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.

Polymorphic phase boundaries and enhanced piezoelectric response in extended composition range in the lead free ferroelectric BaTi1-xZrxO3

Neutron powder diffraction study of Ba(Ti1-xZrx)O-3 at close composition intervals has revealed coexistence of ferroelectric phases: orthorhombic (Amm2) + tetragonal (P4mm) for 0.02 <= x <= 0.05 and rhombohedral (R3m) + orthorhombic (Amm2) for 0.07 <= x < 0.09. These compositions exhibit relatively enhanced piezoelectric properties as compared to their single phase counterparts outside this composition region, confirming the polymorphic phase boundary nature of the phase coexistence regions. (C) 2013 AIP Publishing LLC.

Efficient gradient-free simplex method for estimation of optical properties in image-guided diffuse optical tomography

Typical image-guided diffuse optical tomographic image reconstruction procedures involve reduction of the number of optical parameters to be reconstructed equal to the number of distinct regions identified in the structural information provided by the traditional imaging modality. This makes the image reconstruction problem less ill-posed compared to traditional underdetermined cases. Still, the methods that are deployed in this case are same as those used for traditional diffuse optical image reconstruction, which involves a regularization term as well as computation of the Jacobian. A gradient-free Nelder-Mead simplex method is proposed here to perform the image reconstruction procedure and is shown to provide solutions that closely match ones obtained using established methods, even in highly noisy data. The proposed method also has the distinct advantage of being more efficient owing to being regularization free, involving only repeated forward calculations. (C) 2013 Society of Photo-Optical Instrumentation Engineers (SPIE)

Rotating beams and non-rotating beams with shared eigenpair for pinned-free boundary condition

In this paper we look for a rotating beam, with pinned-free boundary conditions, whose eigenpair (frequency and mode-shape) is same as that of a uniform non-rotating beam for a particular mode. It is seen that for any given mode, there exists a flexural stiffness function (FSF) for which the ith mode eigenpair of a rotating beam with uniform mass distribution, is identical to that of a corresponding non-rotating beam with same length and mass distribution. Inserting these derived FSF's in a finite element code for a rotating pinned-free beam, the frequencies and mode shapes of a non-rotating pinned-free beam are obtained. For the first mode, a physically realistic equivalent rotating beam is possible, but for higher modes, the FSF has internal singularities. Strategies for addressing these singularities in the FSF for finite element analysis are provided. The proposed functions can be used as test functions for rotating beam codes and also for targeted destiffening of rotating beams.

Closed-form solutions for non-uniform Euler-Bernoulli free-free beams

In this paper, the free vibration of a non-uniform free-free Euler-Bernoulli beam is studied using an inverse problem approach. It is found that the fourth-order governing differential equation for such beams possess a fundamental closed-form solution for certain polynomial variations of the mass and stiffness. An infinite number of non-uniform free-free beams exist, with different mass and stiffness variations, but sharing the same fundamental frequency. A detailed study is conducted for linear, quadratic and cubic variations of mass, and on how to pre-select the internal nodes such that the closed-form solutions exist for the three cases. A special case is also considered where, at the internal nodes, external elastic constraints are present. The derived results are provided as benchmark solutions for the validation of non-uniform free-free beam numerical codes. (C) 2013 Elsevier Ltd. All rights reserved.

Parametrisation-free determination of the shape parameters for the pion electromagnetic form factor

Recent data from high-statistics experiments that have measured the modulus of the pion electromagnetic form factor from threshold to relatively high energies are used as input in a suitable mathematical framework of analytic continuation to find stringent constraints on the shape parameters of the form factor at t = 0. The method uses also as input a precise description of the phase of the form factor in the elastic region based on Fermi-Watson theorem and the analysis of the pi pi scattering amplitude with dispersive Roy equations, and some information on the spacelike region coming from recent high precision experiments. Our analysis confirms the inconsistencies of several data on the modulus, especially from low energies, with analyticity and the input phase, noted in our earlier work. Using the data on the modulus from energies above 0.65 GeV, we obtain, with no specific parametrisation, the prediction < r(pi)(2)> is an element of (0.42, 0.44) fm(2) for the charge radius. The same formalism leads also to very narrow allowed ranges for the higher-order shape parameters at t = 0, with a strong correlation among them.

