Theoretical analysis of photoinduced H-atom elimination in thiophenol

The photoinduced hydrogen elimination reaction in thiophenol via the conical intersections of the dissociative (1)pi sigma* excited state with the bound (1)pi pi* excited state and the electronic ground state has been investigated with ab initio electronic-structure calculations and time-dependent quantum wave-packet calculations. A screening of the coupling constants of the symmetry-allowed coupling modes at the (1)pi pi*-(1)pi sigma* and (1)pi sigma*-S-0 conical intersection shows that the SH torsional mode is by far the most important coupling mode at both conical intersections. A model including three intersecting potential-energy surfaces (S-0, (1)pi pi*, (1)pi sigma*) and two nuclear degrees of freedom (SH stretch and SH torsion) has been constructed on the basis of ab initio complete-active-space self-consistent field and multireference second-order perturbation theory calculations. The nonadiabatic quantum wave-packet dynamics initiated by optical excitation of the (1)pi pi* and (1)pi sigma* states has been explored for this three-state two-coordinate model. The photodissociation dynamics is characterized in terms of snapshots of time-dependent wave packets, time-dependent electronic population probabilities, and the branching ratio of the (2)sigma/(2)pi electronic states of the thiophenoxyl radical. The dependence of the timescale of the photodissociation process and the branching ratio on the initial excitation of the SH stretching and SH torsional vibrations has been analyzed. It is shown that the node structure, which is imposed on the nuclear wave packets by the initial vibrational preparation as well as by the transitions through the conical intersections, has a profound effect on the photodissociation dynamics. The effect of additional weak coupling modes of CC twist (nu(16a)) and ring-distortion (nu(16b)) character has been investigated with three-dimensional and four-dimensional time-dependent wave-packet calculations, and has been found to be minor. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4709608]

An approach to multi-temporal MODIS image analysis using image classification and segmentation

This paper discusses an approach for river mapping and flood evaluation based on multi-temporal time series analysis of satellite images utilizing pixel spectral information for image classification and region-based segmentation for extracting water-covered regions. Analysis of MODIS satellite images is applied in three stages: before flood, during flood and after flood. Water regions are extracted from the MODIS images using image classification (based on spectral information) and image segmentation (based on spatial information). Multi-temporal MODIS images from ``normal'' (non-flood) and flood time-periods are processed in two steps. In the first step, image classifiers such as Support Vector Machines (SVMs) and Artificial Neural Networks (ANNs) separate the image pixels into water and non-water groups based on their spectral features. The classified image is then segmented using spatial features of the water pixels to remove the misclassified water. From the results obtained, we evaluate the performance of the method and conclude that the use of image classification (SVM and ANN) and region-based image segmentation is an accurate and reliable approach for the extraction of water-covered regions. (c) 2012 COSPAR. Published by Elsevier Ltd. All rights reserved.

1-D Hydrogen bonded water in Cu(II)-picolinate coordination polymer: synthesis, crystal structure, and thermogravimetric analysis

A new Cu(II)-picolinate complex was synthesized and characterized by single crystal X-ray crystallography. The complex crystallizes in the centrosymmetric triclinic space group P (1) over bar (no. 2). Picolinate in the complex extends the neutral unit into a 1-D chain through mu(2)-bridging carboxylate. The complex has a hydrogen bonding acceptor in the second coordination sphere allowing lattice water to assemble neighboring chains. Water self-assembles to form a zig-zag 1-D chain. The adjacent chains are assembled by C-H center dot center dot center dot O interactions result in the formation 2-D hydrogen bonded network. The overall hydrogen bonding between water chain and Cu-picolinate network yields a 3-D hydrogen bonded coordination network. X-ray structural analysis, FTIR and thermal analysis have been used to characterize the reported compound in the solid state.

