81 parts per thousand. Pedogenic and non-pedogenic carbonates ranging in age between similar to 1 Ma and 6 Ma have largely similar delta C-13 values and the range of delta C-13 values indicate the dominance of C-4 type of vegetation. However, unlike pedogenic carbonates which showed the dominance of C-3 type of vegetation pre- 7 Ma on the basis of delta C-13 -depleted isotopic values (Singh et al., 2011), delta C-13 values are largely enriched in the corresponding aged non-pedogenic carbonates revealing no information on specific type of vegetation. Likewise, paleoprecipitational reconstructions from delta O-18 values in pedogenic carbonates showed a progressive increase in aridity from similar to 12 Ma to recent excluding short term increases in rainfall/monsoon intensity at around 10 Ma, 5 Ma, and 1.8 Ma (Singh et al., 2012). On the contrary, such reconstructions are not possible from the delta O-18 values of non-pedogenic carbonates and indeed the delta O-18 values of non-pedogenic carbonates are largely depleted to as much as 6 parts per thousand from the corresponding pedogenic carbonates. Such differences in delta C-13 and delta O-18 values of non-pedogenic carbonates from pedogenic carbonates are primarily due to the dependence of the former on groundwater conditions responsible for precipitating carbonate. Further, a comparison of isotopic values between non-pedogenic and pedogenic carbonates can be interpreted that post-6 Ma and pre-6 Ma non-pedogenic carbonates were largely formed by shallow and deep groundwater conditions respectively. The result of these investigative studies therefore, suggests that the stable delta C-13 and delta O-18 values of non-pedogenic carbonates, unlike the pedogenic carbonates and irrespective of nature of calcite fabric, showed their little importance in paleoclimatic and paleoecological reconstructions. (C) 2014 Elsevier B.V. All rights reserved.

UNIQUENESS OF SOLUTIONS TO SCHRODINGER EQUATIONS ON H-TYPE GROUPS

This paper deals with the Schrodinger equation i partial derivative(s)u(z, t; s) - Lu(z, t; s) = 0; where L is the sub-Laplacian on the Heisenberg group. Assume that the initial data f satisfies vertical bar f(z, t)vertical bar less than or similar to q(alpha)(z, t), where q(s) is the heat kernel associated to L. If in addition vertical bar u(z, t; s(0))vertical bar less than or similar to q(beta)(z, t), for some s(0) is an element of R \textbackslash {0}, then we prove that u(z, t; s) = 0 for all s is an element of R whenever alpha beta < s(0)(2). This result holds true in the more general context of H-type groups. We also prove an analogous result for the Grushin operator on Rn+1.

Iodo( trisyl) sulfane: Reactivity of a Stable Alkanesulfenyl Iodide towards Antithyroid Drugs

Iodination of tris(trimethylsilyl)methanethiol (trisylthiol, TsiSH) in tetrahydrofuran provides the new thermally stable alkanesulfenyl iodide iodo(trisyl)sulfane, TsiSI] as a violet solid. Iodo(trisyl)sulfane exhibits iodine-iodine contacts between pairs of TsiSI molecules in the solid state. Properties of TsiSI were studied by vibrational spectroscopy and with the help of density functional calculations. TsiSI reacts in the presence of triethylamine with the antithyroid drugs 6-n-propyl- and 6-methylthiouracil (PTU, MTU) and with N-methylmethimazole (MMI) to form unsymmetric disulfides that were investigated by means of X-ray crystallography. In the solid state, the PTU and MTU derivatives exist as hydrogen-bonded centrosymmetric dimers, whereas the MMI-derived disulfide is an unsymmetric monomer.

