Controlling Light Absorption in Charge-Separating Core/Shell Semiconductor Nanocrystals

Semiconductor nanocrystals of different formulations have been extensively studied for use in thin-film photovoltaics. Materials used in such devices need to satisfy the stringent requirement of having large absorption cross sections. Hence, type-II semiconductor nanocrystals that are generally considered to be poor light absorbers have largely been ignored. In this article, we show that type-II semiconductor nanocrystals can be tailored to match the light-absorption abilities of other types of nanostructures as well as bulk semiconductors. We synthesize type-II ZnTe/CdS core/shell nanocrystals. This material is found to exhibit a tunable band gap as well as absorption cross sections that are comparable to (die. This result has significant implications for thin-film photovoltaics, where the use of type-II nanocrystals instead of pure semiconductors can improve charge separation while also providing a much needed handle to regulate device composition.

Chemical vapor detection using nonlinear electrical properties of carbon nanotube bundles

We demonstrate the electrical transport behavior of carbon nanotubes (CNTs) upon exposure to organic analytes (namely ethanol, benzene, acetone and toluene). The resulting nonlinear current-voltage characteristics revealed a power law dependence of the differential conductivity on the applied bias voltage. Moreover, suppression of differential conductivity at zero bias is found to be dependent on different selective analytes. The power law exponent values have been monitored before, during and after exposure to the chemicals, which revealed a reversible change in the number of electron conducting channels. Therefore, the reduction in the number of conductive paths can be attributed to the interaction of the chemical analyte on the CNT surfaces, which causes a decrease in the differential conductivity of the CNT sample. These results demonstrate chemical selectivity of CNTs due to varying electronic interaction with different chemical analytes.

Solvent-induced changes on the polarity of the triplet excited state of 2-chlorothioxanthone: From time-resolved absorption and resonance Raman spectroscopies

Solvent polarity has been known to influence the triplet state structure and reactivity. Here, we present our experimental and theoretical study on the effect of solvent on the lowest triplet excited state structure of 2-chlorothioxanthone (CTX). Time-resolved absorption (TA) spectroscopy has been employed to understand the triplet state electronic structure; whereas solvent-induced structural changes have been studied using time-resolved resonance Raman (TR3) spectroscopy. Both the DFT and TD-DFT calculations have been performed in the solution phase employing self-consistent reaction field implicit solvation model to support the experimental data. It has been observed that CO stretching frequencies of the excited triplet state are sensitive to the solvent polarity and increase with the increase in the solvent polarity. Both TA and TR3 studies reveal that specific solvent effect (H-bonding) is more pronounced in comparison to the nonspecific solvent effect. (C) 2013 Elsevier B.V. All rights reserved.

Valence band electronic structure of Nd1-xYxMnO3 using X-ray absorption, photoemission and GGA plus U calculations

The electronic structures of Nd1-xYxMnO3 (x=0-0.5) were studied using X-ray absorption near-edge structure (XANES) at the Mn L-3,L-2- and O K-edge along with valence-band photoemission spectroscopy (VB-PES). The systematic increase in white-line intensity of the Mn L-3,L-2-edge with doping, suggests a decrease in the occupancy of Mn 3d orbitals. The O K-edge XANES shows a depletion of unoccupied states above the Fermi energy. The changes in the O K-edge spectra due to doping reflects an increase in the Jahn-Teller distortion. The VB-PES shows broadening of the features associated with Mn 3d and O 2p hybridized states and the shift of these features to a slightly higher binding energy in agreement with our GGA + U calculations. The system shows a net shift of the occupied and unoccupied states away from the Fermi energy with doping. The shift in theoretical site-projected density of states of x=0.5 composition with respect to x=0 suggest a subtle change from a charge transfer to Mott-Hubbard type insulator. (C) 2013 Elsevier B.V. All rights reserved.

Biased PN based impact angle constrained guidance using a nonlinear engagement model

Impact angle constrained guidance laws are important in many applications such as guidance of torpedoes, anti-ballistic missiles and reentry vehicles. In this paper, we design a guidance law which is capable of achieving a wide range of impact angles. Biased proportional navigation guidance uses a bias term in addition to the basic PN command to satisfy additional constraints. Angle constrained BPNG (ACBPNG) uses small angle approximations to derive the bias term for impact angle requirement. We design a modified ACBPNG (MACBPNG) where the required bias term is derived in a closed form considering non-linear equations of motion. Simulations are carried out for a wide range of impact angle requirements. We also analyze capturability from different initial positions and also the launch angles possible at each initial position. The performance of the proposed law is compared with an existing law.