Space-Time Scales of Northward Propagation of Convection during Boreal Summer

This study uses precipitation estimates from the Tropical Rainfall Measuring Mission to quantify the spatial and temporal scales of northward propagation of convection over the Indian monsoon region during boreal summer. Propagating modes of convective systems in the intraseasonal time scales such as the Madden-Julian oscillation can interact with the intertropical convergence zone and bring active and break spells of the Indian summer monsoon. Wavelet analysis was used to quantify the spatial extent (scale) and center of these propagating convective bands, as well as the time period associated with different spatial scales. Results presented here suggest that during a good monsoon year the spatial scale of this oscillation is about 30 degrees centered around 10 degrees N. During weak monsoon years, the scale of propagation decreases and the center shifts farther south closer to the equator. A strong linear relationship is obtained between the center/scale of convective wave bands and intensity of monsoon precipitation over Indian land on the interannual time scale. Moreover, the spatial scale and its center during the break monsoon were found to be similar to an overall weak monsoon year. Based on this analysis, a new index is proposed to quantify the spatial scales associated with propagating convective bands. This automated wavelet-based technique developed here can be used to study meridional propagation of convection in a large volume of datasets from observations and model simulations. The information so obtained can be related to the interannual and intraseasonal variation of Indian monsoon precipitation.

Synthesis, structural analysis and solvatochromic behaviour of 4,6-bis (4-butoxyphenyl)-2-methoxynicotinonitrile mesogen

In this communication, we report the synthesis and characterisation of a new luminescent liquid crystalline material, 4,6-bis (4-butoxyphenyl)-2-methoxynicotinonitrile (3). We have confirmed its structure by Fourier transform infrared and 1H nuclear magnetic resonance spectroscopy, elemental analysis and X-ray single crystal diffraction studies. The newly synthesised compound crystallises in a monoclinic system with the space group C2/c and its cell parameters are found to be a?=?25.181(4) angstrom, b?=?15.651(4)angstrom, c?=?12.703(19) angstrom, V?=?4880.4 (16) angstrom, Z?=?8. The results indicate that the presence of weak CH center dot center dot center dot O and CH center dot center dot center dot N hydrogen bonding as short-range intermolecular interactions are responsible for the formation of its crystal assembly. The measured torsion angle shows the existence of a distorted structure for the molecule wherein 4-butoxyphenylene ring substituent at the fourth position of the central pyridine ring forms a torsion angle chiC(4), C(3), C(10), C(19)] of 40.55 degrees. Its liquid crystalline behaviour was investigated with the aid of polarised optical microscopy and differential scanning calorimetry. The study reveals that the compound displays a broad nematic phase in the range of 78112 degrees C. Further, solution phase optical studies indicate that it is a blue light emitter in different non-polar and polar organic solvents at a concentration of 10-5M.

Spatial Modulation and Space Shift Keying in Single Carrier Communication

Spatial modulation (SM) and space shift keying (SSK) are relatively new modulation techniques which are attractive in multi-antenna communications. Single carrier (SC) systems can avoid the peak-to-average power ratio (PAPR) problem encountered in multicarrier systems. In this paper, we study SM and SSK signaling in cyclic-prefixed SC (CPSC) systems on MIMO-ISI channels. We present a diversity analysis of MIMO-CPSC systems under SSK and SM signaling. Our analysis shows that the diversity order achieved by (n(t), n(r)) SSK scheme and (n(t), n(r), Theta(M)) SM scheme in MIMO-CPSC systems under maximum-likelihood (ML) detection is n(r), where n(t), n(r) denote the number of transmit and receive antennas and Theta(M) denotes the modulation alphabet of size M. Bit error rate (BER) simulation results validate this predicted diversity order. Simulation results also show that MIMO-CPSC with SM and SSK achieves much better performance than MIMO-OFDM with SM and SSK.

