Photobehavior of crystalline 4-styrylcoumarin dimorphs: structure-reactivity correlations

4-Styrylcoumarin crystallizes from chloroform and hexane mixture in two morphologically different modifications. The monoclinic form (needles, P2(1)/c) undergoes stereospecific photodimerization producing anti head-to-tail dimer across pyrone double bond, whereas the triclinic modification (prisms, P ($) over bar 1) dimerizes yielding photodimer of the same configuration, but across styrenic double bond. Single crystal X-ray analyses of the dimorphs reveal the packing differences permitting rationalization of the regio- and stereochemistry of the photoproducts. The significantly low dimer yield from the prismatic crystals is rationalized.

Solvation dynamics, energy distribution and trapping of a light solute ion

In the theoretical treatments of the dynamics of solvation of a newly created ion in a dipolar solvent, the self-motion of the solute is usually ignored. Recently, it has been shown that for a light ion the translational motion of the ion can significantly enhance its own rate of solvation. Therefore, solvation itself may not be the rate determining step in the equilibration. Instead, the rate determining step is the search of the low energy configuration which serves to localize the light ion. In this article a microscopic calculation of the probability distribution of the interaction energy of the nascent charge with the dipolar solvent molecules is presented in order to address this problem of solute trapping. It is found that to a good approximation, this distribution is Gaussian and the second moment of this distribution is exactly equal to the half of its own solvation energy. It is shown that this is in excellent agreement with the simulation results that are available for the model Brownian dipolar lattice and for liquid acetonitrile. If the distortion of the solvent by the ion is negligible then the same relation gives the energy distribution for the solvated ion, with the average centered at the final equilibrium solvation energy. These results are expected to be useful in understanding various chemical processes in dipolar liquids. Another interesting outcome of the present study is a simple dynamic argument that supports Onsager's ''inverse snow-ball'' conjecture of solvation of a light ion. A simple derivation of the semi-phenomenological relation between the solvation time correlation function and the single particle orientation, reported recently by Maroncelli et al. (J. Phys. Chem. 97 (1993) 13), is also presented.

Star formation in giant extragalactic H II regions

Star formation properties in Giant Extragalactic H II Regions (GEHRs) are investigated using optical photometry and evolutionary population synthesis models. Photometric data in $BVR$ bands and in the emission line of H-alpha are obtained by CCD imaging at Vainu Bappu Observatory, Kavalur. Aperture photometry is performed for 180 GEHRs in galaxies NGC 1365, 1566, 2366, 2903, 2997, 3351, 4303, 4449, 4656 and 5253. Thirty six of these GEHRs having published spectroscopic data are studied for star formation properties. The population synthesis model is constructed based on Maeder's stellar evolutionary and Kurucz stellar atmosphere models, to synthesize observational quantities of embedded clusters in GEHRs. The observed H-alpha luminosity is a measure of the number of massive stars while the contribution to BVR bands is from intermediate mass (5-15 solar mass) stars when the cluster is young and from evolving supergiants when the cluster is old (age >/= 6~Myr). Differential reddening between gas and embedded stars is essential to constrain the dereddened cluster colors within the range of youngest clusters. Obscuring dust closely associated with gas, which is distributed in filaments and clumps, as in the case of 30 Doradus, is the most likely configuration giving rise to net reduction of extinction towards stars. The fraction of the stellar photons escaping the nebula unattenuated is estimated to be 50%. GEHRs are rarely found to be simple systems containing stars from single generation. In the present sample such regions in addition to being older than 3~Myr, have their Lyman continuum luminosity reduced by as much as 60%, compared to the observed $B$ band luminosity for a normal IMF. The missing ionizing photons may be escaping the nebula, leading to the ionization of extra-H II region ionized medium. Co-existence of young (age

Variation of surface flashover voltage in SF6 with pressure

Surface flashover characteristics of solid spacers in a rod-plane configuration have been investigated in SF6, at pressures to 400 kPa, for switching impulse voltages to determine the effect of spacer, spacer materials and polarity of applied impulses. The effect of spacer material on the flashover voltage is not significant. For negative polarity impulses, the influence of the spacer is also insignificant. But for positive polarity impulses, at pressures < 200 kPa, the spacer efficiency becomes > 1.0. On the other hand, at pressures > 200 kPa, the presence of spacer drastically reduces the flashover voltage of the system. At about atmospheric pressure also, the spacer efficiency in air has been found to be > 1.0, with the same electrode geometry.

