Lead-free piezoelectric system (Na0.5Bi0.5)TiO3-BaTiO3: Equilibrium structures and irreversible structural transformations driven by electric field and mechanical impact

The structure-property correlation in the lead-free piezoelectric (1 - x)(Na0.5Bi0.5)TiO3-(x)BaTiO3 has been systematically investigated in detail as a function of composition (0 < x <= 0.11), temperature, electric field, and mechanical impact by Raman scattering, ferroelectric, piezoelectric measurement, x-ray, and neutron powder diffraction methods. Although x-ray diffraction study revealed three distinct composition ranges characterizing different structural features in the equilibrium state at room temperature: (i) monoclinic (Cc) + rhombohedral (R3c) for the precritical compositions, 0 <= x <= 0.05, (ii) cubiclike for 0.06 <= x <= 0.0675, and (iii) morphotropic phase boundary (MPB) like for 0.07 <= x < 0.10, Raman and neutron powder diffraction studies revealed identical symmetry for the cubiclike and the MPB compositions. The cubiclike structure undergoes irreversible phase separation by electric poling as well as by pure mechanical impact. This cubiclike phase exhibits relaxor ferroelectricity in its equilibrium state. The short coherence length (similar to 50A degrees) of the out-of-phase octahedral tilts does not allow the normal ferroelectric state to develop below the dipolar freezing temperature, forcing the system to remain in a dipolar glass state at room temperature. Electric poling helps the dipolar glass state to transform to a normal ferroelectric state with a concomitant enhancement in the correlation length of the out-of-phase octahedral tilt.

Linear and nonlinear optical properties of expanded porphyrins: a DMRG study

We study absorption spectra and two photon absorption coefficient of expanded porphyrins (EPs) by the density matrix renormalization group (DMRG) technique. We employ the Pariser-Parr-Pople (PPP) Hamiltonian which includes long-range electron-electron interactions. We find that, in the 4n+2 EPs, there are two prominent low-lying one-photon excitations, while in 4n EPs, there is only one such excitation. We also find that 4n+2 EPs have large two-photon absorption cross sections compared to 4n EPs. The charge density rearrangement in the one-photon excited state is mostly at the pyrrole nitrogen site and at the meso carbon sites. In the two-photon states, the charge density rearrangement occurs mostly at the aza-ring sites. In the one-photon state, the C-C bond length in aza rings shows a tendency to become uniform. In the two-photon state, the bond distortions are on C-N bonds of the pyrrole ring and the adjoining C-C bonds which connect the pyrrole ring to the aza or meso carbon sites.

Flow-enhanced pairing and other unusual effects in Fermi gases in synthetic gauge fields

Recent experiments on fermions in synthetic gauge fields result in systems with a spin-orbit coupling along one spatial axis, a detuning field, and a Zeeman field. We show theoretically that the presence of all three results in interesting and unusual phenomena in a system of interacting fermions (interactions described by a scattering length). For two fermions, bound states appear only over a certain range of the center-of-mass momenta. The deepest bound state appears at a nonzero center-of-mass momentum. For center-of-mass momenta without a bound state, the gauge field induces a resonance-like feature in the scattering continuum resulting in a large scattering phase shift. In the case of many particles, we demonstrate that the system, in a parameter range, shows flow-enhanced pairing, i.e., a Fulde-Farrell-Larkin-Ovchnnikov superfluid state made of robust pairs with a finite center-of-mass momentum. Yet another regime of parameters offers the opportunity to study strongly interacting normal states of spin-orbit-coupled fermionic systems utilizing the resonance-like feature induced by the synthetic gauge field.

