Fine-Tuning Dual Emission and Aggregation-Induced Emission Switching in NPI-BODIPY Dyads

Three new NPI-BODIPY dyads 1-3 (NPI = 1,8-naphthalimide, BODIPY = boron-dipyrromethene) were synthesized, characterized, and studied. The NPI and BODIPY moieties in these dyads are electronically separated by oxoaryl bridges, and the compounds only differ structurally with respect to methyl substituents on the BODIPY fluorophore. The NPI and BODIPY moieties retain their optical features in molecular dyads 1-3. Dyads 1-3 show dual emission in solution originating from the two separate fluorescent units. The variations of the dual emission in these compounds are controlled by the structural flexibilities of the systems. Dyads 13, depending on their molecular flexibilities, show considerably different spectral shapes and dissimilar intensity ratios of the two emission bands. The dyads also show significant aggregation-induced emission switching (AIES) on formation of nano-aggregates in THF/H2O with changes in emission color from green to red. Whereas the flexible and aggregation-prone compound 1 shows AIES, rigid systems with less favorable intermolecular interactions (i.e., 2 and 3) show aggregation-induced quenching of emission. Correlations of the emission intensity and structural flexibility were found to be reversed in solution and aggregated states. Photophysical and structural investigations suggested that intermolecular interactions (e. g., pi-pi stacking) play a major role in controlling the emission of these compounds in the aggregated state.

Variations in the pulsation and spectral characteristics of OAO 1657-415

We present broad-band pulsation and spectral characteristics of the accreting X-ray pulsar OAO 1657-415 with a 2.2 d long Suzaku observation carried out covering its orbital phase range similar to 0.12-0.34, with respect to the mid-eclipse. During the last third of the observation, the X-ray count rate in both the X-ray Imaging Spectrometer (XIS) and the HXD-PIN instruments increased by a factor of more than 10. During this observation, the hardness ratio also changed by a factor of more than 5, uncorrelated with the intensity variations. In two segments of the observation, lasting for similar to 30-50 ks, the hardness ratio is very high. In these segments, the spectrum shows a large absorption column density and correspondingly large equivalent widths of the iron fluorescence lines. We found no conclusive evidence for the presence of a cyclotron line in the broad-band X-ray spectrum with Suzaku. The pulse profile, especially in the XIS energy band, shows evolution with time but not so with energy. We discuss the nature of the intensity variations, and variations of the absorption column density and emission lines during the duration of the observation as would be expected due to a clumpy stellar wind of the supergiant companion star. These results indicate that OAO 1657-415 has characteristics intermediate to the normal supergiant systems and the systems that show fast X-ray transient phenomena.

A spectral multiscale method for wave propagation analysis: Atomistic-continuum coupled simulation

In this paper, we present a new multiscale method which is capable of coupling atomistic and continuum domains for high frequency wave propagation analysis. The problem of non-physical wave reflection, which occurs due to the change in system description across the interface between two scales, can be satisfactorily overcome by the proposed method. We propose an efficient spectral domain decomposition of the total fine scale displacement along with a potent macroscale equation in the Laplace domain to eliminate the spurious interfacial reflection. We use Laplace transform based spectral finite element method to model the macroscale, which provides the optimum approximations for required dynamic responses of the outer atoms of the simulated microscale region very accurately. This new method shows excellent agreement between the proposed multiscale model and the full molecular dynamics (MD) results. Numerical experiments of wave propagation in a 1D harmonic lattice, a 1D lattice with Lennard-Jones potential, a 2D square Bravais lattice, and a 2D triangular lattice with microcrack demonstrate the accuracy and the robustness of the method. In addition, under certain conditions, this method can simulate complex dynamics of crystalline solids involving different spatial and/or temporal scales with sufficient accuracy and efficiency. (C) 2014 Elsevier B.V. All rights reserved.

Asynchronous Gossip for Averaging and Spectral Ranking

We consider two variants of the classical gossip algorithm. The first variant is a version of asynchronous stochastic approximation. We highlight a fundamental difficulty associated with the classical asynchronous gossip scheme, viz., that it may not converge to a desired average, and suggest an alternative scheme based on reinforcement learning that has guaranteed convergence to the desired average. We then discuss a potential application to a wireless network setting with simultaneous link activation constraints. The second variant is a gossip algorithm for distributed computation of the Perron-Frobenius eigenvector of a nonnegative matrix. While the first variant draws upon a reinforcement learning algorithm for an average cost controlled Markov decision problem, the second variant draws upon a reinforcement learning algorithm for risk-sensitive control. We then discuss potential applications of the second variant to ranking schemes, reputation networks, and principal component analysis.