Communication: Benzene dimer-The free energy landscape

Establishing the relative orientation of the two benzene molecules in the dimer has remained an enigmatic challenge. Consensus has narrowed the choice of structures to either a T-shape, that may be tilted, or a parallel displaced arrangement, but the relatively small energy differences makes identifying the global minimum difficult. Here we report an ab initio Car-Parrinello Molecular Dynamics based metadynamics computation of the free-energy landscape of the benzene dimer. Our calculations show that although competing structures may be isoenergetic, free energy always favors a tilted T-shape geometry at all temperatures where the bound benzene dimer exist. (C) 2013 AIP Publishing LLC.

Strong-coupling expansion for ultracold bosons in an optical lattice at finite temperatures in the presence of superfluidity

We develop a strong-coupling (t << U) expansion technique for calculating the density profile for bosonic atoms trapped in an optical lattice with an overall harmonic trap at finite temperature and finite on-site interaction in the presence of superfluid regions. Our results match well with quantum Monte Carlo simulations at finite temperature. We also show that the superfluid order parameter never vanishes in the trap due to the proximity effect. Our calculations for the scaled density in the vacuum-to-superfluid transition agree well with the experimental data for appropriate temperatures. We present calculations for the entropy per particle as a function of temperature which can be used to calibrate the temperature in experiments. We also discuss issues connected with the demonstration of universal quantum critical scaling in the experiments.

Cross-Hetero-Dehydrogenative Coupling Reaction of Phosphites: A Catalytic Metal-Free Phosphorylation of Amines and Alcohols

Phosphorylation of amines, alcohols, and sulfoximines are accomplished using molecular iodine as a catalyst and H2O2 as the sole oxidant under mild reaction conditions. This method provides an easy route for synthesizing a variety of phosphoramidates, phosphorus triesters and sulfoximine-derived phosphoramidates which are of biological importance.

Gibbs free energy of formation of rhodium sulfides

Using a solid-state electrochemical technique, thermodynamic properties of three sulfide phases (RhS0.882, Rh3S4, Rh2S3) in the binary system (Rh + S) are measured as a function of temperature over the range from (925 to 1275) K. Single crystal CaF2 is used as the electrolyte. The auxiliary electrode consisting of (CaS + CaF2) is designed in such a way that the sulfur chemical potential converts into an equivalent fluorine potential at each electrode. The sulfur potentials at the measuring electrodes are established by the mixtures of (Rh + RhS0.882), (RhS0.882 + Rh3S4) and (Rh3S4 + Rh2S3) respectively. A gas mixture (H-2 + H2S + Ar) of known composition fixes the sulfur potential at the reference electrode. A novel cell design with physical separation of rhodium sulfides in the measuring electrode from CaS in the auxiliary electrode is used to prevent interaction between the two sulfide phases. They equilibrate only via the gas phase in a hermetically sealed reference enclosure. Standard Gibbs energy changes for the following reactions are calculated from the electromotive force of three cells: 2.2667Rh (s) + S-2 (g) -> 2.2667RhS(0.882) (s), Delta(r)G degrees +/- 2330/(J . mol(-1)) = -288690 + 146.18 (T/K), 4.44RhS(0.882) (s) + S-2 (g) -> 1.48Rh(3)S(4) (s), Delta(r)G degrees +/- 2245/(J . mol(-1)) = -245596 + 164.31 (T/K), 4Rh(3)S(4) (s) + S-2 (g) -> 6Rh(2)S(3) (s), Delta(r)G degrees +/- 2490/(J . mol(-1)) = -230957 + 160: 03 (T/K). Standard entropy and enthalpy of formation of rhodium sulfides from elements in their normal standard states at T = 298.15 K are evaluated. (C) 2013 Elsevier Ltd. All rights reserved.

Long ranged structural modulation in the pre-morphotropic phase boundary cubic-like state of the lead-free piezoelectric Na1/2Bi1/2TiO3-BaTiO3

The nature of the pre-morphotropic phase boundary (MPB) cubic-like state in the lead-free piezoelectric ceramics (1-x)Na1/2Bi1/2TiO3-(x)BaTiO3 at x similar to 0.06 has been examined in detail by electric field and temperature dependent neutron diffraction, x-ray diffraction, dielectric and ferroelectric characterization. The superlattice reflections in the neutron diffraction patterns cannot be explained with the tetragonal P4bm and the rhombohedral (R3c) phase coexistence model. The cubic like state is rather a result of long ranged modulated complex octahedral tilt. This modulated structure exhibits anomalously large dielectric dispersion. The modulated structure transforms to a MPB state on poling. The field-stabilized MPB state is destroyed and the modulated structure is restored on heating the poled specimen above the Vogel-Fulcher freezing temperature. The results show the predominant role of competing octahedral tilts in determining the nature of structural and polar states in Na1/2Bi1/2TiO3-based ferroelectrics. (C) 2013 AIP Publishing LLC.