Comparative Study of Protein Unfolding in Aqueous Urea and Dimethyl Sulfoxide Solutions: Surface Polarity, Solvent Specificity, and Sequence of Secondary Structure Melting

Elucidation of possible pathways between folded (native) and unfolded states of a protein is a challenging task, as the intermediates are often hard to detect. Here, we alter the solvent environment in a controlled manner by choosing two different cosolvents of water, urea, and dimethyl sulfoxide (DMSO) and study unfolding of four different proteins to understand the respective sequence of melting by computer simulation methods. We indeed find interesting differences in the sequence of melting of alpha helices and beta sheets in these two solvents. For example, in 8 M urea solution, beta-sheet parts of a protein are found to unfold preferentially, followed by the unfolding of alpha helices. In contrast, 8 M DMSO solution unfolds alpha helices first, followed by the separation of beta sheets for the majority of proteins. Sequence of unfolding events in four different alpha/beta proteins and also in chicken villin head piece (HP-36) both in urea and DMSO solutions demonstrate that the unfolding pathways are determined jointly by relative exposure of polar and nonpolar residues of a protein and the mode of molecular action of a solvent on that protein.

Phase transformation, improved ferroelectric and magnetic properties of (1-x) BiFeO3-xPb(Zr0.52Ti0.48)O-3 solid solutions

The authors prepared (1 - x) BiFeO3 - (x)Pb(Zr0.52Ti0.48)O-3 for x <= 0.30 by sol-gel method and investigated the material's structures, magnetic and electrical properties. Detailed Rietveld analysis of X-ray diffraction data revealed that the system retains distorted rhombohedral R3c structure for x <= 0.10 but transforms to monoclinic (Cc) structure for x > 0.10. Disappearance of some Raman modes corresponding to A1 modes and the decrease in the intensities of the remaining A1 modes with increasing x in the Raman spectra, which is a clear indication of structural modification and symmetry changes brought about by PZT doping. Enhanced magnetization with PZT doping content may be attributed to the gradual change and destruction in the spin cycloid structure of BiFeO3. The leakage current density at 3.5 kV/cm was reduced by approximately three orders of magnitude by doping PZT (x = 0.30), compared with BFO ceramics. (C) 2014 AIP Publishing LLC.

Frequency Domain Based Solution for Certain Class of Wave Equations: An exhaustive study of Numerical Solutions

The paper discusses the frequency domain based solution for a certain class of wave equations such as: a second order partial differential equation in one variable with constant and varying coefficients (Cantilever beam) and a coupled second order partial differential equation in two variables with constant and varying coefficients (Timoshenko beam). The exact solution of the Cantilever beam with uniform and varying cross-section and the Timoshenko beam with uniform cross-section is available. However, the exact solution for Timoshenko beam with varying cross-section is not available. Laplace spectral methods are used to solve these problems exactly in frequency domain. The numerical solution in frequency domain is done by discretisation in space by approximating the unknown function using spectral functions like Chebyshev polynomials, Legendre polynomials and also Normal polynomials. Different numerical methods such as Galerkin Method, Petrov- Galerkin method, Method of moments and Collocation method or the Pseudo-spectral method in frequency domain are studied and compared with the available exact solution. An approximate solution is also obtained for the Timoshenko beam with varying cross-section using Laplace Spectral Element Method (LSEM). The group speeds are computed exactly for the Cantilever beam and Timoshenko beam with uniform cross-section and is compared with the group speeds obtained numerically. The shear mode and the bending modes of the Timoshenko beam with uniform cross-section are separated numerically by applying a modulated pulse as the shear force and the corresponding group speeds for varying taper parameter in are obtained numerically by varying the frequency of the input pulse. An approximate expression for calculating group speeds corresponding to the shear mode and the bending mode, and also the cut-off frequency is obtained. Finally, we show that the cut-off frequency disappears for large in, for epsilon > 0 and increases for large in, for epsilon < 0.

