Pressure Dependence of Glass Transition in As2Te3 Glass

Amorphous solids prepared from their melt state exhibit glass transition phenomenon upon heating. Viscosity, specific heat, and thermal expansion coefficient of the amorphous solids show rapid changes at the glass transition temperature (T-g). Generally, application of high pressure increases the T-g and this increase (a positive dT(g)/dP) has been understood adequately with free volume and entropy models which are purely thermodynamic in origin. In this study, the electrical resistivity of semiconducting As2Te3 glass at high pressures as a function of temperature has been measured in a Bridgman anvil apparatus. Electrical resistivity showed a pronounced change at T-g. The T-g estimated from the slope change in the resistivity-temperature plot shows a decreasing trend (negative dT(g)/dP). The dT(g)/dP was found to be -2.36 degrees C/kbar for a linear fit and -2.99 degrees C/kbar for a polynomial fit in the pressure range 1 bar to 9 kbar. Chalcogenide glasses like Se, As2Se3, and As30Se30Te40 show a positive dT(g)/dP which is very well understood in terms of the thermodynamic models. The negative dT(g)/dP (which is generally uncommon in liquids) observed for As2Te3 glass is against the predictions of the thermodynamic models. The Adam-Gibbs model of viscosity suggests a direct relationship between the isothermal pressure derivative of viscosity and the relaxational expansion coefficient. When the sign of the thermal expansion coefficient is negative, dT(g)/dP = Delta k/Delta alpha will be less than zero, which can result in a negative dT(g)/dP. In general, chalcogenides rich in tellurium show a negative thermal expansion coefficient (NTE) in the supercooled and stable liquid states. Hence, the negative dT(g)/dP observed in this study can be understood on the basis of the Adams-Gibbs model. An electronic model proposed by deNeufville and Rockstad finds a linear relation between T-g and the optical band gap (E-g for covalent semiconducting glasses when they are grouped according to their average coordination number. The electrical band gap (Delta E) of As2Te3 glass decreases with pressure. The optical and electrical band gaps are related as Delta E-g = 2 Delta E; thus, a negative dT(g)/dP is expected when As2Te3 glass is subjected to high pressures. In this sense, As2Te3 is a unique glass where its variation of T-g with pressure can be understood by both electronic and thermodynamic models.

Modelling of optical transport behavior of organic photovoltaic devices with nano-pillar transparent conducting electrodes

Optical transport behavior of organic photo-voltaic devices with nano-pillar transparent electrodes is investigated in this paper in order to understand possible enhancement of their charge-collection efficiency. Modeling and simulations of optical transport due to this architecture show an interesting regime of length-scale dependent optical characteristics. An electromagnetic wave propagation model is employed with simulation objectives toward understanding the mechanism of optical scattering and waveguide effects due to the nano-pillars and effective transmission through the active layer. Partial filling of gaps between the nano-pillars due to the nano-fabrication process is taken into consideration. Observations made in this paper will facilitate appropriate design rules for nano-pillar electrodes. (C) 2014 AIP Publishing LLC.

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.

Time resolved terahertz spectroscopy of low frequency electronic resonances and optical pump-induced terahertz photoconductivity in reduced graphene oxide membrane

Towards ultrafast optoelectronic applications of single and a few layer reduced graphene oxide (RGO), we study time domain terahertz spectroscopy and optical pump induced changes in terahertz conductivity of self-supported RGO membrane in the spectral window of 0.5-3.5 THz. The real and imaginary parts of conductivity spectra clearly reveal low frequency resonances, attributed to the energy gaps due to the van Hove singularities in the density of states flanking the Dirac points arising due to the relative rotation of the graphene layers. Further, optical pump induced terahertz conductivity is positive, pointing to the dominance of intraband scattering processes. The relaxation dynamics of the photo-excited carriers consists of three cooling pathways: the faster (similar to 450 fs) one due to optical phonon emission followed by disorder mediated large momentum and large energy acoustic phonon emission with a time constant of a few ps (called the super-collision mechanism) and a very large time (similar to 100 ps) arising from the deep trap states. The frequency dependence of the dynamic conductivity at different delay times is analyzed in term of Drude-Smith model. (C) 2014 Published by Elsevier Ltd.