Anthracene-Containing Conjugated Polymer Showing Four Optical Transitions Upon Doping: A Spectroscopic Study

An anthracene-containing poly(arylene-ethynylene)-alt-poly(arylene-vinylene) (PAE-PAV) of general constitutional unit (PhCCAnthrCCPhCHCHAnthrCHCH)(n) bearing two 2-ethylhexyloxy solubilizing side chains on each phenylene (Ph) unit has been synthesized and characterized. The basic electrochemical characterization was done, showing the existence of two non-reversible oxidation and one reversible reduction peaks. The optical properties, the real and imaginary part of the dielectric function, were probed using spectroscopic ellipsometry (SE). The vibrational structure of the undoped/doped polymer was investigated using Fourier transformed infrared spectroscopy. A strong change in the polaronic absorption was observed during the doping, which after modeling revealed the existence of two separated transitions. The optical changes upon doping were additionally recorded using the SE technique. Similar to the results from FT-IR spectroscopy, two new in-the-gap absorptions were found. Moreover, the electrical conductivity as well as the mobility of positive carriers were measured. In the undoped state, the conductivity of the polymer was found to be below the detection limit (the conductivity increased to 0.69 S cm(-1). (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 338-346

Stabilization of metastable tetragonal phase in a rhombohedral magnetoelectric multiferroic BiFeO3-PbTiO3

The phase formation behaviour of the magnetoelectric multiferroic 0.8BiFeO(3)-0.2PbTiO(3) was studied as a function of heat treatment at different temperatures of a sol-gel derived powder. While under ordinary synthesis conditions this composition exhibits antiferromagnetic ordering and a rhombohedral structure; the sol-gel-enabled low-temperature synthesis could stabilize a tetragonal metastable phase along with the stable rhombohedral phase, mimicking a morphotropic phase boundary state. The phase coexistence state exhibits relatively enhanced ferromagnetic correlation. The same system with a relatively higher PbTiO3 concentration, 0.65BiFeO(3)-0.35PbTiO(3), on the other hand, exhibits a rhombohedral metastable phase. These results suggest that the occurrence of metastable phases is a very common feature in the BiFeO3-PbTiO3 magnetoelectric ferroelectric system and that it affects the ferroelectric and magnetic properties of system quite remarkably.

CFD Analysis of two phase flow with a prediction of torque demand of a Bi-lobe rotor of a mixing chamber

An attempt to study the fluid dynamic behavior of two phase flow comprising of solid and liquid with nearly equal density in a geometrical case that has an industrial significance in theareas like processing of polymers, food, pharma ceutical, paints. In this work,crystalline silica is considered as the dispersed medium in glycerin. In the CFD analysis carried out,the two phase components are considered to be premixed homogeneously at the initial state. The flow in a cylinder that has an axially driven bi-lobe rotor, a typical blender used in polymer industry for mixing or kneading to render the multi-component mixture to homogeneous condition is considered. A viscous, incompressible, isothermal flow is considered with an assumption that the components do not undergo any physical change and the solids are rigid and mix in fully wetting conditions. Silica with a particle diameter of 0.4 mm is considered and flow is analyzed for different mixing fractions. An industry standard CFD code is used for solving 3D-RANS equations. As the outcome of the study the torque demand by the bi-lobe rotor for different mixture fractions which are estimated show a behavioral consistency to the expected physical phenomena occurring in the domain considered.

Damping of Sands for Varying Saturation

A series of resonant column tests have been performed in the torsional mode of vibration to assess the effect of saturation, starting from the near dry state to the fully saturated state, on the damping ratio of sands corresponding to the threshold strain level. Tests were carried out on three different gradations of sand for various combinations of relative density and effective confining pressure. For fine sands, a certain optimum degree of saturation exists at which the damping ratio minimizes; it is known that a decrease in Sr from a fully saturated state leads to a continuous increase in the matric suction. With an increase in the relative density, the optimum degree of saturation for fine sand increases marginally from 1.38 to 1.49%, but does not show any dependency on the effective confining pressure. In contrast, the minimum values of the damping ratio for medium and coarse sands are found to always correspond to the near dry state. The damping ratio decreases continuously with increases in relative density and effective confining pressure. The threshold strain level has been found to decrease continuously with increases in relative density and effective confining pressure. (C) 2013 American Society of Civil Engineers.

