Solvatochromism of 9,10-phenanthrenequinone: An electronic and resonance Raman spectroscopic study

Solvent effects play a vital role in various chemical, physical, and biological processes. To gain a fundamental understanding of the solute-solvent interactions and their implications on the energy level re-ordering and structure, UV-VIS absorption, resonance Raman spectroscopic, and density functional theory calculation studies on 9,10-phenanthrenequinone (PQ) in different solvents of diverse solvent polarity has been carried out. The solvatochromic analysis of the absorption spectra of PQ in protic dipolar solvents suggests that the longest (1n-pi(1)*; S-1 state) and the shorter (1 pi-pi(1)*; S-2 state) wavelength band undergoes a hypsochromic and bathochromic shift due to intermolecular hydrogen bond weakening and strengthening, respectively. It also indicates that hydrogen bonding plays a major role in the differential solvation of the S-2 state relative to the ground state. Raman excitation profiles of PQ (400-1800 cm(-1)) in various solvents followed their corresponding absorption spectra therefore the enhancements on resonant excitation are from single-state rather than mixed states. The hyperchromism of the longer wavelength band is attributed to intensity borrowing from the nearby allowed electronic transition through vibronic coupling. Computational calculation with C-2 nu symmetry constraint on the S-2 state resulted in an imaginary frequency along the low-frequency out-of-plane torsional modes involving the C=O site and therefore, we hypothesize that this mode could be involved in the vibronic coupling. (C) 2015 AIP Publishing LLC.

Cross-correlation-aided transport in stochastically driven accretion flows

The origin of linear instability resulting in rotating sheared accretion flows has remained a controversial subject for a long time. While some explanations of such non-normal transient growth of disturbances in the Rayleigh stable limit were available for magnetized accretion flows, similar instabilities in the absence of magnetic perturbations remained unexplained. This dichotomy was resolved in two recent publications by Chattopadhyay and co-workers Mukhopadhyay and Chattopadhyay, J. Phys. A 46, 035501 (2013); Nath et al., Phys. Rev. E 88, 013010 (2013)] where it was shown that such instabilities, especially for nonmagnetized accretion flows, were introduced through interaction of the inherent stochastic noise in the system (even a ``cold'' accretion flow at 3000Kis too ``hot'' in the statistical parlance and is capable of inducing strong thermal modes) with the underlying Taylor-Couette flow profiles. Both studies, however, excluded the additional energy influx (or efflux) that could result from nonzero cross correlation of a noise perturbing the velocity flow, say, with the noise that is driving the vorticity flow (or equivalently the magnetic field and magnetic vorticity flow dynamics). Through the introduction of such a time symmetry violating effect, in this article we show that nonzero noise cross correlations essentially renormalize the strength of temporal correlations. Apart from an overall boost in the energy rate (both for spatial and temporal correlations, and hence in the ensemble averaged energy spectra), this results in mutual competition in growth rates of affected variables often resulting in suppression of oscillating Alfven waves at small times while leading to faster saturations at relatively longer time scales. The effects are seen to be more pronounced with magnetic field fluxes where the noise cross correlation magnifies the strength of the field concerned. Another remarkable feature noted specifically for the autocorrelation functions is the removal of energy degeneracy in the temporal profiles of fast growing non-normal modes leading to faster saturation with minimum oscillations. These results, including those presented in the previous two publications, now convincingly explain subcritical transition to turbulence in the linear limit for all possible situations that could now serve as the benchmark for nonlinear stability studies in Keplerian accretion disks.

Image-Segmentation Technique to Analyze Deformation Profiles in Different Direct Shear Tests

Results from interface shear tests on sand-geosynthetic interfaces are examined in light of surface roughness of the interacting geosynthetic material. Three different types of interface shear tests carried out in the frame of direct shear-test setup are compared to understand the effect of parameters like box fixity and symmetry on the interface shear characteristics. Formation of shear bands close to the interface is visualized in the tests and the bands are analyzed using image-segmentation techniques in MATLAB. A woven geotextile with moderate roughness and a geomembrane with minimal roughness are used in the tests. The effect of surface roughness of the geosynthetic material on the formation of shear bands, movement of sand particles, and interface shear parameters are studied and compared through visual observations, image analyses, and image-segmentation techniques.

