Transferability of Multipole Charge Density Parameters for Supramolecular Synthons: A New Tool for Quantitative Crystal Engineering

The modularity of the supramolecular synthon is used to obtain transferability of charge density derived multipolar parameters for structural fragments, thus creating an opportunity to derive charge density maps for new compounds. On the basis of high resolution X-ray diffraction data obtained at 100 K for three compounds methoxybenzoic acid, acetanilide, and 4-methyl-benzoic acid, multipole parameters for O-H center dot center dot center dot O carboxylic acid dimer and N-H center dot center dot center dot O amide infinite chain synthon fragments have been derived. The robustness associated with these supramolecular synthons has been used to model charge density derived multipolar parameters for 4-(acetylamino)benzoic acid and 4-methylacetanilide. The study provides pointers to the design and fabrication of a synthon library of high resolution X-ray diffraction data sets. It has been demonstrated that the derived charge density features can be exploited in both intra- and intermolecular space for any organic compound based on transferability of multipole parameters. The supramolecular synthon based fragments approach (SBFA) has been compared with experimental charge density data to check the reliability of use of this methodology for transferring charge density derived multipole parameters.

Quantum Properties in Transport Through Nanoscopic Rings:Charge-Spin Separation and Interference Effects

Many of the most intriguing quantum effects are observed or could be measured in transport experiments through nanoscopic systems such as quantum dots, wires and rings formed by large molecules or arrays of quantum dots. In particular, the separation of charge and spin degrees of freedom and interference effects have important consequences in the conductivity through these systems. Charge-spin separation was predicted theoretically in one-dimensional strongly inter-acting systems (Luttinger liquids) and, although observed indirectly in several materials formed by chains of correlated electrons, it still lacks direct observation. We present results on transport properties through Aharonov-Bohmrings (pierced by a magnetic flux) with one or more channels represented by paradigmatic strongly-correlated models. For a wide range of parameters we observe characteristic dips in the conductance as a function of magnetic flux which are a signature of spin and charge separation. Interference effects could also be controlled in certain molecules and interesting properties could be observed. We analyze transport properties of conjugated molecules, benzene in particular, and find that the conductance depends on the lead configuration. In molecules with translational symmetry, the conductance can be controlled by breaking or restoring this symmetry, e.g. by the application of a local external potential. These results open the possibility of observing these peculiar physical properties in anisotropic ladder systems and in real nanoscopic and molecular devices.

The effects of charge density and concentration on the composition of polyelectrolyte complexes

Polyelectrolyte complex formation involving carboxymethylcellulose and quaternized poly(vinylpyridine) as the polyions has been studied using viscosity and u.v. spectroscopic methods. The influence of charge density and molecular weight of two polycations on the composition of the complex has been investigated at two different concentrations. The charge density of the polycation is found to have different influences on the composition at different concentrations. The molecular weight of the polycation and the location of the ionic site on the polycation do not show any effect on the composition. A drastic increase in the viscosity of the polyion mixture containing quaternized poly(2-vinylpyridine) in the non-stoichiometric ratio shows evidence for the existence of the soluble polyelectrolyte complex. The results are analysed on the basis of the relative extension of the polyelectrolyte chains.

A possible origin of viscosity in Keplerian accretion disks due to secondary perturbation: Turbulent transport without magnetic fields

The origin of hydrodynamic turbulence in rotating shear flow is a long standing puzzle. Resolving it is especially important in astrophysics when the flow's angular momentum profile is Keplerian which forms an accretion disk having negligible molecular viscosity. Hence, any viscosity in such systems must be due to turbulence, arguably governed by magnetorotational instability, especially when temperature T greater than or similar to 10(5). However, such disks around quiescent cataclysmic variables, protoplanetary and star-forming disks, and the outer regions of disks in active galactic nuclei are practically neutral in charge because of their low temperature, and thus are not expected to be coupled with magnetic fields enough to generate any transport due to the magnetorotational instability. This flow is similar to plane Couette flow including the Coriolis force, at least locally. What drives their turbulence and then transport, when such flows do not exhibit any unstable mode under linear hydrodynamic perturbation? We demonstrate that the three-dimensional secondary disturbance to the primarily perturbed flow that triggers elliptical instability may generate significant turbulent viscosity in the range 0.0001 less than or similar to nu(t) less than or similar to 0.1, which can explain transport in accretion flows.

Geometry and quadratic nonlinearity of charge transfer complexes in solution using depolarized hyper-Rayleigh scattering