A Hybrid Multilevel Inverter System Based on Dodecagonal Space Vectors for Medium Voltage IM Drives

Dodecagonal (12-sided) space vector pulsewidth modulation (PWM) schemes are characterized by the complete absence of (6n +/- 1)th-order harmonics (for odd n) in the phase voltages, within the linear modulation range and beyond, including over-modulation. This paper presents a new topology suitable for the realization of such multilevel inverter schemes for induction motor (IM) drives, by cascading two-level inverters with flying-capacitor-inverter fed floating H-bridge cells. Now, any standard IM may be used to get the dodecagonal operation which hitherto was possible only with open-end winding IM. To minimize the current total harmonic distortion (THD), a strategy for synchronous PWM is also proposed. It is shown that the proposed method is capable of obtaining better THD figures, compared to conventional dodecagonal schemes. The topology and the PWM strategy are validated through analysis and subsequently verified experimentally.

Analysing modifica-tions in the synthesis of multiple state mechanical devices using configuration space and topology graphs

Automated synthesis of mechanical designs is an important step towards the development of an intelligent CAD system. Research into methods for supporting conceptual design using automated synthesis has attracted much attention in the past decades. In our research, ten experimental studies are conducted to find out how designers synthesize solution concepts for multi-state mechanical devices. The designers are asked to think aloud, while carrying out the synthesis. These design synthesis processes are video recorded. It has been found that modification of kinematic pairs and mechanisms is the major activity carried out by all the designers. This paper presents an analysis of these synthesis processes using configuration space and topology graph to identify and classify the types of modifications that take place. Understanding of these modification processes and the context in which they happened is crucial to develop a system for supporting design synthesis of multiple state mechanical devices that is capable of creating a comprehensive variety of solution alternatives.

Discriminative feature analysis and selection for document classification

Classification of a large document collection involves dealing with a huge feature space where each distinct word is a feature. In such an environment, classification is a costly task both in terms of running time and computing resources. Further it will not guarantee optimal results because it is likely to overfit by considering every feature for classification. In such a context, feature selection is inevitable. This work analyses the feature selection methods, explores the relations among them and attempts to find a minimal subset of features which are discriminative for document classification.

Assimilation of endmember variability in spectral for urban land cover extraction mixture analysis

Variable Endmember Constrained Least Square (VECLS) technique is proposed to account endmember variability in the linear mixture model by incorporating the variance for each class, the signals of which varies from pixel to pixel due to change in urban land cover (LC) structures. VECLS is first tested with a computer simulated three class endmember considering four bands having small, medium and large variability with three different spatial resolutions. The technique is next validated with real datasets of IKONOS, Landsat ETM+ and MODIS. The results show that correlation between actual and estimated proportion is higher by an average of 0.25 for the artificial datasets compared to a situation where variability is not considered. With IKONOS, Landsat ETM+ and MODIS data, the average correlation increased by 0.15 for 2 and 3 classes and by 0.19 for 4 classes, when compared to single endmember per class. (C) 2013 COSPAR. Published by Elsevier Ltd. All rights reserved.

Formulation of a mathematical approach to regional frequency analysis

Estimation of design quantiles of hydrometeorological variables at critical locations in river basins is necessary for hydrological applications. To arrive at reliable estimates for locations (sites) where no or limited records are available, various regional frequency analysis (RFA) procedures have been developed over the past five decades. The most widely used procedure is based on index-flood approach and L-moments. It assumes that values of scale and shape parameters of frequency distribution are identical across all the sites in a homogeneous region. In real-world scenario, this assumption may not be valid even if a region is statistically homogeneous. To address this issue, a novel mathematical approach is proposed. It involves (i) identification of an appropriate frequency distribution to fit the random variable being analyzed for homogeneous region, (ii) use of a proposed transformation mechanism to map observations of the variable from original space to a dimensionless space where the form of distribution does not change, and variation in values of its parameters is minimal across sites, (iii) construction of a growth curve in the dimensionless space, and (iv) mapping the curve to the original space for the target site by applying inverse transformation to arrive at required quantile(s) for the site. Effectiveness of the proposed approach (PA) in predicting quantiles for ungauged sites is demonstrated through Monte Carlo simulation experiments considering five frequency distributions that are widely used in RFA, and by case study on watersheds in conterminous United States. Results indicate that the PA outperforms methods based on index-flood approach.

