Perturbation of the infrared spectrum of lanthanum cobaltate induced by vibronic coupling

Anomalous changes in the infrared intensity of the cobalt-oxygen stretching modes in the infrared spectrum of lanthanum cobaltate (LaCoO3) suggest vibronic coupling. This phenomenon has been studied by infrared vibrational spectroscopy both by temperature-induced changes of spin-state occupation and pressure-induced changes of the crystal field splitting 10Dq.

Long-Range Visible Fluorescence Tunability Using Component-Modulated Coupled Quantum Dots

A simple route for tailoring emissions in the visible wavelength region by chemically coupling quantum dots composed of ZnSe and CdS is reported. coupled quantum dots offer a novel route for tuning electronic transitions via band-offset engineering at the material interface. This novel class of asymmetric. coupled quantum structures may offer a basis for a diverse set of building blocks for optoelectronic devices, ultrahigh density memories, and quantum information processing.

Resonance de-enhancement in the 2(1)A(g) state of trans-azobenzene

We analyze the origin of de-enhancement for a number of vibrational modes in the 2(1)A(g) excited state of trans-azobenzene. We have used the time-dependent wave packet analysis of the RR intensities by including the multimode damping effects in the calculation. This avoids the use of unrealistically large values for the damping parameter. It is concluded that the de-enhancement is caused by the interference between the two uncoupled electronic states, and that the intensities observed under the so-called symmetry forbidden 2(1)A(g) <-- 1(1)A(g) transition are purely due to resonance excitation. It is also observed that the use of the time-dependent approach to study the de-enhancement effects caused by multiple electronic states on the RR intensities is not necessarily useful if one is interested in the structural dynamics.

Some unusual features in the Raman spectrum of amorphous-carbon films obtained by pyrolysis of maleic anhydride

Laser micro-Raman spectroscopic measurements were done on the amorphous conducting carbon films obtained from maleic anhydride by pyrolysis process. We have found a predominant broad peak around 1140 cm(-1), in addition to the normally observed peaks in amorphous carbons around 1350 and 1600 cm(-1), and peak of medium intensity around 800 cm(-1). Here we discuss the possibility of conjugated polymer like bond alternating structure which can give rise to these unusual Raman features. (C) 1997 American Institute of Physics.

Time-resolved resonance Raman spectroscopic studies on the triplet excited state of fluoranil

Perfluoro substituted organic compounds have attracted attention owing to their unique structure and reactivity induced by the perfluoro effect. Fluoranil, a perfluoro derivative of p-benzoquinone, is the subject of this paper. Although the perfluoro effect in the ground state seems to have been well understood there is no information available about such effects on the excited state. Here, the time-resolved resonance Raman spectra of the triplet excited state of fluoranil are reported along with the Raman excitation profiles (REPs) of the various vibrational modes. The vibrational spectral analyses have been carried out by analogy with the fluoranil ground state, triplet benzoquinone, and triplet chloranil vibrational spectral assignments. Also, the assignments are further supported by the calculated frequencies using ab initio theoretical methods. It is observed that for fluoranil in the triplet excited state, due to the perfluoro effect, the structure is considerably less distorted than benzoquinone and also the electron delocalization in the pi* antibonding orbital is less than that of triplet excited state of benzoquinone.

Transient absorption studies on 3,6-dibromo polyvinylcarbazole and its model compounds

3,6-Dibromo-N-ethylcarbazole (DBNEC) and its polymeric analogue poly-3,6-dibromovinylcarbazole (PDBVCz) were studied by transient absorption spectroscopy. The transient absorption spectrum of the 3,6-dibromo-N-ethylcarbazole radical cation and decay rate constants of radical cations of 3,6-dibromo-N-ethylcarbazole and its polymeric analogue are presented. In the case of unsubstituted carbazole, the ratio of the yield of radical cation of monomer to polymer is 2.0, whereas in the case of PDBVCz, under the same experimental conditions, the yield of the radical cation is an order of magnitude less in comparison with the monomer model compound DBNEC. This drastic difference in yield has been correlated to the difference in the conformational structure of the polymer as evidenced by nuclear magnetic resonance spectroscopy. (C) 1997 Elsevier Science S.A.