Structural and electrical properties of radio frequency magnetron sputtered tantalum oxide films: Influence of post-deposition annealing

The as-deposited and annealed radio frequency reactive magnetron sputtered tantalum oxide (Ta2O5) films were characterized by studying the chemical binding configuration, structural and electrical properties. X-ray photoelectron spectroscopy and X-ray diffraction analysis of the films elucidate that the film annealed at 673 K was stoichiometric with orthorhombic beta-phase Ta2O5. The dielectric constant values of the tantalum oxide capacitors with the sandwich structure of Al/Ta2O5/Si were in the range from 14 to 26 depending on the post-deposition annealing temperature. The leakage current density was < 20 nA cm(-2) at the gate bias voltage of 0.04 MV/cm for the annealed films. The electrical conduction mechanism observed in the films was Poole-Frenkel. (C) 2010 Elsevier Ltd. All rights reserved.

Water-modeling study of the surface disturbances in continuous slab caster

The present work is based on four static molds using nozzles of different port diameter, port angle, and immersion depth. It has been observed that the meniscus is wavy. The wave amplitude shows a parabolic variation with the nozzle exit velocity. The dimensionless amplitude is found to vary linearly with the Froude number. Vortex formation and bubble entrainment by the wave occurs at the meniscus beyond a critical flow rate, depending upon the nozzle configuration, immersion depth, and the mold aspect ratio.

Electronic structure of early 3d-transition-metal oxides by analysis of the 2p core-level photoemission spectra

The electronic structures of a wide range of early transition-metal (TM) compounds, including Ti and V oxides with metal valences ranging from 2+ to 5+ and formal d-electron numbers ranging from 0 to 2, have been investigated by a configuration-interaction cluster model analysis of the core-level metal 2p x-ray photoemission spectra (XPS). Inelastic energy-loss backgrounds calculated from experimentally measured electron-energy-loss spectra (EELS) were subtracted from the XPS spectra to remove extrinsic loss features. Parameter values deduced for the charge-transfer energy Delta and the d-d Coulomb repulsion energy U are shown to continue the systematic trends established previously for the late TM compounds, giving support to a charge-transfer mechanism for the satellite structures. The early TM compounds are characterized by a large metal d-ligand p hybridization energy, resulting in strong covalency in these compounds. Values for Delta and U suggest that many early TM compounds should be reclassified as intermediate between the charge-transfer regime and the Mott-Hubbard regime.

Fast algorithm for data exchange in reconfigurable tree structures

This paper presents a fast algorithm for data exchange in a network of processors organized as a reconfigurable tree structure. For a given data exchange table, the algorithm generates a sequence of tree configurations in which the data exchanges are to be executed. A significant feature of the algorithm is that each exchange is executed in a tree configuration in which the source and destination nodes are adjacent to each other. It has been proved in a theorem that for every pair of nodes in the reconfigurable tree structure, there always exists two and only two configurations in which these two nodes are adjacent to each other. The algorithm utilizes this fact and determines the solution so as to optimize both the number of configurations required and the time to perform the data exchanges. Analysis of the algorithm shows that it has linear time complexity, and provides a large reduction in run-time as compared to a previously proposed algorithm. This is well-confirmed from the experimental results obtained by executing a large number of randomly-generated data exchange tables. Another significant feature of the algorithm is that the bit-size of the routing information code is always two bits, irrespective of the number of nodes in the tree. This not only increases the speed of the algorithm but also results in simpler hardware inside each node.

Lipid conformational nomenclature: a general method

We propose a conformational nomenclature for amphiphilic lipid molecules that is general and compatible with the stereospecific numbering scheme, in contrast to earlier methods in which discrepancies with the sn-scheme lead to contradictory assignments of the absolute configuration of the system. The present method can be rationally extended to different classes of lipids, both natural and synthetic. It is simple and provides a convenient framework for conformational studies on widely varying classes of lipids.

A transfer matrix approach for evaluation of the response of a multi-layer infinite plate to a two-dimensional pressure excitation

A 6 X 6 transfer matrix is presented to evaluate the response of a multi-layer infinite plate to a given two-dimensional pressure excitation on one of its faces or, alternatively, to evaluate the acoustic pressure distribution excited by the normal velocity components of the radiating surfaces. It is shown that the present transfer matrix is a general case embodying the transfer matrices of normal excitation and one-dimensional pressure excitation due to an oblique incident wave. It is also shown that the present transfer matrix obeys the necessary checks to categorize the physically symmetric multi-layer plate as dynamically symmetric. Expressions are derived to obtain the wave propagation parameters, such as the transmission, absorption and reflection coefficients, in terms of the elements of the transfer matrix presented. Numerical results for transmission loss and reflection coefficients of a two-layer configuration are presented to illustrate the effect of angles of incidence, layer characteristics and ambient media.

