Approaches toward (eta(2)-HX) (X = H, SiR (R = Me-3 or Me2Ph), CH3) sigma-complexes of ruthenium

Two new Ru(II)-complexes RuH(Tpms)(PPh3)(2)] 1 (Tpms - (C3H3N2)(3)CSO3, tris-(pyrazolyl) methane sulfonate) and Ru(OTf)(Tpms)(PPh3)(2)] 2 (OTf = CF3SO3) have been synthesized and characterized wherein Ru-H and Ru-OTf are the key reactive centers. Reaction of 1 with HOTf results in the Ru(eta(2)-H-2)(Tpms)(PPh3)(2)]OTf] complex 3, whereas reaction of 1 with Me3SiOTf affords the dihydrogen complex 3 and complex 1 through an unobserved sigma-silane intermediate. In addition, an attempt to characterize the sigma methane complex via reaction of complex 1 with CH3OTf yields complex 2 and free methane. On the other hand, reaction of Ru(OTf)(Tpms)(PPh3)(2)] 2 with H-2 and PhMe2SiH at low temperature resulted in sigma-H-2, 3 and a probable sigma-silane complexes, respectively. However, no sigma-methane complex was observed for the reaction of complex 2 with methane even at low temperature. (C) 2014 Elsevier B. V. All rights reserved.

Quantum simulation using fidelity-profile optimization

Experimental quantum simulation of a Hamiltonian H requires unitary operator decomposition (UOD) of its evolution unitary U = exp(-iHt) in terms of native unitary operators of the experimental system. Here, using a genetic algorithm, we numerically evaluate the most generic UOD (valid over a continuous range of Hamiltonian parameters) of the unitary operator U, termed fidelity-profile optimization. The optimization is obtained by systematically evaluating the functional dependence of experimental unitary operators (such as single-qubit rotations and time-evolution unitaries of the system interactions) to the Hamiltonian (H) parameters. Using this technique, we have solved the experimental unitary decomposition of a controlled-phase gate (for any phase value), the evolution unitary of the Heisenberg XY interaction, and simulation of the Dzyaloshinskii-Moriya (DM) interaction in the presence of the Heisenberg XY interaction. Using these decompositions, we studied the entanglement dynamics of a Bell state in the DM interaction and experimentally verified the entanglement preservation procedure of Hou et al. Ann. Phys. (N.Y.) 327, 292 (2012)] in a nuclear magnetic resonance quantum information processor.

Majorana edge modes in the Kitaev model

We study the Majorana modes, both equilibrium and Floquet, which can appear at the edges of the Kitaev model on the honeycomb lattice. We first present the analytical solutions known for the equilibrium Majorana edge modes for both zigzag and armchair edges of a semi-infinite Kitaev model and chart the parameter regimes in which they appear. We then examine how edge modes can be generated if the Kitaev coupling on the bonds perpendicular to the edge is varied periodically in time as periodic delta-function kicks. We derive a general condition for the appearance and disappearance of the Floquet edge modes as a function of the drive frequency for a generic d-dimensional integrable system. We confirm this general condition for the Kitaev model with a finite width by mapping it to a one-dimensional model. Our numerical and analytical study of this problem shows that Floquet Majorana modes can appear on some edges in the kicked system even when the corresponding equilibrium Hamiltonian has no Majorana mode solutions on those edges. We support our analytical studies by numerics for a finite sized system which show that periodic kicks can generate modes at the edges and the corners of the lattice.

Topological blocking in quantum quench dynamics

We study the nonequilibrium dynamics of quenching through a quantum critical point in topological systems, focusing on one of their defining features: ground-state degeneracies and associated topological sectors. We present the notion of ``topological blocking,'' experienced by the dynamics due to a mismatch in degeneracies between two phases, and we argue that the dynamic evolution of the quench depends strongly on the topological sector being probed. We demonstrate this interplay between quench and topology in models stemming from two extensively studied systems, the transverse Ising chain and the Kitaev honeycomb model. Through nonlocal maps of each of these systems, we effectively study spinless fermionic p-wave paired topological superconductors. Confining the systems to ring and toroidal geometries, respectively, enables us to cleanly address degeneracies, subtle issues of fermion occupation and parity, and mismatches between topological sectors. We show that various features of the quench, which are related to Kibble-Zurek physics, are sensitive to the topological sector being probed, in particular, the overlap between the time-evolved initial ground state and an appropriate low-energy state of the final Hamiltonian. While most of our study is confined to translationally invariant systems, where momentum is a convenient quantum number, we briefly consider the effect of disorder and illustrate how this can influence the quench in a qualitatively different way depending on the topological sector considered.