A charge self-consistent LDA plus DMFT study of the spectral properties of hexagonal NiS

The electronic structure and spectral properties of hexagonal NiS have been studied in the high temperature paramagnetic phase and low temperature anti-ferromagnetic phase. The calculations have been performed using charge self-consistent density-functional theory in local density approximation combined with dynamical mean-field theory (LDA+DMFT). The photoemission spectra (PES) and optical properties have been computed and compared with the experimental data. Our results show that the dynamical correlation effects are important to understand the spectral and optical properties of NiS. These effects have been analyzed in detail by means of the computed real and imaginary part of the self-energy.

The Tetrablock as a Spectral Set

The tetrablock, roughly speaking, is the set of all linear fractional maps that map the open unit disc to itself. A formal definition of this inhomogeneous domain is given below. This paper considers triples of commuting bounded operators (A,B,P) that have the tetrablock as a spectral set. Such a triple is named a tetrablock contraction. The motivation comes from the success of model theory in another inhomogeneous domain, namely, the symmetrized bidisc F. A pair of commuting bounded operators (S,P) with Gamma as a spectral set is called a Gamma-contraction, and always has a dilation. The two domains are related intricately as the Lemma 3.2 below shows. Given a triple (A, B, P) as above, we associate with it a pair (F-1, F-2), called its fundamental operators. We show that (A,B,P) dilates if the fundamental operators F-1 and F-2 satisfy certain commutativity conditions. Moreover, the dilation space is no bigger than the minimal isometric dilation space of the contraction P. Whether these commutativity conditions are necessary, too, is not known. what we have shown is that if there is a tetrablock isometric dilation on the minimal isometric dilation space of P. then those commutativity conditions necessarily get imposed on the fundamental operators. En route, we decipher the structure of a tetrablock unitary (this is the candidate as the dilation triple) and a tertrablock isometry (the restriction of a tetrablock unitary to a joint invariant sub-space). We derive new results about r-contractions and apply them to tetrablock contractions. The methods applied are motivated by 11]. Although the calculations are lengthy and more complicated, they beautifully reveal that the dilation depends on the mutual relationship of the two fundamental operators, so that certain conditions need to be satisfied. The question of whether all tetrablock contractions dilate or not is unresolved.

Wave propagation analysis in adhesively bonded composite joints using the wavelet spectral finite element method

A wavelet spectral finite element (WSFE) model is developed for studying transient dynamics and wave propagation in adhesively bonded composite joints. The adherands are formulated as shear deformable beams using the first order shear deformation theory (FSDT) to obtain accurate results for high frequency wave propagation. Equations of motion governing wave motion in the bonded beams are derived using Hamilton's principle. The adhesive layer is modeled as a line of continuously distributed tension/compression and shear springs. Daubechies compactly supported wavelet scaling functions are used to transform the governing partial differential equations from time domain to frequency domain. The dynamic stiffness matrix is derived under the spectral finite element framework relating the nodal forces and displacements in the transformed frequency domain. Time domain results for wave propagation in a lap joint are validated with conventional finite element simulations using Abaqus. Frequency domain spectrum and dispersion relation results are presented and discussed. The developed WSFE model yields efficient and accurate analysis of wave propagation in adhesively-bonded composite joints. (C) 2014 Elsevier Ltd. All rights reserved.

Estimates of site response based on spectral ratio between horizontal and vertical components of ambient vibrations in the source zone of 2001 Bhuj earthquake

We investigated the site response characteristics of Kachchh rift basin over the meizoseismal area of the 2001, Mw 7.6, Bhuj (NW India) earthquake using the spectral ratio of the horizontal and vertical components of ambient vibrations. Using the available knowledge on the regional geology of Kachchh and well documented ground responses from the earthquake, we evaluated the H/V curves pattern across sediment filled valleys and uplifted areas generally characterized by weathered sandstones. Although our HIV curves showed a largely fuzzy nature, we found that the hierarchical clustering method was useful for comparing large numbers of response curves and identifying the areas with similar responses. Broad and plateau shaped peaks of a cluster of curves within the valley region suggests the possibility of basin effects within valley. Fundamental resonance frequencies (f(0)) are found in the narrow range of 0.1-2.3 Hz and their spatial distribution demarcated the uplifted regions from the valleys. In contrary, low HIV peak amplitudes (A(0) = 2-4) were observed on the uplifted areas and varying values (2-9) were found within valleys. Compared to the amplification factors, the liquefaction indices (kg) were able to effectively indicate the areas which experienced severe liquefaction. The amplification ranges obtained in the current study were found to be comparable to those obtained from earthquake data for a limited number of seismic stations located on uplifted areas; however the values on the valley region may not reflect their true amplification potential due to basin effects. Our study highlights the practical usefulness as well as limitations of the HIV method to study complex geological settings as Kachchh. (C) 2014 Elsevier Ltd. All rights reserved.