Mechanism of ?-cleavage in the excited states of keto sulfides

The beta-cleavage process in photoexcited ketones of structure RCOCH2X (X = CH2CH3, OCH3, SCH3; R = CH3, Ph) has been studied using the configuration interaction procedure within the framework of MINDO/3. The results explain qualitatively why the beta-cleavage process is faster than the alpha-cleavage process in keto sulfides while in keto ethers the reverse is true.

Modeling of a reacting nanofilm on a composite substrate

This article provides a detailed computational analysis of the reaction of dense nanofilms and the heat transfer characteristics on a composite substrate. Although traditional energetic compounds based on organic materials have similar energy per unit weight, non-organic material in nanofilm configuration offers much higher energy density and higher flame speed. The reaction of a multilayer thin film of aluminum and copper oxide has been studied by varying the substrate material and thicknesses. The numerical analysis of the thermal transport of the reacting film deposited on the substrate combined a hybrid approach in which a traditional two-dimensional black box theory was used in conjunction with the sandwich model to estimate the appropriate heat flux on the substrate accounting for the heat loss to the surroundings. A procedure to estimate this heat flux using stoichiometric calculations is provided. This work highlights two important findings. One is that there is very little difference in the temperature profiles between a single substrate of silica and a composite substrate of silicon silica. Secondly, with increase in substrate thickness, the quenching effect is progressively diminished at a given speed. These findings show that the composite substrate is effective and that the average speed and quenching of flames depend on the thickness of the silica substrate, and can be controlled by a careful choice of the substrate configuration. (C) 2011 Elsevier Ltd. All rights reserved.

High swirl-inducing piston bowls in small diesel engines for emission reduction

Detailed three-dimensional CFD simulations involving flow and combustion chemistry are used to study the effect of swirl induced by re-entrant piston bowl geometries on pollutant emissions from a single-cylinder diesel engine. The baseline engine configuration consists of a hemispherical piston bowl and an injector with finite sac volume. The first iteration involved using a torroidal, slightly re-entrant bowl geometry, and a sac-less injector. Pollutant emission measurements indicated a reduction in emissions with this modification. Simulations on both configurations were then conducted to understand the effect of the changes. The simulation results indicate that the selected piston bowl geometry could actually be reducing the in-cylinder swirl and turbulence and the emission reduction may be entirely due to the introduction of the sac-less injector. In-cylinder air motion was then studied in a number of combustion chamber geometries, and a geometry which produced the highest in-cylinder swirl and Turbulence Kinetic Energy (TKE) around the compression top dead centre (TDC) was identified. The optimal nature of this re-entrant piston bowl geometry is confirmed by detailed combustion simulations and emission predictions. (C) 2010 Elsevier Ltd. All rights reserved.

Sputtered thin-film strain gauges for differential pressure measurement

A differential pressure transducer with sputtered gold films as strain gauges has been designed and fabricated. The construction details of the sensing element assembly are given. The details of the strain gauge film configuration employed and the thin-film deposition process are also presented. Information on the output characteristics of the differential pressure transducer such as effect of pressure cycles on output, thermal stability, bidirectional calibration results obtained and individual gauge stability is reported.

S-nets: A Petri net based model for performance evaluation of real-time scheduling algorithms

A new class of nets, called S-nets, is introduced for the performance analysis of scheduling algorithms used in real-time systems Deterministic timed Petri nets do not adequately model the scheduling of resources encountered in real-time systems, and need to be augmented with resource places and signal places, and a scheduler block, to facilitate the modeling of scheduling algorithms. The tokens are colored, and the transition firing rules are suitably modified. Further, the concept of transition folding is used, to get intuitively simple models of multiframe real-time systems. Two generic performance measures, called �load index� and �balance index,� which characterize the resource utilization and the uniformity of workload distribution, respectively, are defined. The utility of S-nets for evaluating heuristic-based scheduling schemes is illustrated by considering three heuristics for real-time scheduling. S-nets are useful in tuning the hardware configuration and the underlying scheduling policy, so that the system utilization is maximized, and the workload distribution among the computing resources is balanced.