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The chelating dithioether 1,2-bis(2-methoxyethylthio)benzene. a novel solvent extractant for Pd(II), is aimed to be utilised in the selective recovery of palladium from spent automotive catalysts. For that, the extraction system has been further customised, including the choice of an appropriate diluent (1,2-dichlorobenzene) as well as an effective stripping agent (0.5 M thiourea in 0.1 M HCl), which both have been selected from a number of potential agents. It is shown in batch experiments that the selectivity for Pd(II) is maintained when the organic phase (10(-2) M 1,2-bis(2-methoxyethylthio)benzene in 1,2-dichlorobenzene) is used several times to extract an oxidising leach solution. According to the McCabe-Thiele plot two theoretical stages are needed to extract more than 98% of the Pd(II) contained in that solution. The calculation of the thermodynamic quantities Delta H degrees. Delta S degrees and Delta G degrees reveals that the reaction is entropy driven - the temperature has only a slight influence on the extraction yield. It is demonstrated that the mono-oxidised extractant has a catalytic effect on the extraction kinetics when the aqueous phase contains highly concentrated hydrochloric acid. HPLC measurements prove the presence of small quantities of 1-(2-methoxyethylsulfinyl)-2-(2-methoxyethylthio) benzene in the organic phase.
There is a demand for new and robust PdII extractants due to growing recycling rates. Chelating dithioethers are promising substances for solvent extraction as they form stable square-planar complexes with PdII. We have modified unsaturated dithioethers, which are known to coordinate PdII, and adapted them to the requirements of industrial practice. The ligands are analogues of 1,2-dithioethene with varying electron-withdrawing backbones and polar end-groups. The crystal structures of several ligands and their palladium complexes were determined as well as their electro- and photochemical properties, complex stability and behaviour in solution. Solvent extraction experiments showed the superiority of some of our ligands over conventionally used extractants in terms of their very fast reaction rates. With highly selective 1,2-bis(2-methoxyethylthio)benzene (4) it is possible to extract PdII from a highly acidic medium in the presence of other base and palladium-group metals.
As an extension of recent findings on the recovery of palladium with dithioether extractants, single crystals of the chelating vicinal thioether sulfoxide ligand rac-1-[(2-methoxyethyl)sulfanyl]-2-[(2-methoxyethyl)sulfinyl]benzene, C12H18O3S2, (I), and its square-planar dichloridopalladium complex, rac-dichlorido{1-[(2-methoxyethyl)sulfanyl]-2-[(2-methoxyethyl)sulfinyl]benzene-?2S,S'}palladium(II), [PdCl2(C12H18O3S2)], (II), have been synthesized and their structures analysed. The molecular structure of (II) is the first ever characterized involving a dihalogenidePdII complex in which the palladium is bonded to both a thioether and a sulfoxide functional group. The structural and stereochemical characteristics of the ligand are compared with those of the analogous dithioether compound [Traeger et al. (2012). Eur. J. Inorg. Chem. pp. 23412352]. The sulfinyl O atom suppresses the electron-pushing and mesomeric effect of the SC...;CS unit in ligand (I), resulting in bond lengths significantly different than in the dithioether reference compound. In contrast, in complex (II), those bond lengths are nearly the same as in the analogous dithioether complex. As observed previously, there is an interaction between the central PdII atom and the O atom that is situated above the plane.
Current models of eye movement control are derived from theories assuming serial processing of single items or from theories based on parallel processing of multiple items at a time. This issue has persisted because most investigated paradigms generated data compatible with both serial and parallel models. Here, we study eye movements in a sequential scanning task, where stimulus n indicates the position of the next stimulus n + 1. We investigate whether eye movements are controlled by sequential attention shifts when the task requires serial order of processing. Our measures of distributed processing in the form of parafoveal-on-foveal effects, long-range modulations of target selection, and skipping saccades provide evidence against models strictly based on serial attention shifts. We conclude that our results lend support to parallel processing as a strategy for eye movement control.
The problem of how complex quantum systems eventually come to rest lies at the heart of statistical mechanics. The maximum-entropy principle describes which quantum states can be expected in equilibrium, but not how closed quantum many-body systems dynamically equilibrate. Here, we report the experimental observation of the non-equilibrium dynamics of a density wave of ultracold bosonic atoms in an optical lattice in the regime of strong correlations. Using an optical superlattice, we follow its dynamics in terms of quasi-local densities, currents and coherences-all showing a fast relaxation towards equilibrium values. Numerical calculations based on matrix-product states are in an excellent quantitative agreement with the experimental data. The system fulfills the promise of being a dynamical quantum simulator, in that the controlled dynamics runs for longer times than present classical algorithms can keep track of.