Magnetic frustration and dielectric relaxation in insulating Nd2NiMnO6 double perovskites

We have investigated structural, dielectric, and magnetic properties of polycrystalline double perovskite Nd2NiMnO6 compound. The compound crystallizes in monoclinic P2(1)/n symmetry and is partially B-site disordered depending on the synthesis conditions. It undergoes second-order ferromagnetic transition at 192K and shows glassy behaviour at low temperature. The glassy phase is due to anti-site disorder within the homogeneous sample. Temperature and frequency dependent dielectric measurements reveal colossal values of dielectric constant and is best interpreted using Maxwell-Wagner interfacial polarization model. Impedance spectroscopy has been used to analyse the intrinsic dielectric response. This enabled us to differentiate the conduction process at the grain and grain boundaries. Arrhenius behaviour is favoured at the grain boundary, while variable range hopping mechanism is considered most suitable within the grain region. dc conductivity measurements corroborate variable range hopping conduction. (C) 2015 AIP Publishing LLC.

Study of structures, energies and vibrational frequencies of (O-2)(n)(+) (n=2-5) clusters by GGA and meta-GGA density functional methods

Using Generalized Gradient Approximation (GGA) and meta-GGA density functional methods, structures, binding energies and harmonic vibrational frequencies for the clusters O-4(+), O-6(+), O-8(+) and O-10(+) have been calculated. The stable structures of O-4(+), O-6(+), O-8(+) and O-10(+) have point groups D-2h, D-3h, D-4h, and D-5h optimized on the quartet, sextet, octet and dectet potential energy surfaces, respectively. Rectangular (D-2h) O-4(+) has been found to be more stable compared to trans-planar (C-2h) on the quartet potential energy surface. Cyclic structure (D-3h) of CA cluster ion has been calculated to be more stable than other structures. Binding energy (B.E.) of the cyclic O-6(+) is in good agreement with experimental measurement. The zero-point corrected B.E. of O-8(+) with D4h symmetry on the octet potential energy surface and zero-point corrected B.E. of O-10(+) with D-5h symmetry on the dectet potential energy surface are also in good agreement with experimental values. The B.E. value for O-4(+) is close to the experimental value when single point energy is calculated by Brueckner coupled-cluster method, BD(T). (C) 2014 Elsevier B.V. All rights reserved.

Active Viscoelastic Matter: From Bacterial Drag Reduction to Turbulent Solids

A paradigm for internally driven matter is the active nematic liquid crystal, whereby the equations of a conventional nematic are supplemented by a minimal active stress that violates time-reversal symmetry. In practice, active fluids may have not only liquid-crystalline but also viscoelastic polymer degrees of freedom. Here we explore the resulting interplay by coupling an active nematic to a minimal model of polymer rheology. We find that adding a polymer can greatly increase the complexity of spontaneous flow, but can also have calming effects, thereby increasing the net throughput of spontaneous flow along a pipe (a ``drag-reduction'' effect). Remarkably, active turbulence can also arise after switching on activity in a sufficiently soft elastomeric solid.

Viscosity bound for anisotropic superfluids in higher derivative gravity

In the present paper, based on the principles of gauge/gravity duality we analytically compute the shear viscosity to entropy (eta/s) ratio corresponding to the super fluid phase in Einstein Gauss-Bonnet gravity. From our analysis we note that the ratio indeed receives a finite temperature correction below certain critical temperature (T < T-c). This proves the non universality of eta/s ratio in higher derivative theories of gravity. We also compute the upper bound for the Gauss-Bonnet coupling (lambda) corresponding to the symmetry broken phase and note that the upper bound on the coupling does not seem to change as long as we are close to the critical point of the phase diagram. However the corresponding lower bound of the eta/s ratio seems to get modified due to the finite temperature effects.

Characterization of friction at three contact pairs by photoelastic Isotropic point (IP)

Friction coefficient between a circular-disk periphery and V-block surface was determined by introducing the concept of isotropic point (IP) in isochromatic field of the disk under three-point symmetric loading. IP position on the symmetry axis depends on active coefficient of friction during experiment. We extend this work to asymmetric loading of circular disk in which case two frictional contact pairs out of three loading contacts, independently control the unconstrained IP location. Photoelastic experiment is conducted on particular case of asymmetric three-point loading of circular disk. Basics of digital image processing are used to extract few essential parameters from experimental image, particularly IP location. Analytical solution by Flamant for half plane with a concentrated load, is utilized to derive stress components for required loading configurations of the disk. IP is observed, in analytical simulations of three-point asymmetric normal loading, to move from vertical axis to the boundary along an ellipse-like curve. When friction is included in the analysis, IP approaches the center with increase in loading friction and it goes away with increase in support friction. With all these insights, using experimental IP information, friction angles at three contact pairs of circular disk under asymmetric loading, are determined.