An extended finite-element model coupled with level set method for analysis of growth of corrosion pits in metallic structures

Mass balance between metal and electrolytic solution, separated by a moving interface, in stable pit growth results in a set of governing equations which are solved for concentration field and interface position (pit boundary evolution). The interface experiences a jump discontinuity in metal concentration. The extended finite-element model (XFEM) handles this jump discontinuity by using discontinuous-derivative enrichment formulation, eliminating the requirement of using front conforming mesh and re-meshing after each time step as in the conventional finite-element method. However, prior interface location is required so as to solve the governing equations for concentration field for which a numerical technique, the level set method, is used for tracking the interface explicitly and updating it over time. The level set method is chosen as it is independent of shape and location of the interface. Thus, a combined XFEM and level set method is developed in this paper. Numerical analysis for pitting corrosion of stainless steel 304 is presented. The above proposed model is validated by comparing the numerical results with experimental results, exact solutions and some other approximate solutions. An empirical model for pitting potential is also derived based on the finite-element results. Studies show that pitting profile depends on factors such as ion concentration, solution pH and temperature to a large extent. Studying the individual and combined effects of these factors on pitting potential is worth knowing, as pitting potential directly influences corrosion rate.

Evaluating FuncSION: A software for automated synthesis of design solutions for stimulating ideation during mechanical conceptual design

The goal of the work reported in this paper is to use automated, combinatorial synthesis to generate alternative solutions to be used as stimuli by designers for ideation. FuncSION, a computational synthesis tool that can automatically synthesize solution concepts for mechanical devices by combining building blocks from a library, is used for this purpose. The objectives of FuncSION are to help generate a variety of functional requirements for a given problem and a variety of concepts to fulfill these functions. A distinctive feature of FuncSION is its focus on automated generation of spatial configurations, an aspect rarely addressed by other computational synthesis programs. This paper provides an overview of FuncSION in terms of representation of design problems, representation of building blocks, and rules with which building blocks are combined to generate concepts at three levels of abstraction: topological, spatial, and physical. The paper then provides a detailed account of evaluating FuncSION for its effectiveness in providing stimuli for enhanced ideation.

Digestive ripening and green synthesis of ultra-small (r < 2 nm) stable ZnO quantum dots

Given the recent reports pertaining to novel optical properties of ultra-small quantum dots (QDs) (r <2 nm), this nanomaterial is of relevance to both technology and science. However it is well known that in these size regimes most chalocogenide QD dispersions are unstable. Since applications often require use of QD dispersions (e.g. for deployment on a substrate), stabilizing these ultra-small particles is of practical relevance. In this work we demonstrate a facile, green, solution approach for synthesis of stable, ultra-small ZnO QDs having radius less than 2 nm. The particle size is calculated using Brits' equation and confirmed by transmission electron micrographs. ZnO QDs reported remain stable for > 120 days in ethanol (at similar to 298-303 K). We report digestive ripening (DR) in TEA capped ZnO QDs; this occurs rapidly over a short duration of 5 min. To explain this observation we propose a suitable mechanism based on the Lee's theory, which correlates the tendency of DR with the observed zeta potentials of the dispersed medium. To the best of our knowledge this is the (i) first report on DR in oxide QDs, as well as the first direct experimental verification of Lee's theory, and (ii) most rapid DR reported so far. The facile nature of the method presented here makes ultra-small ZnO readily accessible for fundamental exploration and technologically relevant applications. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

SOLUTIONS OF A SYSTEM OF FORCED BURGERS EQUATION IN TERMS OF GENERALIZED LAGUERRE POLYNOMIALS

In this article, we obtain explicit solutions of a linear PDE subject to a class of radial square integrable functions with a monotonically increasing weight function |x|(n-1)e(beta vertical bar x vertical bar 2)/2, beta >= 0, x is an element of R-n. This linear PDE is obtained from a system of forced Burgers equation via the Cole-Hopf transformation. For any spatial dimension n > 1, the solution is expressed in terms of a family of weighted generalized Laguerre polynomials. We also discuss the large time behaviour of the solution of the system of forced Burgers equation.