IR spectroscopy as a probe for C-H center dot center dot center dot X hydrogen bonded supramolecular synthons

Weak hydrogen bonds of the type C-H center dot center dot center dot X (X: N, O, S and halogens) have evoked considerable interest over the years, especially in the context of crystal engineering. However, association patterns of weak hydrogen bonds are generally difficult to characterize, and yet the identification of such patterns is of interest, especially in high throughput work or where single crystal X-ray analysis is difficult or impossible. To obtain structural information on such assemblies, we describe here a five step IR spectroscopic method that identifies supramolecular synthons in weak hydrogen bonded dimer assemblies, bifurcated systems, and p-electron mediated synthons. The synthons studied here contain C-H groups as hydrogen bond donors. The method involves: (i) identifying simple compounds/cocrystals/salts that contain the hydrogen bonded dimer synthon of interest or linear hydrogen bonded assemblies between the same functionalities; (ii) scanning infrared (IR) spectra of the compounds; (iii) identifying characteristic spectral differences between dimer and linear; (iv) assigning identified bands as marker bands for identification of the supramolecular synthon, and finally (v) identifying synthons in compounds whose crystal structures are not known. The method has been effectively implemented for assemblies involving dimer/linear weak hydrogen bonds in nitrobenzenes (C-H center dot center dot center dot O-NO), nitro-dimethylamino compounds (NMe2 center dot center dot center dot O2N), chalcones (C-H center dot center dot center dot O=C), benzonitriles (C-H center dot center dot center dot N C) and fluorobenzoic acids (C-H center dot center dot center dot F-C). Two other special cases of C-H center dot center dot center dot pi and N-H center dot center dot center dot pi synthons were studied in which the band shape of the C-H stretch in hydrocarbons and the N-H deformation in aminobenzenes was examined.

A Suzaku view of IGR J16393-4643

The pulsar IGR J16393-4643 belongs to a class of highly absorbed supergiant high-mass X-ray binaries (HMXBs), characterized by a very high column density of absorbing matter. We present the results of simultaneous broad-band pulsation and spectrum analysis from a 44-ks Suzaku observation of the source. The orbital intensity profile created with the Swift Burst Alert Telescope (Swift-BAT) light curve shows an indication of IGR J16393-4643 being an eclipsing system with a short eclipse semi-angle theta(E) similar to 17 degrees. For a supergiant companion star with a 20-R-circle dot radius, this implies an inclination of the orbital plane in the range 39 degrees-57 degrees, whereas for a main-sequence B star as the companion with a 10-R-circle dot radius, the inclination of the orbital plane is in the range 60 degrees-77 degrees. Pulse profiles created for different energy bands have complex morphology, which shows some energy dependence and increases in pulse fraction with energy. We have also investigated broad-band spectral characteristics, phase-averaged spectra and resolving the pulse phase into peak and trough phases. The phase-averaged spectrum has a very high N-H(similar to 3 x 10(23) cm(-2)) and is described by a power law (Gamma similar to 0.9) with a high-energy cut-off above 20 keV. We find a change in the spectral index in the peak and trough phases, implying an underlying change in the source spectrum.

CH-RES-TOCSY: Enantiomers spectral resolution and measurement of heteronuclear residual dipolar couplings

A new 2D NMR technique cited as CH-RES-TOCSY, for complete unraveling the spectra of enantiomers and for the measurement of structurally important C-HRDC sis reported. The spectral overlap and complexity of peaks were reduced by the blend of selective excitation and homo-decoupling. Differential values of C-H RDCs of enantiomers (R and S) are exploited to separate the enantiomeric peaks. The complete unraveling of the spectra of both the enantiomers is achieved by incorporating a TOCSY mixing blockprior to signal acquisition. The additional application of the method is demonstrated for the assignment of symmetric isomers. (C) 2015 Elsevier B.V. All rights reserved.