Non-Abelian gauge redundancy and entropic ambiguities

The von Neumann entropy of a generic quantum state is not unique unless the state can be uniquely decomposed as a sum of extremal or pure states. Therefore one reaches the remarkable possibility that there may be many entropies for a given state. We show that this happens if the GNS representation (of the algebra of observables in some quantum state) is reducible, and some representations in the decomposition occur with non-trivial degeneracy. This ambiguity in entropy, which can occur at zero temperature, can often be traced to a gauge symmetry emergent from the non-trivial topological character of the configuration space of the underlying system. We also establish the analogue of an H-theorem for this entropy by showing that its evolution is Markovian, determined by a stochastic matrix. After demonstrating this entropy ambiguity for the simple example of the algebra of 2 x 2 matrices, we argue that the degeneracies in the GNS representation can be interpreted as an emergent broken gauge symmetry, and play an important role in the analysis of emergent entropy due to non-Abelian anomalies. We work out the simplest situation with such non-Abelian symmetry, that of an ethylene molecule.

Optical and dielectric study of strontium modified barium zirconium titanate ceramic prepared by high energy ball milling

Strontium modified barium zirconium titanate with general formula Ba1-xSrxZr0.05Ti0.95O3 ceramics have been prepared by solid state and high energy ball milling technique. The X-ray diffraction and Rietveld refinement studies show that all the compositions have single phase symmetry. The composition BaZr0.05Ti0.95O3 shows orthorhombic symmetric with space group Amm2. The structure changes from orthorhombic to tetragonal with strontium doping up to x = 0.3 and with further addition, changes to cubic. The scanning electron micrographs show that the grain size decreases with increase in strontium content. The temperature dependent dielectric behavior shows three phase transition in the parent material which merges with an increase in Sr content The transition temperature and dielectric constant decreases with an increase in Sr concentration. The phase transition becomes more diffused with increment in doping concentration. The ferroelectric behavior of the ceramics is studied by the hysteresis loop. The optical behavior is studied by the UV-visible spectroscopy and found that the optical band gap increases with Sr concentration. (C) 2015 Elsevier B.V. All rights reserved.

Design of symmetric TIM barrel proteins from first principles

Background: Computational protein design is a rapidly maturing field within structural biology, with the goal of designing proteins with custom structures and functions. Such proteins could find widespread medical and industrial applications. Here, we have adapted algorithms from the Rosetta software suite to design much larger proteins, based on ideal geometric and topological criteria. Furthermore, we have developed techniques to incorporate symmetry into designed structures. For our first design attempt, we targeted the (alpha/beta)(8) TIM barrel scaffold. We gained novel insights into TIM barrel folding mechanisms from studying natural TIM barrel structures, and from analyzing previous TIM barrel design attempts. Methods: Computational protein design and analysis was performed using the Rosetta software suite and custom scripts. Genes encoding all designed proteins were synthesized and cloned on the pET20-b vector. Standard circular dichroism and gel chromatographic experiments were performed to determine protein biophysical characteristics. 1D NMR and 2D HSQC experiments were performed to determine protein structural characteristics. Results: Extensive protein design simulations coupled with ab initio modeling yielded several all-atom models of ideal, 4-fold symmetric TIM barrels. Four such models were experimentally characterized. The best designed structure (Symmetrin-1) contained a polar, histidine-rich pore, forming an extensive hydrogen bonding network. Symmetrin-1 was easily expressed and readily soluble. It showed circular dichroism spectra characteristic of well-folded alpha/beta proteins. Temperature melting experiments revealed cooperative and reversible unfolding, with a T-m of 44 degrees C and a Gibbs free energy of unfolding (Delta G degrees) of 8.0 kJ/mol. Urea denaturing experiments confirmed these observations, revealing a C-m of 1.6 M and a Delta G degrees of 8.3 kJ/mol. Symmetrin-1 adopted a monomeric conformation, with an apparent molecular weight of 32.12 kDa, and displayed well resolved 1D-NMR spectra. However, the HSQC spectrum revealed somewhat molten characteristics. Conclusions: Despite the detection of molten characteristics, the creation of a soluble, cooperatively folding protein represents an advancement over previous attempts at TIM barrel design. Strategies to further improve Symmetrin-1 are elaborated. Our techniques may be used to create other large, internally symmetric proteins.

