Cation-templated 2-D Mn(II)-oxalate framework with an acyclic tetrameric water cluster

The single-crystal X-ray structure of a cation-templated manganese-oxalate coordination polymer [NH(C2H5)(3)][Mn-2(ox)(3)]center dot(5H(2)O)] (1) is reported. In 1, triethylammonium cation is entrapped between the cavities of 2-D honeycomb layers constructed by oxalate and water. The acyclic tetrameric water clusters and discrete water assemble the parallel 2-D honeycomb oxalate layers via an intricate array of hydrogen bonds into an overall 3-D network. The magnetic susceptibility, with and without the water cluster, are reported with infrared and EPR studies.

Near-Room-Temperature Colossal Magnetodielectricity and Multiglass Properties in Partially Disordered La2NiMnO6

We report magnetic, dielectric, and magnetodielectric responses of the pure monoclinic bulk phase of partially disordered La2NiMnO6, exhibiting a spectrum of unusual properties and establish that this compound is an intrinsically multiglass system with a large magnetodielectric coupling (8%-20%) over a wide range of temperatures (150-300 K). Specifically, our results establish a unique way to obtain colossal magnetodielectricity, independent of any striction effects, by engineering the asymmetric hopping contribution to the dielectric constant via the tuning of the relative-spin orientations between neighboring magnetic ions in a transition-metal oxide system. We discuss the role of antisite (Ni-Mn) disorder in emergence of these unusual properties.

Diffusion ordered spectroscopy for resolution of double bonded cis, trans-isomers

NMR spectroscopic separation of double bonded cis- and trans-isomers, that have different molecular shapes but identical mass have been carried out using Diffusion Ordered Spectroscopy (DOSY). The mixtures of fumaric acid and maleic acid, that have similar hydrodynamic radii, have resolved been on the basis of their diffusion coefficients arising due to their different tendencies to associate with micelles or reverse micelles. Sodium dodecyl sulfate (SDS) and Dioctyl sulfosuccinate sodium salt (AOT) have been used as the media to mimic the chromatographic conditions, modify the average mobility and to achieve differential diffusion rates. The best separation of the components has been achieved by Dioctyl sulfosuccinate sodium salt (AOT) in D2O solution. (C) 2012 Elsevier B.V. All rights reserved.

Robust solver based on modified particle swarm optimization for improved solution of diffusion transport through containment facilities

Accurate estimation of mass transport parameters is necessary for overall design and evaluation processes of the waste disposal facilities. The mass transport parameters, such as effective diffusion coefficient, retardation factor and diffusion accessible porosity, are estimated from observed diffusion data by inverse analysis. Recently, particle swarm optimization (PSO) algorithm has been used to develop inverse model for estimating these parameters that alleviated existing limitations in the inverse analysis. However, PSO solver yields different solutions in successive runs because of the stochastic nature of the algorithm and also because of the presence of multiple optimum solutions. Thus the estimated mean solution from independent runs is significantly different from the best solution. In this paper, two variants of the PSO algorithms are proposed to improve the performance of the inverse analysis. The proposed algorithms use perturbation equation for the gbest particle to gain information around gbest region on the search space and catfish particles in alternative iterations to improve exploration capabilities. Performance comparison of developed solvers on synthetic test data for two different diffusion problems reveals that one of the proposed solvers, CPPSO, significantly improves overall performance with improved best, worst and mean fitness values. The developed solver is further used to estimate transport parameters from 12 sets of experimentally observed diffusion data obtained from three diffusion problems and compared with published values from the literature. The proposed solver is quick, simple and robust on different diffusion problems. (C) 2012 Elsevier Ltd. All rights reserved.

Diffusion mechanism in XSi2 and X5Si3 (X= Nb, Mo, V) phases

In view of the importance of the suicides in the high temperature applications, the diffusion behaviour is compared in different systems for two types of silicides, XSi2 and X5Si3 (X=Nb, Mo, V). Atomic mechanism of diffusion and defects present in the structure are discussed. In both the phases, Si has faster diffusion rate than the metal species. This is expected from the nearest neighbour (NN) bonds present in the XSi2 phase but rather unusual in the X5Si3 phase. Relative mobilities of the species calculated indicate the presence of high concentration of Si antisites. Moreover, the concentration of the defects is different in different systems to find different diffusion rates.