STOKES' SYSTEM IN A DOMAIN WITH OSCILLATING BOUNDARY: HOMOGENIZATION AND ERROR ANALYSIS OF AN INTERIOR OPTIMAL CONTROL PROBLEM

Homogenization and error analysis of an optimal interior control problem in the framework of Stokes' system, on a domain with rapidly oscillating boundary, are the subject matters of this article. We consider a three dimensional domain constituted of a parallelepiped with a large number of rectangular cylinders at the top of it. An interior control is applied in a proper subdomain of the parallelepiped, away from the oscillating volume. We consider two types of functionals, namely a functional involving the L-2-norm of the state variable and another one involving its H-1-norm. The asymptotic analysis of optimality systems for both cases, when the cross sectional area of the rectangular cylinders tends to zero, is done here. Our major contribution is to derive error estimates for the state, the co-state and the associated pressures, in appropriate functional spaces.

A Donor-Acceptor-Donor Structured Organic Conductor with S center dot center dot center dot S Chalcogen Bonding

A novel thiophene derivative 7,9-di(thiophen-2-yl)-8H-cyclopentaa]acenaphthylen-8-one (DTCPA) is shown to exhibit high electrical conductivity (1.97 x 10(-2) +/- 0.0018 S/cm at RT) in the crystalline state. The material shows two orders of increase in conductivity from normal solid to single crystalline state. The crystal structure has S center dot center dot center dot S chalcogen bonding, C-H center dot center dot center dot O hydrogen bonding, and pi center dot center dot center dot pi stacking as the major intermolecular interactions. The nature and strength of the S center dot center dot center dot S interactions in this structure have been evaluated by theoretical charge density analysis, and its contribution to the crystal packing quantified by Hirshfeld surface analysis. Further, thermal and morphological characterizations have been carried out, and the second harmonic generation (SHG) efficiency has been measured using the Kurtz-Perry method.

Constraining gravity using entanglement in AdS/CFT

We investigate constraints imposed by entanglement on gravity in the context of holography. First, by demanding that relative entropy is positive and using the Ryu-Takayanagi entropy functional, we find certain constraints at a nonlinear level for the dual gravity. Second, by considering Gauss-Bonnet gravity, we show that for a class of small perturbations around the vacuum state, the positivity of the two point function of the field theory stress tensor guarantees the positivity of the relative entropy. Further, if we impose that the entangling surface closes off smoothly in the bulk interior, we find restrictions on the coupling constant in Gauss-Bonnet gravity. We also give an example of an anisotropic excited state in an unstable phase with broken conformal invariance which leads to a negative relative entropy.

Correlation between thermodynamic anomalies and pathways of ice nucleation in supercooled water

The well-known classical nucleation theory (CNT) for the free energy barrier towards formation of a nucleus of critical size of the new stable phase within the parent metastable phase fails to take into account the influence of other metastable phases having density/order intermediate between the parent metastable phase and the final stable phase. This lacuna can be more serious than capillary approximation or spherical shape assumption made in CNT. This issue is particularly significant in ice nucleation because liquid water shows rich phase diagram consisting of two (high and low density) liquid phases in supercooled state. The explanations of thermodynamic and dynamic anomalies of supercooled water often invoke the possible influence of a liquid-liquid transition between two metastable liquid phases. To investigate both the role of thermodynamic anomalies and presence of distinct metastable liquid phases in supercooled water on ice nucleation, we employ density functional theoretical approach to find nucleation free energy barrier in different regions of phase diagram. The theory makes a number of striking predictions, such as a dramatic lowering of nucleation barrier due to presence of a metastable intermediate phase and crossover in the dependence of free energy barrier on temperature near liquid-liquid critical point. These predictions can be tested by computer simulations as well as by controlled experiments. (C) 2014 AIP Publishing LLC.

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.