Crosshole traveltime tomography using particle swarm optimization a near-surface field example
(2012)
Particle swarm optimization (PSO) is a relatively new global optimization approach inspired by the social behavior of bird flocking and fish schooling. Although this approach has proven to provide excellent convergence rates in different optimization problems, it has seldom been applied to inverse geophysical problems. Until today, published geophysical applications mainly focus on finding an optimum solution for simple, 1D inverse problems. We have applied PSO-based optimization strategies to reconstruct 2D P-wave velocity fields from crosshole traveltime data sets. Our inversion strategy also includes generating and analyzing a representative ensemble of acceptable models, which allows us to appraise uncertainty and nonuniqueness issues. The potential of our strategy was tested on field data collected at a well-constrained test site in Horstwalde, Germany. At this field site, the shallow subsurface mainly consists of sand- and gravel-dominated glaciofluvial sediments, which, as known from several boreholes and other geophysical experiments, exhibit some well-defined layering at the scale of our crosshole seismic data. Thus, we have implemented a flexible, layer-based model parameterization, which, compared with standard cell-based parameterizations, allows for significantly reducing the number of unknown model parameters and for efficiently implementing a priori model constraints. Comparing the 2D velocity fields resulting from our PSO strategy to independent borehole and direct-push data illustrated the benefits of choosing an efficient global optimization approach. These include a straightforward and understandable appraisal of nonuniqueness issues as well as the possibility of an improved and also more objective interpretation.
We investigate the effect of intermode coupling and anharmonicity on the excitation and relaxation dynamics of CO on Cu(100). The nonadiabatic coupling of the adsorbate to the surface is treated perturbatively using a position-dependent state-resolved transition rate model. Using the potential energy surface of Marquardt et al. [J. Chem. Phys. 132, 074108 (2010)], which provides an accurate description of intermode interactions, we propose a four-dimensional model that represents simultaneously the diffusion and the desorption of the adsorbate. The system is driven by both rational and optimized infrared laser pulses to favor either selective mode and state excitations or lateral displacement along the diffusion coordinate. The dissipative dynamics is simulated using the reduced density matrix in its Lindblad form. We show that coupling between the degrees of freedom, mediated by the creation and annihilation of electron-hole pairs in the metal substrate, significantly affects the system excitation and relaxation dynamics. In particular, the angular degrees of freedom appear to play an important role in the energy redistribution among the molecule-surface vibrations. We also show that coherent excitation using simple IR pulses can achieve population transfer to a specific target to some extent but does not allow enforcement of the directionality to the diffusion motion.
Black hole initial data are usually produced using Bowen-York-type puncture initial data or by applying an excision boundary condition. The benefits of the Bowen-York initial data are the ability to specify the spin and momentum of the system as parameters of the initial data. In an attempt to extend these benefits to other formulations of the Einstein constraints, the puncture method is reformulated using distributions as source terms. It is shown how the Bowen-York puncture black hole initial data and the trumpet variation are generated by distributional sources. A heuristic argument is presented to argue that these sources are the general sources of spin and momentum. In order to clarify the meaning of other distributional sources, an exact family of initial data with generalized sources to the Hamiltonian constraint are studied; spinning trumpet black hole initial data and black hole initial data with higher order momentum sources are also studied.
Generalized space-time fractional diffusion equation with composite fractional time derivative
(2012)
We investigate the solution of space-time fractional diffusion equations with a generalized Riemann-Liouville time fractional derivative and Riesz-Feller space fractional derivative. The Laplace and Fourier transform methods are applied to solve the proposed fractional diffusion equation. The results are represented by using the Mittag-Leffler functions and the Fox H-function. Special cases of the initial and boundary conditions are considered. Numerical scheme and Grunwald-Letnikov approximation are also used to solve the space-time fractional diffusion equation. The fractional moments of the fundamental solution of the considered space-time fractional diffusion equation are obtained. Many known results are special cases of those obtained in this paper. We investigate also the solution of a space-time fractional diffusion equations with a singular term of the form delta(x). t-beta/Gamma(1-beta) (beta > 0).
Pure and europium (Eu3+) doped ZrO2 synthesized by an oil-in-water microemulsion reaction method were investigated by in situ and ex situ X-ray diffraction (XRD), ex situ Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), steady state and time-resolved photoluminescence (PL) spectroscopies. Based on the Raman spectra excited at three different wavelengths i.e. 488, 514 and 633 nm and measured in the spectral range of 150-4000 cm(-1) the correlation between the phonon spectra of ZrO2 and luminescence of europium is clearly evidenced. The PL investigations span a variety of steady-state and time resolved measurements recorded either after direct excitation of the Eu3+ f-f transitions or indirect excitation into UV charge-transfer bands. After annealing at 500 degrees C, the overall Eu3+ emission is dominated by Eu3+ located in tetragonal symmetry lattice sites with a crystal-field splitting of the D-5(0)-F-7(1) emission of 20 cm(-1). Annealing of ZrO2 at 1000 degrees C leads to a superposition of Eu3+ emissions from tetragonal and monoclinic lattice sites with monoclinic crystal-field splitting of 200 cm(-1) for the D-5(0)-F-7(1) transition. At all temperatures, a non-negligible amorphous/disordered content is also measured and determined to be of monoclinic nature. It was found that the evolutions with calcination temperature of the average PL lifetimes corresponding to europium emission in the tetragonal and monoclinic sites and the monoclinic phase content of the Eu3+ doped ZrO2 samples follow a similar trend. By use of specific excitation conditions, the distribution of europium on the amorphous/disordered surface or ordered/crystalline sites can be identified and related to the phase content of zirconia. The role of zirconia host as a sensitizer for the europium PL is also discussed in both tetragonal and monoclinic phases.