Microwave spectrum and structure of C(6)H(5)CCH center dot center dot center dot H(2)S complex

Rotational spectra of C(6)H(5)CCH center dot center dot center dot H(2)S, C(6)H(5)CCH center dot center dot center dot H(2)(34)S, C(6)H(5)CCH center dot center dot center dot HDS, C(6)H(5)CCH center dot center dot center dot D(2)S and C(6) H(5)CCD center dot center dot center dot H(2)S complexes have been observed using a pulsed nozzle Fourier transform microwave spectrometer. The observed spectrum is consistent with a structure in which hydrogen sulfide is located over the phenyl ring pi cloud and the distance between the centers of masses of the two monomers is 3.74 +/- 0.01 angstrom. In the complex, the H(2)S unit is shifted from the phenyl ring center towards the acetylene group. The vibrationally averaged structure has an effective Cs symmetry. Ab initio calculations were performed at MP2/aug-cc-pVDZ level of theory to locate the possible geometries of the complex. The calculations reveal the experimentally observed structure to be more stable than a coplanar arrangement of the monomers, which was observed for the C(6)H(5)CCH center dot center dot center dot H(2)O complex. Atoms in molecule theoretical analysis shows the presence of S-H center dot center dot center dot pi hydrogen bond. For the parent isotopologue, each transition frequency was found to split into two resulting from an interchange of the equivalent hydrogens of H(2)S unit in the complex. (C) 2011 Elsevier Inc. All rights reserved.

Time-Resolved Resonance Raman Spectroscopy: Exploring Reactive Intermediates

The study of reaction mechanisms involves systematic investigations of the correlation between structure, reactivity, and time. The challenge is to be able to observe the chemical changes undergone by reactants as they change into products via one or several intermediates such as electronic excited states (singlet and triplet), radicals, radical ions, carbocations, carbanions, carbenes, nitrenes, nitrinium ions, etc. The vast array of intermediates and timescales means there is no single ``do-it-all'' technique. The simultaneous advances in contemporary time-resolved Raman spectroscopic techniques and computational methods have done much towards visualizing molecular fingerprint snapshots of the reactive intermediates in the microsecond to femtosecond time domain. Raman spectroscopy and its sensitive counterpart resonance Raman spectroscopy have been well proven as means for determining molecular structure, chemical bonding, reactivity, and dynamics of short-lived intermediates in solution phase and are advantageous in comparison to commonly used time-resolved absorption and emission spectroscopy. Today time-resolved Raman spectroscopy is a mature technique; its development owes much to the advent of pulsed tunable lasers, highly efficient spectrometers, and high speed, highly sensitive multichannel detectors able to collect a complete spectrum. This review article will provide a brief chronological development of the experimental setup and demonstrate how experimentalists have conquered numerous challenges to obtain background-free (removing fluorescence), intense, and highly spectrally resolved Raman spectra in the nanosecond to microsecond (ns-mu s) and picosecond (ps) time domains and, perhaps surprisingly, laid the foundations for new techniques such as spatially offset Raman spectroscopy.

A hybrid pre-whitening technique for detection of additive spread spectrum watermarks in audio signals

Pre-whitening techniques are employed in blind correlation detection of additive spread spectrum watermarks in audio signals to reduce the host signal interference. A direct deterministic whitening (DDW) scheme is derived in this paper from the frequency domain analysis of the time domain correlation process. Our experimental studies reveal that, the Savitzky-Golay Whitening (SGW), which is otherwise inferior to DDW technique, performs better when the audio signal is predominantly lowpass. The novelty of this paper lies in exploiting the complementary nature to the two whitening techniques to obtain a hybrid whitening (HbW) scheme. In the hybrid scheme the DDW and SGW techniques are selectively applied, based on short time spectral characteristics of the audio signal. The hybrid scheme extends the reliability of watermark detection to a wider range of audio signals.