Studies on a frustrated Heisenberg spin chain with alternating ferromagnetic and antiferromagnetic exchanges

We study Heisenberg spin-1/2 and spin-1 chains with alternating ferromagnetic (J(1)(F)) and antiferromagnetic (J(1)(A)) nearest-neighbor interactions and a ferromagnetic next-nearest-neighbor interaction (J(2)(F)). In this model frustration is present due to the non-zero J(2)(F). The model with site spin s behaves like a Haldane spin chain, with site spin 2s in the limit of vanishing J(2)(F) and large J(1)(F)/J(1)(A). We show that the exact ground state of the model can be found along a line in the parameter space. For fixed J(1)(F), the phase diagram in the space of J(1)(A)-J(2)(F) is determined using numerical techniques complemented by analytical calculations. A number of quantities, including the structure factor, energy gap, entanglement entropy and zero temperature magnetization, are studied to understand the complete phase diagram. An interesting and potentially important feature of this model is that it can exhibit a macroscopic magnetization jump in the presence of a magnetic field; we study this using an effective Hamiltonian.

Diffusing-wave spectroscopy in an inhomogeneous object: Local viscoelastic spectra from ultrasound-assisted measurement of correlation decay arising from the ultrasound focal volume

We demonstrate diffusing-wave spectroscopy (DWS) in a localized region of a viscoelastically inhomogeneous object by measurement of the intensity autocorrelation g(2)(tau)] that captures only the decay introduced by the temperature-induced Brownian motion in the region. The region is roughly specified by the focal volume of an ultrasound transducer which introduces region specific mechanical vibration owing to insonification. Essential characteristics of the localized non-Markovian dynamics are contained in the decay of the modulation depth M(tau)], introduced by the ultrasound forcing in the focal volume selected, on g(2)(tau). The modulation depth M(tau(i)) at any delay time tau(i) can be measured by short-time Fourier transform of g(2)(tau) and measurement of the magnitude of the spectrum at the ultrasound drive frequency. By following the established theoretical framework of DWS, we are able to connect the decay in M(tau) to the mean-squared displacement (MSD) of scattering centers and the MSD to G*(omega), the complex viscoelastic spectrum. A two-region composite polyvinyl alcohol phantom with different viscoelastic properties is selected for demonstrating local DWS-based recovery of G*(omega) corresponding to these regions from the measured region specific M(tau(i))vs tau(i). The ultrasound-assisted measurement of MSD is verified by simulating, using a generalized Langevin equation (GLE), the dynamics of the particles in the region selected as well as by the usual DWS experiment without the ultrasound. It is shown that whereas the MSD obtained by solving the GLE without the ultrasound forcing agreed with its experimental counterpart covering small and large values of tau, the match was good only in the initial transients in regard to experimental measurements with ultrasound.

Edge states of a three-dimensional topological insulator

We use the bulk Hamiltonian for a three-dimensional topological insulator such as Bi-2 Se-3 to study the states which appear on its various surfaces and along the edge between two surfaces. We use both analytical methods based on the surface Hamiltonians (which are derived from the bulk Hamiltonian) and numerical methods based on a lattice discretization of the bulk Hamiltonian. We find that the application of a potential barrier along an edge can give rise to states localized at that edge. These states have an unusual energy-momentum dispersion which can be controlled by applying a potential along the edge; in particular, the velocity of these states can be tuned to zero. The scattering and conductance across the edge is studied as a function of the edge potential. We show that a magnetic field in a particular direction can also give rise to zero energy states on certain edges. We point out possible experimental ways of looking for the various edge states.