Diffusion mechanism in the mu phase in Nb-X (X = Ni, Co, Fe) systems

Nb is one of the common refractory elements added in Ni, Co and Fe based superalloys. This lead to the formation of brittle topological close packed (tcp) mu phase, which is deleterious to the structure. It mainly grows by interdiffusion and in the present article, the interdiffusion process in different Nb-X (X=Ni, Co, Fe) systems is discussed. The activation energy for interdiffusion is lower in the Co-Nb system (173 kJ/mol) than Fe-Nb system (233 kJ/mol), which is again lower than the value found in the Ni-Nb system (319.7 kJ/mol). The mole fraction of Nb in this phase is less than Fe or Co at stoichiometric compositions in the Nb-Fe (that is Fe7Nb6) and Nb-Co (that is Co7Nb6) systems. On the other hand, the mole fraction of Nb is higher than Ni in the same phase (Ni6Nb2) in Ni-Nb system. However, in all the phases, Nb has lower diffusion rate. Possible diffusion mechanism in this phase is discussed with respect to the crystal structure.

Interplay of localized and itinerant character of Ru ions: Tl2Ru2O7 versus Hg2Ru2O7

We carry out a comparative study of the electronic structure of two pyrochlore ruthenate compounds, Tl2Ru2O7 and Hg2Ru2O7, in terms of first principles calculations. Our study reveals the Ru d electrons in Hg2Ru2O7 to be much more delocalized compared to that in Tl2Ru2O7. The subtle change in the Ru-d bandwidths in the two compounds, triggered by the differences in Hg 5d-Ru 4d hybridization compared to that of Tl 5d-Ru 4d, bring in the observed differences in behavior. Our study further shows that the development of long range noncollinear antiferromagnetic structure at low temperature is sufficient to produce the insulating solution in Hg2Ru2O7, in line with the prediction from recent nuclear magnetic resonance study.

A versatile resolving agent for diffusion edited separation of enantiomers, complex mixtures and constitutional isomers

The study is the first report of the utilization of a crown ether as a new and versatile resolving agent for the diffusion edited separation of enantiomers, complex mixtures and constitutional isomers. As a consequence of different binding affinities of enantiomers of a chiral molecule and individual components of the complex mixtures with the crown ether, the molecules diffuse at different rates. The enhanced separation achieved due to matrix assisted diffusion permitted their separation in the diffusion dimension. The generality and wide utility of the new resolving agent and the methodology are demonstrated on diverse examples, such as an organic chiral molecule, constitutional isomers and complex mixture of molecules possessing different functional groups that possess nearly identical molecular weights.

Use of Fick's law and Maxwell–Stefan equations in computation of multicomponent diffusion

This article does not have an abstract.

Effect of pressure on the ionic conductivity of Li+ and Cl- ions in water

A molecular dynamics simulation study of aqueous solution of LiCl is reported as a function of pressure. Experimental measurements of conductivity of Li+ ion as a function of pressure shows an increase in conductivity with pressure. Our simulations are able to reproduce the observed trend in conductivity. A number of relevant properties have been computed in order to understand the reasons for the increase in conductivity with pressure. These include radial distribution function, void and neck distributions, hydration or coordination numbers, diffusivity, velocity autocorrelation functions, angles between ion-oxygen and dipole of water as well as OH vector, mean residence time for water in the hydration shell, etc. These show that the increase in pressure acts as a structure breaker. The decay of the self part of the intermediate scattering function at small wave number k shows a bi-exponential decay at 1 bar which changes to single exponential decay at higher pressures. The k dependence of the ratio of the self part of the full width at half maximum of the dynamic structure factor to 2Dk(2) exhibits trends which suggest that the void structure of water is playing a role. These support the view that the changes in void and neck distributions in water can account for changes in conductivity or diffusivity of Li+ with pressure. These results can be understood in terms of the levitation effect. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4756909]

Diffusion mechanism in the gold-copper system

Interdiffusion study is conducted in the Au-Cu system, which has complete solid solution in the higher temperature range and ordered phases in the lower temperature range. First experiments are conducted at higher temperatures, where atoms can diffuse randomly. Higher values of interdiffusion coefficients are found in the range of 40-50 at.% Cu. This trend is explained with the help of thermodynamic factor and possible concentration of vacancies. Following an experiment is conducted at 623 K (350 degrees C), where the ordered phases are grown. The interdiffusion coefficients at this temperature are compared after extrapolating the data calculated at higher temperatures.