High-Rate Vector Quantization for Noisy Channels With Applications to Wideband Speech Spectrum Compression

This paper considers the high-rate performance of source coding for noisy discrete symmetric channels with random index assignment (IA). Accurate analytical models are developed to characterize the expected distortion performance of vector quantization (VQ) for a large class of distortion measures. It is shown that when the point density is continuous, the distortion can be approximated as the sum of the source quantization distortion and the channel-error induced distortion. Expressions are also derived for the continuous point density that minimizes the expected distortion. Next, for the case of mean squared error distortion, a more accurate analytical model for the distortion is derived by allowing the point density to have a singular component. The extent of the singularity is also characterized. These results provide analytical models for the expected distortion performance of both conventional VQ as well as for channel-optimized VQ. As a practical example, compression of the linear predictive coding parameters in the wideband speech spectrum is considered, with the log spectral distortion as performance metric. The theory is able to correctly predict the channel error rate that is permissible for operation at a particular level of distortion.

Nature and Properties of a Repulsive Fermi Gas in the Upper Branch of the Energy Spectrum

We generalize the Nozieres-Schmitt-Rink method to study the repulsive Fermi gas in the absence of molecule formation, i.e., in the so-called ``upper branch.'' We find that the system remains stable except close to resonance at sufficiently low temperatures. With increasing scattering length, the energy density of the system attains a maximum at a positive scattering length before resonance. This is shown to arise from Pauli blocking which causes the bound states of fermion pairs of different momenta to disappear at different scattering lengths. At the point of maximum energy, the compressibility of the system is substantially reduced, leading to a sizable uniform density core in a trapped gas. The change in spin susceptibility with increasing scattering length is moderate and does not indicate any magnetic instability. These features should also manifest in Fermi gases with unequal masses and/or spin populations.

The fluorescence of Nd3+ in lead borate and bismuth borate glasses with large stimulated emission cross section

The stimulated emission cross section σp for the 1060 nm transition of Nd3+ in lead borate and bismuth borate glasses has been determined from fluorescence measurements. The compositional dependence of σp, which has been evaluated using radiative transition probability, refractive index of the host glass, effective fluorescence linewidth, and position of the band, with PbO/Bi2O3 content is investigated. The σp values of the 1060 nm band of Nd3+ for lead borate and bismuth borate glasses are found to be in the range 2.6–5.7×10−20 cm2 at 298 K and 3.0–6.3×10−20 cm2 at 4.2 K. The σp values are comparatively large suggesting the possible utilization of these materials in laser applications.

Analysis of integrated optofluidic lab-on-a-chip fluorescence biosensor based on transmittance of light through a fluidic gap

Sensitivity analysis is an important aspect to be looked into while designing lab-on-a-chip systems. In this paper we will be showing with appropriate design that the best sensitivity of the fluorescence biosensor is achieved for an optimal width of fluidic gap, corresponding to a particular mode spot size. We will be also showing that the sensitivity of the biosensor is affected by efficiency of light coupling, which is influenced by changes in the width of fluidic gap, refractive index of the fluid and higher order modes.

The spectral index-luminosity relationship for steep-spectrum cores in extra-galactic radio-sources

The spectral index-luminosity relationship for steep-spectrum cores in galaxies and quasars has been investigated, and it is found that the sample of galaxies supports earlier suggestions of a strong correlation, while there is weak evidence for a similar relationship for the quasars. It is shown that a strong spectral index-luminosity correlation can be used to set an upper limit to the velocities of the radio-emitting material which is expelled from the nucleus in the form of collimated beams or jets having relativistic bulk velocities. The data on cores in galaxies indicate that the Lorentz factors of the radiating material are less than about 2.

Simultaneous multilayer scanning and detection for multiphoton fluorescence microscopy

Fast three-dimensional (3D) imaging requires parallel optical slicing of a specimen with an efficient detection scheme. The generation of multiple localized dot-like excitation structures solves the problem of simultaneous slicing multiple specimen layers, but an efficient detection scheme is necessary. Confocal theta detection (detection at 90 degrees to the optical axis) provides a suitable detection platform that is capable of cross-talk-free fluorescence detection from each nanodot (axial dimension approximate to 150 nm). Additionally, this technique has the unique feature of imaging a specimen at a large working distance with super-resolution capabilities. Polarization studies show distinct field structures for fixed and fluid samples, indicating a non-negligible field-dipole interaction. The realization of the proposed imaging technique will advance and diversify multiphoton fluorescence microscopy for numerous applications in nanobioimaging and optical engineering.