Tailoring the Microstructural, Optical, and Electrical Properties of Nanocrystalline WO3 Thin Films Using Al Doping

We have studied the influence of Al doping on the microstructural, optical, and electrical properties of spray-deposited WO3 thin films. XRD analyses confirm that all the films are of polycrystalline WO3 in nature, possessing monoclinic structure. EDX profiles of the Al-doped films show aluminum peaks implying incorporation of Al ions into WO3 lattice. On Al doping, the average crystallite size decreases due to increase in the density of nucleation centers at the time of film growth. The observed variation in the lattice parameter values on Al doping is attributed to the incorporation of Al ions into WO3 lattice. Enhancement in the direct optical band gap compared to the undoped film has been observed on Al doping due to decrease in the width of allowed energy states near the conduction band edge. The refractive indices of the films follow the Cauchy relation of normal dispersion. Electrical resistivity compared to the undoped film has been found to increase on Al doping.

Improved quasiparticle wave functions and mean field for G(0)W(0) calculations: Initialization with the COHSEX operator

The GW approximation to the electron self-energy has become a standard method for ab initio calculation of excited-state properties of condensed-matter systems. In many calculations, the G W self-energy operator, E, is taken to be diagonal in the density functional theory (DFT) Kohn-Sham basis within the G0 W0 scheme. However, there are known situations in which this diagonal Go Wo approximation starting from DFT is inadequate. We present two schemes to resolve such problems. The first, which we called sc-COHSEX-PG W, involves construction of an improved mean field using the static limit of GW, known as COHSEX (Coulomb hole and screened exchange), which is significantly simpler to treat than GW W. In this scheme, frequency-dependent self energy E(N), is constructed and taken to be diagonal in the COHSEX orbitals after the system is solved self-consistently within this formalism. The second method is called off diagonal-COHSEX G W (od-COHSEX-PG W). In this method, one does not self-consistently change the mean-field starting point but diagonalizes the COHSEX Hamiltonian within the Kohn-Sham basis to obtain quasiparticle wave functions and uses the resulting orbitals to construct the G W E in the diagonal form. We apply both methods to a molecular system, silane, and to two bulk systems, Si and Ge under pressure. For silane, both methods give good quasiparticle wave functions and energies. Both methods give good band gaps for bulk silicon and maintain good agreement with experiment. Further, the sc-COHSEX-PGW method solves the qualitatively incorrect DFT mean-field starting point (having a band overlap) in bulk Ge under pressure.

Vertex Cover Gets Faster and Harder on Low Degree Graphs

The problem of finding an optimal vertex cover in a graph is a classic NP-complete problem, and is a special case of the hitting set question. On the other hand, the hitting set problem, when asked in the context of induced geometric objects, often turns out to be exactly the vertex cover problem on restricted classes of graphs. In this work we explore a particular instance of such a phenomenon. We consider the problem of hitting all axis-parallel slabs induced by a point set P, and show that it is equivalent to the problem of finding a vertex cover on a graph whose edge set is the union of two Hamiltonian Paths. We show the latter problem to be NP-complete, and also give an algorithm to find a vertex cover of size at most k, on graphs of maximum degree four, whose running time is 1.2637(k) n(O(1)).

Development and Evaluation of Statistical Downscaling Models for Monthly Precipitation

Several statistical downscaling models have been developed in the past couple of decades to assess the hydrologic impacts of climate change by projecting the station-scale hydrological variables from large-scale atmospheric variables simulated by general circulation models (GCMs). This paper presents and compares different statistical downscaling models that use multiple linear regression (MLR), positive coefficient regression (PCR), stepwise regression (SR), and support vector machine (SVM) techniques for estimating monthly rainfall amounts in the state of Florida. Mean sea level pressure, air temperature, geopotential height, specific humidity, U wind, and V wind are used as the explanatory variables/predictors in the downscaling models. Data for these variables are obtained from the National Centers for Environmental Prediction-National Center for Atmospheric Research (NCEP-NCAR) reanalysis dataset and the Canadian Centre for Climate Modelling and Analysis (CCCma) Coupled Global Climate Model, version 3 (CGCM3) GCM simulations. The principal component analysis (PCA) and fuzzy c-means clustering method (FCM) are used as part of downscaling model to reduce the dimensionality of the dataset and identify the clusters in the data, respectively. Evaluation of the performances of the models using different error and statistical measures indicates that the SVM-based model performed better than all the other models in reproducing most monthly rainfall statistics at 18 sites. Output from the third-generation CGCM3 GCM for the A1B scenario was used for future projections. For the projection period 2001-10, MLR was used to relate variables at the GCM and NCEP grid scales. Use of MLR in linking the predictor variables at the GCM and NCEP grid scales yielded better reproduction of monthly rainfall statistics at most of the stations (12 out of 18) compared to those by spatial interpolation technique used in earlier studies.