A spectral element for wave propagation in honeycomb sandwich construction considering core flexibility

Spectral elements are found to be extremely resourceful to study the wave propagation characteristics of structures at high frequencies. Most of the aerospace structures use honeycomb sandwich constructions. The existing spectral elements use single layer theories for a sandwich construction wherein the two face sheets vibrate together and this model is sufficient for low frequency excitations. At high frequencies, the two face sheets vibrate independently. The Extended Higher order SAndwich Plate theory (EHSaPT) is suitable for representing the independent motion of the face sheets. A 1D spectral element based on EHSaPT is developed in this work. The wave number and the wave speed characteristics are obtained using the developed spectral element. It is shown that the developed spectral element is capable of representing independent wave motions of the face sheets. The propagation speeds of a high frequency modulated pulse in the face sheets and the core of a honeycomb sandwich are demonstrated. Responses of a typical honeycomb sandwich beam to high frequency shock loads are obtained using the developed spectral element and the response match very well with the finite element results. It is shown that the developed spectral element is able to represent the flexibility of the core resulting into independent wave motions in the face sheets, for which a finite element method needs huge degrees of freedom. (C) 2015 Elsevier Ltd. All rights reserved.

Spectral Zero-Crossings: Localization Properties and Applications

We present an analysis of the rate of sign changes in the discrete Fourier spectrum of a sequence. The sign changes of either the real or imaginary parts of the spectrum are considered, and the rate of sign changes is termed as the spectral zero-crossing rate (SZCR). We show that SZCR carries information pertaining to the locations of transients within the temporal observation window. We show duality with temporal zero-crossing rate analysis by expressing the spectrum of a signal as a sum of sinusoids with random phases. This extension leads to spectral-domain iterative filtering approaches to stabilize the spectral zero-crossing rate and to improve upon the location estimates. The localization properties are compared with group-delay-based localization metrics in a stylized signal setting well-known in speech processing literature. We show applications to epoch estimation in voiced speech signals using the SZCR on the integrated linear prediction residue. The performance of the SZCR-based epoch localization technique is competitive with the state-of-the-art epoch estimation techniques that are based on average pitch period.

Multi-transform based spectral element to include first order shear deformation in plates

For obtaining dynamic response of structure to high frequency shock excitation spectral elements have several advantages over conventional methods. At higher frequencies transverse shear and rotary inertia have a predominant role. These are represented by the First order Shear Deformation Theory (FSDT). But not much work is reported on spectral elements with FSDT. This work presents a new spectral element based on the FSDT/Mindlin Plate Theory which is essential for wave propagation analysis of sandwich plates. Multi-transformation method is used to solve the coupled partial differential equations, i.e., Laplace transforms for temporal approximation and wavelet transforms for spatial approximation. The formulation takes into account the axial-flexure and shear coupling. The ability of the element to represent different modes of wave motion is demonstrated. Impact on the derived wave motion characteristics in the absence of the developed spectral element is discussed. The transient response using the formulated element is validated by the results obtained using Finite Element Method (FEM) which needs significant computational effort. Experimental results are provided which confirms the need to having the developed spectral element for the high frequency response of structures. (C) 2015 Elsevier Ltd. All rights reserved.

Tuning the metal-insulator transition in NdNiO3 heterostructures via Fermi surface instability and spin fluctuations

We employed in situ pulsed laser deposition (PLD) and angle-resolved photoemission spectroscopy (ARPES) to investigate the mechanism of the metal-insulator transition (MIT) in NdNiO3 (NNO) thin films, grown on NdGaO3(110) and LaAlO3(100) substrates. In the metallic phase, we observe three-dimensional hole and electron Fermi surface (FS) pockets formed from strongly renormalized bands with well-defined quasiparticles. Upon cooling across the MIT in NNO/NGO sample, the quasiparticles lose coherence via a spectral weight transfer from near the Fermi level to localized states forming at higher binding energies. In the case of NNO/LAO, the bands are apparently shifted upward with an additional holelike pocket forming at the corner of the Brillouin zone. We find that the renormalization effects are strongly anisotropic and are stronger in NNO/NGO than NNO/LAO. Our study reveals that substrate-induced strain tunes the crystal field splitting, which changes the FS properties, nesting conditions, and spin-fluctuation strength, and thereby controls the MIT via the formation of an electronic order parameter with QAF similar to (1/4,1/4,1/4 +/- delta).