Nonlinear and linear autopilot performance comparison of tactical flight vehicle

n this paper, three-axis autopilot of a tactical flight vehicle has been designed for surface to air application. Both nonlinear and linear design synthesis and analysis have been carried out pertaining to present flight vehicle. Lateral autopilot performance has been compared by tracking lateral acceleration components along yaw and pitch plane at higher angles of attack in presence of side force and aerodynamic nonlinearity. The nonlinear lateral autopilot design is based on dynamic inversion and time scale separation principle. The linear lateral autopilot design is based on three-loop topology. Roll autopilot robustness performance has been enhanced against unmodeled roll disturbances by backstepping technique. Complete performance comparison results of both nonlinear and linear controller based on six degrees of freedom simulation along with stability and robustness studies with respect to plant parameter variation have been discussed in the paper.

Closed-form nonlinear sectional analysis of pretwisted anisotropic beam with multiple delaminations

Fiber reinforced laminated composite open-section beams are widely used as bearingless rotor flex beams because of their high specific strength and stiffness as well as fatigue life. These laminated composite structures exhibit a number of different failure modes, including fiber-matrix debonding within individual layers, delamination or separation of the layers, transverse cracks through one or more layers and fiber fracture. Delamination is a predominant failure mode in continuous fiber reinforced laminated composites and often initiate near the free edges of the structure. The appearance of delaminations in the composite rotorcraft flexbeams can lead to deterioration of the mechanical properties and, in turn, the helicopter performance as well as safety. Understanding and predicting the influence of free-edge delamination on the overall behavior of the laminates will provide quantitative measures of the extent of the damage and help ensure their damage tolerance.

A Kushner-Stratonovich Monte Carlo filter applied to nonlinear dynamical system identification

A Monte Carlo filter, based on the idea of averaging over characteristics and fashioned after a particle-based time-discretized approximation to the Kushner-Stratonovich (KS) nonlinear filtering equation, is proposed. A key aspect of the new filter is the gain-like additive update, designed to approximate the innovation integral in the KS equation and implemented through an annealing-type iterative procedure, which is aimed at rendering the innovation (observation prediction mismatch) for a given time-step to a zero-mean Brownian increment corresponding to the measurement noise. This may be contrasted with the weight-based multiplicative updates in most particle filters that are known to precipitate the numerical problem of weight collapse within a finite-ensemble setting. A study to estimate the a-priori error bounds in the proposed scheme is undertaken. The numerical evidence, presently gathered from the assessed performance of the proposed and a few other competing filters on a class of nonlinear dynamic system identification and target tracking problems, is suggestive of the remarkably improved convergence and accuracy of the new filter. (C) 2013 Elsevier B.V. All rights reserved.

Electronic structure of Nd1-xYxMnO3 from Mn K edge absorption spectroscopy and DFT methods

The electronic structure of Nd1-xYxMnO3 (x-0-0.5) is studied using x-ray absorption near-edge structure (XANES) spectroscopy at the Mn K-edge along with the DFT-based LSDA+U and real space cluster calculations. The main edge of the spectra does not show any variation with doping. The pre-edge shows two distinct features which appear well-separated with doping. The intensity of the pre-edge decreases with doping. The theoretical XANES were calculated using real space multiple scattering methods which reproduces the entire experimental spectra at the main edge as well as the pre-edge. Density functional theory calculations are used to obtain the Mn 4p, Mn 3d and O 2p density of states. For x=0, the site-projected density of states at 1.7 eV above Fermi energy shows a singular peak of unoccupied e(g) (spin-up) states which is hybridized Mn 4p and O 2p states. For x=0.5, this feature develops at a higher energy and is highly delocalized and overlaps with the 3d spin-down states which changes the pre-edge intensity. The Mn 4p DOS for both compositions, show considerable difference between the individual p(x), p(y) and p(z)), states. For x=0.5, there is a considerable change in the 4p orbital polarization suggesting changes in the Jahn-Teller effect with doping. (C) 2013 Elsevier Ltd. All rights reserved.