Analysis and design of split-capacitor resistive-inductive passive damping for LCL filters in grid-connected inverters

Grid-connected inverters require a third-order LCL filter to meet standards such as the IEEE Std. 519-1992 while being compact and cost-effective. LCL filter introduces resonance, which needs to be damped through active or passive methods. Passive damping schemes have less control complexity and are more reliable. This study explores the split-capacitor resistive-inductive (SC-RL) passive damping scheme. The SC-RL damped LCL filter is modelled using state space approach. Using this model, the power loss and damping are analysed. Based on the analysis, the SC-RL scheme is shown to have lower losses than other simpler passive damping methods. This makes the SC-RL scheme suitable for high power applications. A method for component selection that minimises the power loss in the damping resistors while keeping the system well damped is proposed. The design selection takes into account the influence of switching frequency, resonance frequency and the choice of inductance and capacitance values of the filter on the damping component selection. The use of normalised parameters makes it suitable for a wide range of design applications. Analytical results show the losses and quality factor to be in the range of 0.05-0.1% and 2.0-2.5, respectively, which are validated experimentally.

Characterization and Space-Time Downscaling of the Inundation Extent over the Inner Niger Delta Using GIEMS and MODIS Data

The objective in this work is to develop downscaling methodologies to obtain a long time record of inundation extent at high spatial resolution based on the existing low spatial resolution results of the Global Inundation Extent from Multi-Satellites (GIEMS) dataset. In semiarid regions, high-spatial-resolution a priori information can be provided by visible and infrared observations from the Moderate Resolution Imaging Spectroradiometer (MODIS). The study concentrates on the Inner Niger Delta where MODIS-derived inundation extent has been estimated at a 500-m resolution. The space-time variability is first analyzed using a principal component analysis (PCA). This is particularly effective to understand the inundation variability, interpolate in time, or fill in missing values. Two innovative methods are developed (linear regression and matrix inversion) both based on the PCA representation. These GIEMS downscaling techniques have been calibrated using the 500-m MODIS data. The downscaled fields show the expected space-time behaviors from MODIS. A 20-yr dataset of the inundation extent at 500 m is derived from this analysis for the Inner Niger Delta. The methods are very general and may be applied to many basins and to other variables than inundation, provided enough a priori high-spatial-resolution information is available. The derived high-spatial-resolution dataset will be used in the framework of the Surface Water Ocean Topography (SWOT) mission to develop and test the instrument simulator as well as to select the calibration validation sites (with high space-time inundation variability). In addition, once SWOT observations are available, the downscaled methodology will be calibrated on them in order to downscale the GIEMS datasets and to extend the SWOT benefits back in time to 1993.

Bit Error Probability Analysis of SSK in DF Relaying with Threshold-Based Best Relay Selection and Selection Combining

In this letter, we analyze the end-to-end average bit error probability (ABEP) of space shift keying (SSK) in cooperative relaying with decode-and-forward (DF) protocol, considering multiple relays with a threshold based best relay selection, and selection combining of direct and relayed paths at the destination. We derive an exact analytical expression for the end-to-end ABEP in closed-form for binary SSK, where analytical results agree with simulation results. For non-binary SSK, approximate analytical and simulation results are presented.

Error analysis of discontinuous Galerkin methods for the Stokes problem under minimal regularity

In this article, we analyse several discontinuous Galerkin (DG) methods for the Stokes problem under minimal regularity on the solution. We assume that the velocity u belongs to H-0(1)(Omega)](d) and the pressure p is an element of L-0(2)(Omega). First, we analyse standard DG methods assuming that the right-hand side f belongs to H-1(Omega) boolean AND L-1(Omega)](d). A DG method that is well defined for f belonging to H-1(Omega)](d) is then investigated. The methods under study include stabilized DG methods using equal-order spaces and inf-sup stable ones where the pressure space is one polynomial degree less than the velocity space.