Diffusion and growth mechanism of phases in the Pd-Sn system

Growth mechanism of phases and atomic mechanism of diffusion are discussed in the Pd-Sn system. The Kirkendall marker plane location indicates that the PdSn4 phase grows because of diffusion of Sn. Atomic arrangement in the crystal indicates that Sn can diffuse through its own sublattice but Pd cannot diffuse unless antisites are present. The negligible diffusion of Pd indicates the absence of Pd antisites. The activation energy value indicates that the contribution from grain boundary diffusion cannot be neglected although experiments were conducted in the homologous temperature range of 0.7-0.79.

Directional Diffusion Regulator (DDR) for some numerical solvers of hyperbolic conservation laws

A computational tool called ``Directional Diffusion Regulator (DDR)'' is proposed to bring forth real multidimensional physics into the upwind discretization in some numerical schemes of hyperbolic conservation laws. The direction based regulator when used with dimension splitting solvers, is set to moderate the excess multidimensional diffusion and hence cause genuine multidimensional upwinding like effect. The basic idea of this regulator driven method is to retain a full upwind scheme across local discontinuities, with the upwind bias decreasing smoothly to a minimum in the farthest direction. The discontinuous solutions are quantified as gradients and the regulator parameter across a typical finite volume interface or a finite difference interpolation point is formulated based on fractional local maximum gradient in any of the weak solution flow variables (say density, pressure, temperature, Mach number or even wave velocity etc.). DDR is applied to both the non-convective as well as whole unsplit dissipative flux terms of some numerical schemes, mainly of Local Lax-Friedrichs, to solve some benchmark problems describing inviscid compressible flow, shallow water dynamics and magneto-hydrodynamics. The first order solutions consistently improved depending on the extent of grid non-alignment to discontinuities, with the major influence due to regulation of non-convective diffusion. The application is also experimented on schemes such as Roe, Jameson-Schmidt-Turkel and some second order accurate methods. The consistent improvement in accuracy either at moderate or marked levels, for a variety of problems and with increasing grid size, reasonably indicate a scope for DDR as a regular tool to impart genuine multidimensional upwinding effect in a simpler framework. (C) 2012 Elsevier Inc. All rights reserved.

A Chemodosimetric Probe Based on a Conjugated Oxidized Bis-Indolyl System for Selective Naked-Eye Sensing of Cyanide Ions in Water

A new bis-indolyl-based colorimetric probe has been synthesized. This allows a Michael-type adduct formation for the detection of cyanide ions. The probe shows a remarkable color change from red to colorless upon addition of the cyanide ions in pure water. The cyanide ion reacts with the probe and removes the conjugation of the bis-indolyl moiety of the probe with that of the 4-substituted aromatic ring. This renders the probe colorless. The mechanism of the reaction of the probe with the cyanide ion was established by using 1H and 13C NMR spectroscopy, mass spectrometry, and kinetic studies.

Metal-Ion Metathesis in Metal-Organic Frameworks: A Synthetic Route to New Metal-Organic Frameworks

A porous metalorganic framework, Mn(H3O)(Mn4Cl)(3)(hmtt)(8)] (POST-65), was prepared by the reaction of 5,5',10,10',15,15'-hexamethyltruxene-2,7,12-tricarboxylic acid (H(3)hmtt) with MnCl2 under solvothermal conditions. POST-65(Mn) was subjected to post-synthetic modification with Fe, Co, Ni, and Cu according to an ion-exchange method that resulted in the formation of three isomorphous frameworks, POST-65(Co/Ni/Cu), as well as a new framework, POST-65(Fe). The ion-exchanged samples could not be prepared by regular solvothermal reactions. The complete exchange of the metal ions and retention of the framework structure were verified by inductively coupled plasmaatomic emission spectrometry (ICP-AES), powder X-ray diffraction (PXRD), and BrunauerEmmettTeller (BET) surface-area analysis. Single-crystal X-ray diffractions studies revealed a single-crystal-to-single-crystal (SCSC)-transformation nature of the ion-exchange process. Hydrogen-sorption and magnetization measurements showed metal-specific properties of POST-65.