Combining data sets of satellite-retrieved products for basin-scale water balance study: 2. Evaluation on the Mississippi Basin and closure correction model

In this study, we applied the integration methodology developed in the companion paper by Aires (2014) by using real satellite observations over the Mississippi Basin. The methodology provides basin-scale estimates of the four water budget components (precipitation P, evapotranspiration E, water storage change Delta S, and runoff R) in a two-step process: the Simple Weighting (SW) integration and a Postprocessing Filtering (PF) that imposes the water budget closure. A comparison with in situ observations of P and E demonstrated that PF improved the estimation of both components. A Closure Correction Model (CCM) has been derived from the integrated product (SW+PF) that allows to correct each observation data set independently, unlike the SW+PF method which requires simultaneous estimates of the four components. The CCM allows to standardize the various data sets for each component and highly decrease the budget residual (P - E - Delta S - R). As a direct application, the CCM was combined with the water budget equation to reconstruct missing values in any component. Results of a Monte Carlo experiment with synthetic gaps demonstrated the good performances of the method, except for the runoff data that has a variability of the same order of magnitude as the budget residual. Similarly, we proposed a reconstruction of Delta S between 1990 and 2002 where no Gravity Recovery and Climate Experiment data are available. Unlike most of the studies dealing with the water budget closure at the basin scale, only satellite observations and in situ runoff measurements are used. Consequently, the integrated data sets are model independent and can be used for model calibration or validation.

Sensitivity of polarization fluctuations to the nature of protein-water interactions: Study of biological water in four different protein-water systems

Since the time of Kirkwood, observed deviations in magnitude of the dielectric constant of aqueous protein solution from that of neat water (similar to 80) and slower decay of polarization have been subjects of enormous interest, controversy, and debate. Most of the common proteins have large permanent dipole moments (often more than 100 D) that can influence structure and dynamics of even distant water molecules, thereby affecting collective polarization fluctuation of the solution, which in turn can significantly alter solution's dielectric constant. Therefore, distance dependence of polarization fluctuation can provide important insight into the nature of biological water. We explore these aspects by studying aqueous solutions of four different proteins of different characteristics and varying sizes, chicken villin headpiece subdomain (HP-36), immunoglobulin binding domain protein G (GB1), hen-egg white lysozyme (LYS), and Myoglobin (MYO). We simulate fairly large systems consisting of single protein molecule and 20000-30000 water molecules (varied according to the protein size), providing a concentration in the range of similar to 2-3 mM. We find that the calculated dielectric constant of the system shows a noticeable increment in all the cases compared to that of neat water. Total dipole moment auto time correlation function of water < dM(W) (0)delta M-W (t) > is found to be sensitive to the nature of the protein. Surprisingly, dipole moment of the protein and total dipole moment of the water molecules are found to be only weakly coupled. Shellwise decomposition of water molecules around protein reveals higher density of first layer compared to the succeeding ones. We also calculate heuristic effective dielectric constant of successive layers and find that the layer adjacent to protein has much lower value (similar to 50). However, progressive layers exhibit successive increment of dielectric constant, finally reaching a value close to that of bulk 4-5 layers away. We also calculate shellwise orientational correlation function and tetrahedral order parameter to understand the local dynamics and structural re-arrangement of water. Theoretical analysis providing simple method for calculation of shellwise local dielectric constant and implication of these findings are elaborately discussed in the present work. (C) 2014 AIP Publishing LLC.

Lineage delimitation and description of nine new species of bush frogs (Anura: Raorchestes, Rhacophoridae) from the Western Ghats Escarpment

Bush frogs of the genus Raorchestes are distributed mainly in the Western Ghats Escarpment of Peninsular India. The inventory of species in this genus is incomplete and there is ambiguity in the systematic status of species recognized by morphological criteria. To address the dual problem of taxon sampling and systematic uncertainty in bush frogs, we used a large-scale spatial sampling design, explicitly incorporating the geographic and ecological heterogeneity of the Western Ghats. We then used a hierarchical multi-criteria approach by combining mitochondrial phylogeny, genetic distance, geographic range, morphology and advertisement call to delimit bush frog lineages. Our analyses revealed the existence of a large number of new lineages with varying levels of genetic divergence. Here, we provide diagnoses and descriptions for nine lineages that exhibit divergence across multiple axes. The discovery of new lineages that exhibit high divergence across wide ranges of elevation and across the major massifs highlights the large gaps in historical sampling. These discoveries underscore the significance of addressing inadequate knowledge of species distribution, namely the ``Wallacean shortfall'', in addressing the problem of taxon sampling and unknown diversity in tropical hotspots. A biogeographically informed sampling and analytical approach was critical in detecting and delineating lineages in a consistent manner across the genus. Through increased taxon sampling, we were also able to discern a number of well-supported sub-clades that were either unresolved or absent in earlier phylogenetic reconstructions and identify a number of shallow divergent lineages which require further examination for assessment of their taxonomic status.