Mapping adaptive resonance theory onto ring and mesh architectures

In recent years, parallel computers have been attracting attention for simulating artificial neural networks (ANN). This is due to the inherent parallelism in ANN. This work is aimed at studying ways of parallelizing adaptive resonance theory (ART), a popular neural network algorithm. The core computations of ART are separated and different strategies of parallelizing ART are discussed. We present mapping strategies for ART 2-A neural network onto ring and mesh architectures. The required parallel architecture is simulated using a parallel architectural simulator, PROTEUS and parallel programs are written using a superset of C for the algorithms presented. A simulation-based scalability study of the algorithm-architecture match is carried out. The various overheads are identified in order to suggest ways of improving the performance. Our main objective is to find out the performance of the ART2-A network on different parallel architectures. (C) 1999 Elsevier Science B.V. All rights reserved.

Photogenerated radical intermediates of vitamin K-1: a time-resolved resonance Raman study

Quinones play a vital role in the process of electron transfer in bacterial photosynthetic reaction centers. It is of interest to investigate the photochemical reactions involving quinones with a view to elucidating the structure-function relationships in the biological processes. Resonance Raman spectra of radical anions and the time-resolved resonance Raman spectra of vitamin K-1 (model compound for Q(A) in Rhodopseudomonas viridis, a bacterial photosynthetic reception center) are presented. The photochemical intermediates of vitamin K-1, viz. radical anion, ketyl radical and o-quinone methide have been identified. The vibrational assignments of all these intermediates are made on the basis of comparison with our earlier TR3 studies on radical anions of naphthoquinone and menaquinone. (C) 1999 Elsevier Science B.V. All rights reserved.

Synthesis and vesicle formation from dimeric pseudoglyceryl lipids with (CH2)(m) spacers: pronounced m-value dependence of thermal properties, vesicle fusion, and cholesterol complexation

Eight new dimeric lipids, in which the two Me2N+ ion headgroups are separated by a variable number of polymethylene units [-(CH2)(m)-], have been synthesized. The electron micrograph (TEM) and dynamic light scattering (DLS) of their aqueous dispersions confirmed the formation of vesicular-type aggregates. The vesicle sizes and morphologies were found to depend strongly on the m value, the method, and thermal history of the vesicle preparation. Information on the thermotropic properties of the resulting vesicles was obtained from microcalorimetry and temperature-dependent fluorescence anisotropy measurements. Interestingly, the T-m values for these vesicles revealed a nonlinear dependence on spacer chain length (m value). These vesicles were able to entrap riboflavin. The rates of permeation of the OH- ion under an imposed transmembrane pH gradient were also found to depend significantly on the m value. X-Ray diffraction of the cast films of the lipid dispersions elucidated the nature and the thickness of these membrane organizations, and it was revealed that these lipids organize in three different ways depending on the m value. The EPR spin-probe method with the doxylstearic acids 5NS, 12NS, and 16NS, spin-labeled at various positions of stearic acid, was used to establish, the chain-flexibility gradient and homogeneity of these bilayer assemblies. The apparent fusogenic propensities of these bipolar tetraether lipids were investigated in the presence of Na2SO4 with fluorescence-resonance energy-transfer fusion assay. Small unilamellar vesicles formed from 1 and three representative biscationic lipids were also studied with fluorescence anisotropy and H-1 NMR spectroscopic techniques in the absence and the presence of varying amounts of cholesterol.

EPR and photoluminescence studies of ZnO:Mn nanophosphors prepared by solution combustion route

Nanocrystalline ZnO:Mn (0.1 mol%) phosphors have been successfully prepared by self propagating, gas producing solution combustion method. The powder X-ray diffraction of as-formed ZnO:Mn sample shows, hexagonal wurtzite phase with particle size of similar to 40 nm. For Mn doped ZnO, the lattice parameters and volume of unit cell (a=3.23065 angstrom, c=5.27563 angstrom and V=47.684 (angstrom)(3)) are found to be greater than that of undoped ZnO (a=3.19993 angstrom, c=5.22546 angstrom and V=46.336 (angstrom)(3)). The SEM micrographs reveal that besides the spherical crystals, the powders also contained several voids and pores. The TEM photograph also shows the particles are approximately spherical in nature. The FTIR spectrum shows two peaks at similar to 3428 and 1598 cm(-1) which are attributed to O-H stretching and H-O-H bending vibration. The PL spectra of ZnO:Mn indicate a strong green emission peak at 526 nm and a weak red emission at 636 nm corresponding to T-4(1) -> (6)A(1) transition of Mn2+ ions. The EPR spectrum exhibits fine structure transition which will be split into six hyperfine components due to Mn-55 hyperfine coupling giving rise to all 30 allowed transitions. From EPR spectra the spin-Hamiltonian parameters have been evaluated and discussed. The magnitude of the hyperfine splitting (A) constant indicates that there exists a moderately covalent bonding between the Mn2+ ions and the surrounding ligands. The number of spins participating in resonance (N), its paramagnetic susceptibility (chi) have been evaluated. (C) 2011 Elsevier B.V. All rights reserved.