Synthesis of Eu3+-activated ZnO superstructures: Photoluminescence, Judd-Ofelt analysis and Sunlight photocatalytic properties

Photoluminescence and photocatalytic properties of Eu-doped ZnO nanoparticles (NPs) were synthesized by facile phyto route. XPS results demonstrated the existence of Eu3+ as dopant into ZnO. Morphologies of the NPs were mainly dependent on Eu3+ and Aloe vera gel. Red shift of energy band gap was due to the creation of intermediate energy states of Eu3+ and oxygen vacancies in the band gap. PL emission of ZnO:Eu3+ (1-11 mol%, 8 ml and 7 mol%, 2-12 ml) exhibit characteristic peaks of D-5(0) -> F-7(2) transitions. From the Judd-Ofelt analysis, intensities of transitions between different.' levels dependent on the symmetry of the local environment of Eu3+ ions. CIE chromaticity co-ordinates confirm reddish emission of the phosphor. Further, NPs exhibit excellent photocatalytic activity for the degradation of Rhodamine B (94%) under Sunlight was attributed to crystallite size, band gap, morphology and oxygen vacancies. In addition, photocatalyst reusability studies were conducted and found that Eu-doped catalyst could be reused several times with negligible decrease in catalytic activity. The present work directs new possibilities to provide some new insights into the design of new phyto synthesized nanophosphors for display devices, photocatalysts with high activity for environmental clean-up and solar energy conversion. (C) 2015 Elsevier B.V. All rights reserved.

Observation of correlated spin-orbit order in a strongly anisotropic quantum wire system

Quantum wires with spin-orbit coupling provide a unique opportunity to simultaneously control the coupling strength and the screened Coulomb interactions where new exotic phases of matter can be explored. Here we report on the observation of an exotic spin-orbit density wave in Pb-atomic wires on Si(557) surfaces by mapping out the evolution of the modulated spin-texture at various conditions with spin-and angle-resolved photoelectron spectroscopy. The results are independently quantified by surface transport measurements. The spin polarization, coherence length, spin dephasing rate and the associated quasiparticle gap decrease simultaneously as the screened Coulomb interaction decreases with increasing excess coverage, providing a new mechanism for generating and manipulating a spin-orbit entanglement effect via electronic interaction. Despite clear evidence of spontaneous spin-rotation symmetry breaking and modulation of spin-momentum structure as a function of excess coverage, the average spin polarization over the Brillouin zone vanishes, indicating that time-reversal symmetry is intact as theoretically predicted.

A Generalization of Gravity

I consider theories of gravity built not just from the metric and affine connection, but also other (possibly higher rank) symmetric tensor(s). The Lagrangian densities are scalars built from them, and the volume forms are related to Cayley's hyperdeterminants. The resulting diff-invariant actions give rise to geometric theories that go beyond the metric paradigm (even metric-less theories are possible), and contain Einstein gravity as a special case. Examples contain theories with generalizeations of Riemannian geometry. The 0-tensor case is related to dilaton gravity. These theories can give rise to new types of spontaneous Lorentz breaking and might be relevant for ``dark'' sector cosmology.

Interrelationship between Interphase Boundaries and Phase Contents near the Critical Compositions of Lead-Free Ferroelectric (Na0.5Bi0.5)TiO3-BaTiO3

Heterophase structures in lead-free perovskite-type ferroelectric solid solutions of (1 - z)(Na0.5Bi0.5)TiO3 - zBaTiO(3) are analysed for a few critical compositions near the morphotropic phase boundary (z = 0.05-0.07). Examples of the phase coexistence and elastic matching of the phases from different symmetry groups are considered to find optimum volume fractions of specific domain types and coexisting phases at the complete stress relief in two-phase samples. Some interrelations between these volume fractions are described using variants of the domain arrangement at changes in the composition and unit-cell parameters. The evaluated room-temperature volume fractions of the ferroelectric monoclinic (Cm symmetry) and tetragonal (P4mm symmetry) phases near the morphotropic phase boundary are in agreement with experimental data.