A Stochastic Chemical Dynamic Approach to Correlate Autoimmunity and Optimal Vitamin-D Range

Motivated by several recent experimental observations that vitamin-D could interact with antigen presenting cells (APCs) and T-lymphocyte cells (T-cells) to promote and to regulate different stages of immune response, we developed a coarse grained but general kinetic model in an attempt to capture the role of vitamin-D in immunomodulatory responses. Our kinetic model, developed using the ideas of chemical network theory, leads to a system of nine coupled equations that we solve both by direct and by stochastic (Gillespie) methods. Both the analyses consistently provide detail information on the dependence of immune response to the variation of critical rate parameters. We find that although vitamin-D plays a negligible role in the initial immune response, it exerts a profound influence in the long term, especially in helping the system to achieve a new, stable steady state. The study explores the role of vitamin-D in preserving an observed bistability in the phase diagram (spanned by system parameters) of immune regulation, thus allowing the response to tolerate a wide range of pathogenic stimulation which could help in resisting autoimmune diseases. We also study how vitamin-D affects the time dependent population of dendritic cells that connect between innate and adaptive immune responses. Variations in dose dependent response of anti-inflammatory and pro-inflammatory T-cell populations to vitamin-D correlate well with recent experimental results. Our kinetic model allows for an estimation of the range of optimum level of vitamin-D required for smooth functioning of the immune system and for control of both hyper-regulation and inflammation. Most importantly, the present study reveals that an overdose or toxic level of vitamin-D or any steroid analogue could give rise to too large a tolerant response, leading to an inefficacy in adaptive immune function.

Checking Liveness Properties of Presburger Counter Systems Using Reachability Analysis

Counter systems are a well-known and powerful modeling notation for specifying infinite-state systems. In this paper we target the problem of checking liveness properties in counter systems. We propose two semi decision techniques towards this, both of which return a formula that encodes the set of reachable states of the system that satisfy a given liveness property. A novel aspect of our techniques is that they use reachability analysis techniques, which are well studied in the literature, as black boxes, and are hence able to compute precise answers on a much wider class of systems than previous approaches for the same problem. Secondly, they compute their results by iterative expansion or contraction, and hence permit an approximate solution to be obtained at any point. We state the formal properties of our techniques, and also provide experimental results using standard benchmarks to show the usefulness of our approaches. Finally, we sketch an extension of our liveness checking approach to check general CTL properties.

Hydrophobic hydration driven self-assembly of curcumin in water: Similarities to nucleation and growth under large metastability, and an analysis of water dynamics at heterogeneous surfaces

As the beneficial effects of curcumin have often been reported to be limited to its small concentrations, we have undertaken a study to find the aggregation properties of curcumin in water by varying the number of monomers. Our molecular dynamics simulation results show that the equilibrated structure is always an aggregated state with remarkable structural rearrangements as we vary the number of curcumin monomers from 4 to 16 monomers. We find that the curcumin monomers form clusters in a very definite pattern where they tend to aggregate both in parallel and anti-parallel orientation of the phenyl rings, often seen in the formation of beta-sheet in proteins. A considerable enhancement in the population of parallel alignments is observed with increasing the system size from 12 to 16 curcumin monomers. Due to the prevalence of such parallel alignment for large system size, a more closely packed cluster is formed with maximum number of hydrophobic contacts. We also follow the pathway of cluster growth, in particular the transition from the initial segregated to the final aggregated state. We find the existence of a metastable structural intermediate involving a number of intermediate-sized clusters dispersed in the solution. We have constructed a free energy landscape of aggregation where the metatsable state has been identified. The course of aggregation bears similarity to nucleation and growth in highly metastable state. The final aggregated form remains stable with the total exclusion of water from its sequestered hydrophobic core. We also investigate water structure near the cluster surface along with their orientation. We find that water molecules form a distorted tetrahedral geometry in the 1st solvation layer of the cluster, interacting rather strongly with the hydrophilic groups at the surface of the curcumin. The dynamics of such quasi-bound water molecules near the surface of curcumin cluster is considerably slower than the bulk signifying a restricted motion as often found in protein hydration layer. (C) 2014 AIP Publishing LLC.