Fluorescence and visual sensing of nitroaromatic explosives using electron rich discrete fluorophores

Several pi-electron rich fluorescent aromatic compounds containing trimethylsilylethynyl functionality have been synthesized by employing Sonogashira coupling reaction and they were characterized fully by NMR (H-1, C-13)/IR spectroscopy. Incorporation of bulky trimethylsilylethynyl groups on the peripheral of the fluorophores prevents self-quenching of the initial intensity through pi-pi interaction and thereby maintains the spectroscopic stability in solution. These compounds showed fluorescence behavior in chloroform solution and were used as selective fluorescence sensors for the detection of electron deficient nitroaromatics. All these fluorophores showed the largest quenching response with high selectivity for nitroaromatics among the various electron deficient aromatic compounds tested. Quantitative analysis of the fluorescence titration profile of 9,10-bis(trimethylsilylethynyl) anthracene with picric acid provided evidence that this particular fluorophore detects picric acid even at ppb level. A sharp visual detection of 2,4,6-trinitrotoluene was observed upon subjecting 1,3,6,8-tetrakis (trimethylsilylethynyl) pyrene fluorophore to increasing quantities of 2,4,6-trinitrotoluene in chloroform. Furthermore, thin film of the fluorophores was made by spin coating of a solution of 1.0 x 10(-3) M in chloroform or dichloromethane on a quartz plate and was used for the detection of vapors of nitroaromatics at room temperature. The vapor-phase sensing experiments suggested that the sensing process is reproducible and quite selective for nitroaromatic compounds. Selective fluorescence quenching response including a sharp visual color change for nitroaromatics makes these fluorophores as promising fluorescence sensory materials for nitroaromatic compounds (NAC) with a detection limit of even ppb level as judged with picric acid.

Cyclic Prefix Based Cooperative Sequential Spectrum Sensing Algorithms for OFDM

This paper considers the problem of spectrum sensing in cognitive radio networks when the primary user is using Orthogonal Frequency Division Multiplexing (OFDM). For this we develop cooperative sequential detection algorithms that use the autocorrelation property of cyclic prefix (CP) used in OFDM systems. We study the effect of timing and frequency offset, IQ-imbalance and uncertainty in noise and transmit power. We also modify the detector to mitigate the effects of these impairments. The performance of the proposed algorithms is studied via simulations. We show that sequential detection can significantly improve the performance over a fixed sample size detector.

Developments in quantum information processing by nuclear magnetic resonance: Use of quadrupolar and dipolar couplings

Use of dipolar and quadrupolar couplings for quantum information processing (QIP) by nuclear magnetic resonance (NMR) is described. In these cases, instead of the individual spins being qubits, the 2(n) energy levels of the spin-system can be treated as an n-qubit system. It is demonstrated that QIP in such systems can be carried out using transition-selective pulses, in (CHCN)-C-3, (CH3CN)-C-13, Li-7 (I = 3/2) and Cs-133 (I = 7/2), oriented in liquid crystals yielding 2 and 3 qubit systems. Creation of pseudopure states, implementation of logic gates and arithmetic operations (half-adder and subtractor) have been carried out in these systems using transition-selective pulses.

Energy transfer efficiency distributions in polymers in solution during folding and unfolding

Distribution of fluorescence resonance energy transfer (FRET) efficiency between the two ends of a Lennard-Jones polymer chain both at equilibrium and during folding and unfolding has been calculated, for the first time, by Brownian dynamics simulations. The distribution of FRET efficiency becomes bimodal during folding of the extended state subsequent to a temperature quench, with the width of the distribution for the extended state broader than that for the folded state. The reverse process of unfolding subsequent to a upward temperature jump shows different characteristics. The distributions show significant viscosity dependence which can be tested against experiments.