Properties of the chalcogenide-carbon nano tubes and graphene composite materials

Composite can deliver more than the individual elemental property of the material. Specifically chalcogenide- multi walled carbon nano tubes and chalcogenide- bilayer graphene composite materials could be interesting for the investigation, which have been less covered by the investigators. We describe micro structural properties of Se55Te25Ge20, Se55Te25Ge20 + 0.025% multi walled carbon nano tubes and Se55Te25Ge20 + 0.025% bilayer graphene materials. This gives realization of the alloying constituents inclusion/or diffusion inside the multi walled carbon nano tubes and bilayer graphene under the homogeneous parent alloy configuration. Raman spectroscopy, X-ray photoelectron spectroscopy, UV/Visible spectroscopy and Fourier transmission infrared spectroscopy have also been carried out under the discussion. A considerable core energy levels peak shifts have been noticed for the composite materials by the X-ray photoelectron spectroscopy. The optical energy band gaps are measured to be varied in between 1.2 and 1.3 eV. In comparison to parent (Se55Te25Ge20) alloy a higher infrared transmission has been observed for the composite materials. Subsequently, variation in physical properties has been explained on the basis of bond formation in solids. (C) 2014 Elsevier B. V. All rights reserved.

Photo-induced optical bleaching in Ge12Sb25S63 amorphous chalcogenide thin films: effect of 532 nm laser illumination

The photo-induced effects of Ge12Sb25S63 films illuminated with 532 nm laser light are investigated from transmission spectra measured by FTIR spectroscopy. The material exhibits photo-bleaching (PB) when exposed to band gap light for a prolonged time in a vacuum. The PB is ascribed to structural changes inside the film as well as surface photooxidation. The amorphous nature of thin films was detected by x-ray diffraction. The chemical composition of the deposited thin films was examined by energy dispersive x-ray analysis (EDAX). The refractive indices of the films were obtained from the transmission spectra based on an inverse synthesis method and the optical band gaps were derived from optical absorption spectra using the Tauc plot. The dispersion of the refractive index is discussed in terms of the single-oscillator Wemple-DiDomenico model. It was found that the mechanism of the optical absorption follows the rule of the allowed non-direct transition. Raman and x-ray photoelectron spectra (XPS) were measured and decomposed into several peaks that correspond to the different structural units which support the optical changes.

Benchmarking sustainability of Indian electricity system: An indicator approach

India needs to significantly increase its electricity consumption levels, in a sustainable manner, if it has to ensure rapid economic development, a goal that remains the most potent tool for delivering adaptation capacity to its poor who will suffer the worst consequences of climate change. Resource/supply constraints faced by conventional energy sources, techno-economic constraints faced by renewable energy sources, and the bounds imposed by climate change on fossil fuel use are likely to undermine India's quest for having a robust electricity system that can effectively contribute to achieving accelerated, sustainable and inclusive economic growth. One possible way out could be transitioning into a sustainable electricity system, which is a trade-off solution having taken into account the economic, social and environmental concerns. As a first step toward understanding this transition, we contribute an indicator based hierarchical multidimensional framework as an analytical tool for sustainability assessment of electricity systems, and validate it for India's national electricity system. We evaluate Indian electricity system using this framework by comparing it with a hypothetical benchmark sustainable electrical system, which was created using best indicator values realized across national electricity systems in the world. This framework, we believe, can be used to examine the social, economic and environmental implications of the current Indian electricity system as well as setting targets for future development. The analysis with the indicator framework provides a deeper understanding of the system, identify and quantify the prevailing sustainability gaps and generate specific targets for interventions. We use this framework to compute national electricity system sustainability index (NESSI) for India. (C) 2014 Elsevier Ltd. All rights reserved.

A new approach to depict bone surfaces in finger imaging using photoacoustic tomography

Imaging the vasculature close around the finger joints is of interest in the field of rheumatology. Locally increased vasculature in the synovial membrane of these joints can be a marker for rheumatoid arthritis. In previous work we showed that part of the photoacoustically induced ultrasound from the epidermis reflects on the bone surface within the finger. These reflected signals could be wrongly interpreted as new photoacoustic sources. In this work we show that a conventional ultrasound reconstruction algorithm, that considers the skin as a collection of ultrasound transmitters and the PA tomography probe as the detector array, can be used to delineate bone surfaces of a finger. This can in the future assist in the localization of the joint gaps. This can provide us with a landmark to localize the region of the inflamed synovial membrane. We test the approach on finger mimicking phantoms.

Novel Design of Honeycombs Using a Seamless Combination of Auxetic and Conventional Cores Toward Phononic Band Gap Engineering

A novel design for the geometric configuration of honeycombs using a seamless combination of auxetic and conventional cores- elements with negative and positive Possion ratios respectively, has been presented. The proposed design has been shown to generate a superior band gap property while retaining all major advantages of a purely conventional or purely auxetic honeycomb structure. Seamless combination ensures that joint cardinality is also retained. Several configurations involving different degree of auxeticity and different proportions auxetic and conventional elements have been analyzed. It has been shown that the preferred configurations open up wide and clean band gap at a significantly lower frequency ranges compared to their pure counterparts. In view of existence of band gaps being desired feature for the phononic applications, reported results might be appealing. Use of such design may enable superior vibration control as well. Proposed configurations can be made isovolumic and iso-weight giving designers a fairer ground of applying such configurations without significantly changing size and weight criteria.