Nonlinear gravity-wave interactions in stratified turbulence

To investigate the dynamics of gravity waves in stratified Boussinesq flows, a model is derived that consists of all three-gravity-wave-mode interactions (the GGG model), excluding interactions involving the vortical mode. The GGG model is a natural extension of weak turbulence theory that accounts for exact three-gravity-wave resonances. The model is examined numerically by means of random, large-scale, high-frequency forcing. An immediate observation is a robust growth of the so-called vertically sheared horizontal flow (VSHF). In addition, there is a forward transfer of energy and equilibration of the nonzero-frequency (sometimes called ``fast'') gravity-wave modes. These results show that gravity-wave-mode interactions by themselves are capable of systematic interscale energy transfer in a stratified fluid. Comparing numerical simulations of the GGG model and the full Boussinesq system, for the range of Froude numbers (Fr) considered (0.05 a parts per thousand currency sign Fr a parts per thousand currency sign 1), in both systems the VSHF is hardest to resolve. When adequately resolved, VSHF growth is more vigorous in the GGG model. Furthermore, a VSHF is observed to form in milder stratification scenarios in the GGG model than the full Boussinesq system. Finally, fully three-dimensional nonzero-frequency gravity-wave modes equilibrate in both systems and their scaling with vertical wavenumber follows similar power-laws. The slopes of the power-laws obtained depend on Fr and approach -2 (from above) at Fr = 0.05, which is the strongest stratification that can be properly resolved with our computational resources.

Kinetically stabilized C-60-toluene solvate nanostructures with a discrete absorption edge enabling supramolecular topotactic molecular exchange

Nanosized fullerene solvates have attracted widespread research attention due to recent interesting discoveries. A particular type of solvate is limited to a fixed number of solvents and designing new solvates within the same family is a fundamental challenge. Here we demonstrate that the hexagonal closed packed (HCP) phase of C-60 solvates, formed with m-xylene, can also be stabilized using toluene. Contrary to the notion on their instability, these can be stabilized from minutes up to months by tuning the occupancy of solvent molecules. Due to high stability, we could record their absorption edge, and measure excitonic life-time, which has not been reported for any C-60 solvate. Despite being solid, absorbance spectrum of the solvates is similar in appearance to that of C-60 in solution. A new absorption band appears at 673 nm. The fluorescence lifetime at 760 nm is similar to 1.2 ns, suggesting an excited state unaffected by solvent-C-60 interaction. Finally, we utilized the unstable set of HCP solvates to exchange with a second solvent by a topotactic exchange mechanism, which rendered near permanent stability to the otherwise few minutes stable solvates. This is also the first example of topotactic exchange in supramolecular crystal, which is widely known in ionic solids. (C) 2014 Elsevier Ltd. All rights reserved.

Study of phase synchronization in multichannel seizure EEG using nonlinear recurrence measure

Complex biological systems such as the human brain can be expected to be inherently nonlinear and hence difficult to model. Most of the previous studies on investigations of brain function have either used linear models or parametric nonlinear models. In this paper, we propose a novel application of a nonlinear measure of phase synchronization based on recurrences, correlation between probabilities of recurrence (CPR), to study seizures in the brain. The advantage of this nonparametric method is that it makes very few assumptions thus making it possible to investigate brain functioning in a data-driven way. We have demonstrated the utility of CPR measure for the study of phase synchronization in multichannel seizure EEG recorded from patients with global as well as focal epilepsy. For the case of global epilepsy, brain synchronization using thresholded CPR matrix of multichannel EEG signals showed clear differences in results obtained for epileptic seizure and pre-seizure. Brain headmaps obtained for seizure and preseizure cases provide meaningful insights about synchronization in the brain in those states. The headmap in the case of focal epilepsy clearly enables us to identify the focus of the epilepsy which provides certain diagnostic value. Comparative studies with linear correlation have shown that the nonlinear measure CPR outperforms the linear correlation measure. (C) 2014 Elsevier Ltd. All rights reserved.

Nonlinear viscoelasticity of entangled wormlike micellar fluid under large-amplitude oscillatory shear: Role of elastic Taylor-Couette instability

The role of elastic Taylor-Couette flow instabilities in the dynamic nonlinear viscoelastic response of an entangled wormlike micellar fluid is studied by large-amplitude oscillatory shear (LAOS) rheology and in situ polarized light scattering over a wide range of strain and angular frequency values, both above and below the linear crossover point. Well inside the nonlinear regime, higher harmonic decomposition of the resulting stress signal reveals that the normalized third harmonic I-3/I-1 shows a power-law behavior with strain amplitude. In addition, I-3/I-1 and the elastic component of stress amplitude sigma(E)(0) show a very prominent maximum at the strain value where the number density (n(v)) of the Taylor vortices is maximum. A subsequent increase in applied strain (gamma) results in the distortions of the vortices and a concomitant decrease in n(v), accompanied by a sharp drop in I-3 and sigma(E)(0). The peak position of the spatial correlation function of the scattered intensity along the vorticity direction also captures the crossover. Lissajous plots indicate an intracycle strain hardening for the values of gamma corresponding to the peak of I-3, similar to that observed for hard-sphere glasses.