Timing and broad-band spectroscopy of 1A 1118-61 with Suzaku

We present a timing and broad-band pulse-phase-resolved spectral analysis of the transient Be X-ray binary pulsar 1A 1118-61 observed during its outburst in 2009 January using Suzaku observations. The Suzaku observations were made twice, once at the peak of the outburst, and the other 13 d later at its declining phase. Pulse profiles from both observations exhibit strong energy dependence with several peaks at low energies and a single peak above similar to 10 keV. A weak, narrow peak is detected at the main dip of the pulse profiles from both observations in the energy bands below 3 keV, indicating the presence of a phase-dependent soft excess in the source continuum. The broad-band energy spectrum of the pulsar could be fitted well with a partial covering cut-off power-law model and a narrow iron fluorescence line. We also detect a broad cyclotron feature at similar to 50 keV from both observations which is a feature common for accretion-powered pulsars with high magnetic field strength. The pulse-phase-resolved spectral analysis shows an increase in the absorption column density of the partial covering component, as well as variation in the covering fraction at the dips of the pulse profiles, which naturally explains energy dependence of the same. The cyclotron line parameters also show significant variation with pulse phase with an similar to 10 keV variation in the cyclotron line energy and a variation in depth by a factor of 3. This can be explained either as the effect of different viewing angles of the dipole field at different pulse phases, or due to a more complex underlying magnetic field geometry.

Spectroscopic Characterization and Modeling of Quadrupolar Charge-Transfer Dyes with Bulky Substituents

Joint experimental and theoretical work is presented on two quadrupolar D-pi-A-pi-D chromophores characterized by the same bulky donor (D) group and two different central cores. The first chromophore, a newly synthesized species with a malononitrile-based acceptor (A) group, has a V-shaped structure that makes its absorption spectrum very broad, covering most of the visible region. The second chromophore has a squaraine-based core and therefore a linear structure, as also evinced from its absorption spectra. Both chromophores show an anomalous red shift of the absorption band upon increasing solvent polarity, a feature that is ascribed to the large, bulky structure of the moleCules. For these molecules, the basic description of polar solvation in terms of a uniform reaction field fails. Indeed, a simple extension of the model to account for two independent reaction fields associated with the two molecular arms quantitatively reproduces the observed linear absorption and fluorescence as well as fluorescence anisotropy spectra, fully rationalizing their nontrivial dependence on solvent polarity. The model derived from the analysis of linear spectra is adopted to predict nonlinear spectra and specifically hyper-Rayleigh scattering and two-photon absorption spectra. In polar solvents, the V-shaped chromophore is predicted to have a large HRS response in a wide spectral region (approximately 600-1300 nm). Anomalously large and largely solvent-dependent HRS responses for the linear chromophores are ascribed to symmetry lowering induced by polar solvation and amplified in this bulky system by the presence of two reaction fields.

Solvent effect on the fluorescence quenching of biologically active carboxamide by aniline and carbon tetrachloride in different solvents using S-V plots

The fluorescence quenching studies of carboxamide namely (E)-N-(3-Chlorophenyl)-2-(3,4,5-trimethoxybenzylideneamino)-4,5,6,7 tetrahydrobenzob]thiophene-3-carboxamide ENCTTTC] by aniline and carbon tetrachloride in six different solvents namely toluene, cyclohexane, n-hexane, n-heptane, n-decane and n-pentane have been carried out at room temperature with a view to understand the quenching mechanisms. The Stern-Volmer (S-V) plots have been found to be nonlinear with a positive deviation for all the solvents studied. In order to interpret these results we have invoked the ground state complex formation and sphere of action static quenching models. Using these models various quenching rate parameters have been determined. The magnitudes of these parameters suggest that sphere of action static quenching model agrees well with the experimental results. Hence the positive deviation is attributed to the static and dynamic quenching. Further, with the use of Finite Sink approximation model, it was possible to check these bimolecular reactions as diffusion-limited and to estimate independently distance parameter R' and mutual diffusion coefficient D. Finally an effort has been made to correlate the values of R' and D with the values of the encounter distance R and the mutual coefficient D determined using the Edward's empirical relation and Stokes Einstein relation. (C) 2011 Elsevier B.V. All rights reserved.