Dynamics of Cricket Sound Production

The clever designs of natural transducers are a great source of inspiration for man-made systems. At small length scales, there are many transducers in nature that we are now beginning to understand and learn from. Here, we present an example of such a transducer that is used by field crickets to produce their characteristic song. This transducer uses two distinct components-a file of discrete teeth and a plectrum that engages intermittently to produce a series of impulses forming the loading, and an approximately triangular membrane, called the harp, that acts as a resonator and vibrates in response to the impulse-train loading. The file-and-plectrum act as a frequency multiplier taking the low wing beat frequency as the input and converting it into an impulse-train of sufficiently high frequency close to the resonant frequency of the harp. The forced vibration response results in beats producing the characteristic sound of the cricket song. With careful measurements of the harp geometry and experimental measurements of its mechanical properties (Young's modulus determined from nanoindentation tests), we construct a finite element (FE) model of the harp and carry out modal analysis to determine its natural frequency. We fine tune the model with appropriate elastic boundary conditions to match the natural frequency of the harp of a particular species-Gryllus bimaculatus. We model impulsive loading based on a loading scheme reported in literature and predict the transient response of the harp. We show that the harp indeed produces beats and its frequency content matches closely that of the recorded song. Subsequently, we use our FE model to show that the natural design is quite robust to perturbations in the file. The characteristic song frequency produced is unaffected by variations in the spacing of file-teeth and even by larger gaps. Based on the understanding of how this natural transducer works, one can design and fabricate efficient microscale acoustic devices such as microelectromechanical systems (MEMS) loudspeakers.

Effect of Chalcogens on Electronic and Photophysical Properties of Vinylene-Based Diketopyrrolopyrrole Copolymers

Three vinylene linked diketopyrrolopyrrole based donor acceptor (D-A) copolymers have been synthesized with phenyl, thienyl, and selenyl units as donors. Optical and electronic properties were investigated with UV-vis absorption spectroscopy, cyclic voltammetry, near edge X-ray absorption spectroscopy, organic field effect transistor (OFET) measurements, and density functional theory (DFT) calculations. Optical and electrochemical band gaps decrease in the order phenyl, thienyl, and selenyl. Only phenyl-based polymers are nonplanar, but the main contributor to the larger band gap is electronic, not structural effects. Thienyl and selenyl polymers exhibit ambipolar charge transport but with higher hole than electron mobility. Experimental and theoretical results predict the selenyl system to have the best transport properties, but OFET measurements prove the thienyl system to be superior with p-channel mobility as high as 0.1 cm(2) V-1 s(-1).

Spectral characterizations and photophysical properties of one-step synthesized blue fluorescent 4 `-aryl substituted 2,2 `:6 `,2 `'-terpyridine for OLEDs application

We have synthesized a series of 4'-aryl substituted 2,2':6',2 `'-terpyridine (terpy) derivatives, namely 4'-(4-methylphenyl)-2,2':6',2 `'-terpyridine (C-1), 4'-(2-furyl)-2,2':6'2 `'-terpyridine (C-2), and 4'-(3,4,5-trimethoxyphenyl)-2,2':6',2 `'-terpyridine (C-3). The synthesized terpy compounds were characterized by elemental analyses, FTIR, NMR (H-1 and C-13), and ESI-Mass spectrometry. Photophysical, electrochemical and thermal properties of terpy compounds were systematically studied. Maximum excitation band was observed between 240 and 330 nm using UV-visible spectra, and maximum emission peaks from PL spectra were observed at 385, 405 and 440 nm for C-1, C-2 and C-3 respectively. Fluorescence lifetime (tau) of the fluorophores was found to be 035 and 1.55 ns at the excitation wavelength of 406 nm for C-1 and C-2 respectively, and tau value for C-3 was found to be 0.29 ns at the excitation wavelength of 468 nm. We noticed that the calculated values of HOMO energy levels were increased from 5.96 (C-1) to 6.08 (C-3) eV, which confirms that C-3 derivative is more electrons donating in nature. The calculated electrochemical band gaps were 2.95, 2.82 and 3.02 eV for C-1, C-2 and C-3 respectively. These blue fluorescent emitter derivatives can be used as an electron transport and electroluminescent material to design the blue fluorescent organic light emitting diode (OLED) applications. (C) 2015 Elsevier B.V: All rights reserved.