Flexibility in Food Extraction Techniques in Urban Free-Ranging Bonnet Macaques, Macaca radiata

Non-human primate populations, other than responding appropriately to naturally occurring challenges, also need to cope with anthropogenic factors such as environmental pollution, resource depletion, and habitat destruction. Populations and individuals are likely to show considerable variations in food extraction abilities, with some populations and individuals more efficient than others at exploiting a set of resources. In this study, we examined among urban free-ranging bonnet macaques, Macaca radiata (a) local differences in food extraction abilities, (b) between-individual variation and within-individual consistency in problem-solving success and the underlying problem-solving characteristics, and (c) behavioral patterns associated with higher efficiency in food extraction. When presented with novel food extraction tasks, the urban macaques having more frequent exposure to novel physical objects in their surroundings, extracted food material from PET bottles and also solved another food extraction task (i.e., extracting an orange from a wire mesh box), more often than those living under more natural conditions. Adults solved the tasks more frequently than juveniles, and females more frequently than males. Both solution-technique and problem-solving characteristics varied across individuals but remained consistent within each individual across the successive presentations of PET bottles. The macaques that solved the tasks showed lesser within-individual variation in their food extraction behavior as compared to those that failed to solve the tasks. A few macaques appropriately modified their problem-solving behavior in accordance with the task requirements and solved the modified versions of the tasks without trial-and-error learning. These observations are ecologically relevant - they demonstrate considerable local differences in food extraction abilities, between-individual variation and within-individual consistency in food extraction techniques among free-ranging bonnet macaques, possibly affecting the species' local adaptability and resilience to environmental changes.

Endocrine Correlates of Musth in Free-Ranging Asian Elephants (Elephas maximus) Determined by Non-Invasive Faecal Steroid Hormone Metabolite Measurements

The occurrence of musth, a period of elevated levels of androgens and heightened sexual activity, has been well documented for the male Asian elephant (Elephas maximus). However, the relationship between androgen-dependent musth and adrenocortical function in this species is unclear. The current study is the first assessment of testicular and adrenocortical function in free-ranging male Asian elephants by measuring levels of testosterone (androgen) and cortisol (glucocorticoid - a physiological indicator of stress) metabolites in faeces. During musth, males expectedly showed significant elevation in faecal testosterone metabolite levels. Interestingly, glucocorticoid metabolite concentrations remained unchanged between musth and non-musth periods. This observation is contrary to that observed with wild and captive African elephant bulls and captive Asian bull elephants. Our results show that musth may not necessarily represent a stressful condition in free-ranging male Asian elephants.

Calculation of Chemical Potentials and Occupancies in Clathrate Hydrates through Monte Carlo Molecular Simulations

The flexibility of the water lattice in clathrate hydrates and guest-guest interactions has been shown in previous studies to significantly affect the values of the thermodynamic properties, such as chemical potentials and free energies. Here we describe methods for computing occupancies, chemical potentials, and free energies that account for the flexibility of water lattice and guest-guest interactions in the hydrate phase. The methods are validated for a wide variety of guest molecules, such as methane, ethane, carbon dioxide, and tetrahydrodfuran by comparing the predicted occupancy values of guest molecules with those obtained from isothermal isobaric semigrand Monte Carlo simulations. The proposed methods extend the van der Waals and Platteuw theory for clathrate hydrates, and the Langmuir constant is calculated based on the structure of the empty hydrate lattice. These methods in combination with development of advanced molecular models for water and guest molecules should lead to a more thermodynamically consistent theory for clathrate hydrates.

Atomic Structure of Quantum Gold Nanowires: Quantification of the Lattice Strain

Theoretical studies exist to compute the atomic arrangement in gold nanowires and the influence on their electronic behavior with decreasing diameter. Experimental studies, e.g., by transmission electron microscopy, on chemically synthesized ultrafine wires are however lacking owing to the unavailability of suitable protocols for sample preparation and the stability of the wires under electron beam irradiation. In this work, we present an atomic scale structural investigation on quantum single crystalline gold nanowires of 2 nm diameter, chemically prepared on a carbon film grid. Using low dose aberration-corrected high resolution (S)TEM, we observe an inhomogeneous strain distribution in the crystal, largely concentrated at the twin boundaries and the surface along with the presence of facets and surface steps leading to a noncircular cross section of the wires. These structural aspects are critical inputs needed to determine their unique electronic character and their potential as a suitable catalyst material. Furthermore, electron-beam-induced structural changes at the atomic scale, having implications on their mechanical behavior and their suitability as interconnects, are discussed.