Growth and electrical transport properties of InGaN/GaN heterostructures grown by PAMBE

InGaN epitaxial films were grown on GaN template by plasma-assisted molecular beam epitaxy. The composition of indium incorporation in single phase InGaN film was found to be 23%. The band gap energy of single phase InGaN was found to be similar to 2.48 eV: The current-voltage (I-V) characteristic of InGaN/GaN heterojunction was found to be rectifying behavior which shows the presence of Schottky barrier at the interface. Log-log plot of the I-V characteristics under forward bias indicates the current conduction mechanism is dominated by space charge limited current mechanism at higher applied voltage, which is usually caused due to the presence of trapping centers. The room temperature barrier height and the ideality factor of the Schottky junction were found to 0.76 eV and 4.9 respectively. The non-ideality of the Schottky junction may be due to the presence of high pit density and dislocation density in InGaN film. (C) 2014 Elsevier Ltd. All rights reserved.

Relative entropy in higher spin holography

We examine relative entropy in the context of the higher spin/CFT duality. We consider 3D bulk configurations in higher spin gravity which are dual to the vacuum and a high temperature state of a CFT with W-algebra symmetries in the presence of a chemical potential for a higher spin current. The relative entropy between these states is then evaluated using the Wilson line functional for holographic entanglement entropy. In the limit of small entangling intervals, the relative entropy should vanish for a generic quantum system. We confirm this behavior by showing that the difference in the expectation values of the modular Hamiltonian between the states matches with the difference in the entanglement entropy in the short-distance regime. Additionally, we compute the relative entropy of states corresponding to smooth solutions in the SL(2, Z) family with respect to the vacuum.

Synthesis, crystal structure and spectroscopic and electrochemical properties of bridged trisbenzoato copper-zinc heterobinuclear complex of 2,2 `-bipyridine

The synthesis of the heterobinuclear copper-zinc complex CuZn(bz)(3)(bpy)(2)]ClO4 (bz = benzoate) from benzoic acid and bipyridine is described. Single crystal X-ray diffraction studies of the heterobinuclear complex reveals the geometry of the benzoato bridged Cu(II)-Zn(II) centre. The copper or zinc atom is pentacoordinate, with two oxygen atoms from bridging benzoato groups and two nitrogen atoms from one bipyridine forming an approximate plane and a bridging oxygen atom from a monodentate benzoate group. The Cu-Zn distance is 3.345 angstrom. The complex is normal paramagnetic having mu(eff) value equal to 1.75 BM, ruling out the possibility of Cu-Cu interaction in the structural unit. The ESR spectrum of the complex in CH3CN at RT exhibit an isotropic four line spectrum centred at g = 2.142 and hyperfine coupling constants A(av) = 63 x 10(-4) cm(-1), characteristic of a mononuclear square-pyramidal copper(II) complexes. At LNT, the complex shows an isotropic spectrum with g(parallel to) = 2.254 and g(perpendicular to) =2.071 and A(parallel to) = 160 x 10(-4) cm(-1). The Hamiltonian parameters are characteristic of distorted square pyramidal geometry. Cyclic voltammetric studies of the complex have indicated quasi-reversible behaviour in acetonitrile solution. (C) 2014 Elsevier B.V. All rights reserved.

Transitory second-order reciprocal connection for two surfaces in point contact

This paper investigates the instantaneous spatial higher pair to lower pair substitute-connection which is kinematically equivalent up to acceleration analysis for two smooth surfaces in point contact. The existing first-order equivalent substitute-connection consisting of a Hooke's joint (U-joint) and a spherical joint (S-joint) connected by an additional link is extended up to second-order. A two step procedure is chalked out for achieving this equivalence. First, the existing method is employed for velocity equivalence. In the second step, the two centers of substitution are obtained as a conjugate relationship involving the principal normal curvatures of the surfaces at the contact point and the screw coordinates of the instantaneous screw axis (ISA) of the first-order relative motion. Unlike the classical planar replacement, this particular substitution cannot be done by merely examining the profiles of the contacting surfaces. An illustrative example of a three-link direct-contact mechanism is presented. (C) 2014 Elsevier Ltd. All rights reserved.