We report large quadratic nonlinearity in a series of 1:1 molecular complexes between methyl substituted benzene donors and quinone acceptors in solution. The first hyperpolarizability, beta(HRS), which is very small for the individual components, becomes large by intermolecular charge transfer (CT) interaction between the donor and the acceptor in the complex. In addition, we have investigated the geometry of these CT complexes in solution using polarization resolved hyper-Rayleigh scattering (HRS). Using linearly (electric field vector along X direction) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D = I-2 omega,I-X,I-X/I-2 omega,I-Z,I-X and D' = I-2 omega,I-X,I-C/I-2 omega,I-Z,I-C in the laboratory fixed XYZ frame by detecting the second harmonic scattered light in a polarization resolved fashion. The experimentally obtained first hyperpolarizability, beta(HRS), and the value of macroscopic depolarization ratios, D and D', are then matched with the theoretically deduced values from single and double configuration interaction calculations performed using the Zerner's intermediate neglect of differential overlap self-consistent reaction field technique. In solution, since several geometries are possible, we have carried out calculations by rotating the acceptor moiety around three different axes keeping the donor molecule fixed at an optimized geometry. These rotations give us the theoretical beta(HRS), D and D' values as a function of the geometry of the complex. The calculated beta(HRS), D, and D' values that closely match with the experimental values, give the dominant equilibrium geometry in solution. All the CT complexes between methyl benzenes and chloranil or 1,2-dichloro-4,5-dicyano-p-benzoquinone investigated here are found to have a slipped parallel stacking of the donors and the acceptors. Furthermore, the geometries are staggered and in some pairs, a twist angle as high as 30 degrees is observed. Thus, we have demonstrated in this paper that the polarization resolved HRS technique along with theoretical calculations can unravel the geometry of CT complexes in solution. (C) 2011 American Institute of Physics. doi:10.1063/1.3514922]

Geometry and quadratic nonlinearity of charge transfer complexes in solution: A theoretical study

In this paper, we have computed the quadratic nonlinear optical (NLO) properties of a class of weak charge transfer (CT) complexes. These weak complexes are formed when the methyl substituted benzenes (donors) are added to strong acceptors like chloranil (CHL) or di-chloro-di-cyano benzoquinone (DDQ) in chloroform or in dichloromethane. The formation of such complexes is manifested by the presence of a broad absorption maximum in the visible range of the spectrum where neither the donor nor the acceptor absorbs. The appearance of this visible band is due to CT interactions, which result in strong NLO responses. We have employed the semiempirical intermediate neglect of differential overlap (INDO/S) Hamiltonian to calculate the energy levels of these CT complexes using single and double configuration interaction (SDCI). The solvent effects are taken into account by using the self-consistent reaction field (SCRF) scheme. The geometry of the complex is obtained by exploring different relative molecular geometries by rotating the acceptor with respect to the fixed donor about three different axes. The theoretical geometry that best fits the experimental energy gaps, beta(HRS) and macroscopic depolarization ratios is taken to be the most probable geometry of the complex. Our studies show that the most probable geometry of these complexes in solution is the parallel displaced structure with a significant twist in some cases. (C) 2011 American Institute of Physics. doi:10.1063/1.3526748]

Prediction of the Indian summer monsoon rainfall using a state-of-the-art coupled ocean-atmosphere model

A state-of-the-art model of the coupled ocean-atmosphere system, the climate forecast system (CFS), from the National Centres for Environmental Prediction (NCEP), USA, has been ported onto the PARAM Padma parallel computing system at the Centre for Development of Advanced Computing (CDAC), Bangalore and retrospective predictions for the summer monsoon (June-September) season of 2009 have been generated, using five initial conditions for the atmosphere and one initial condition for the ocean for May 2009. Whereas a large deficit in the Indian summer monsoon rainfall (ISMR; June-September) was experienced over the Indian region (with the all-India rainfall deficit by 22% of the average), the ensemble average prediction was for above-average rainfall during the summer monsoon. The retrospective predictions of ISMR with CFS from NCEP for 1981-2008 have been analysed. The retrospective predictions from NCEP for the summer monsoon of 1994 and that from CDAC for 2009 have been compared with the simulations for each of the seasons with the stand-alone atmospheric component of the model, the global forecast system (GFS), and observations. It has been shown that the simulation with GFS for 2009 showed deficit rainfall as observed. The large error in the prediction for the monsoon of 2009 can be attributed to a positive Indian Ocean Dipole event seen in the prediction from July onwards, which was not present in the observations. This suggests that the error could be reduced with improvement of the ocean model over the equatorial Indian Ocean.

3,12-dinitro-5,10,15,20-tetraphenylporphyrin- an example of a twisted intramolecular charge-transfer system

he porphyrin ring in the title compound, 10,19-dinitro-2,7,12,17-tetraphenyl-21,22,23,24-tetraazapenta-cyclo[16.2.1.1(3,6).1(8,11).1(13,16)]tetracosa-1,3,5,7,9,11(23),-12,14,16,18(21),19-undecaene 0.5-dichloromethane solvate, C44H28N6O4.0.5CH2Cl2, adopts a saddle conformation with neighbouring pyrrole rings tilted with respect to each other. The two nitro groups are situated on alternate pyrrole rings and have their planes angled away from those of the pyrrole rings, thereby indicating that interaction between the porphyrin and nitro groups is slight.

Gain calibration of CCD systems at VBO

The system gain of two CCD systems in regular use at the Vainu Bappu Observatory, Kavalur, is determined at a few gain settings. The procedure used for the determination of system gain and base-level noise is described in detail. The Photometrics CCD system at the 1-m reflector uses a Thomson-CSF TH 7882 CDA chip coated for increased ultraviolet sensitivity. The gain is programme-selected through the parameter 'cgain' varying between 0 and 4095 in steps of 1. The inverse system gain for this system varies almost linearly from 27.7 electrons DN-1 at cgain = 0 to 1.5 electrons DN-1 at cgain = 500. The readout noise is less than or similar 11 electrons at cgain = 66. The Astromed CCD system at 2.3-m Vainu Bappu Telescope uses a GEC P8603 chip which is also coated for enhanced ultraviolet sensitivity. The amplifier gain is selected in discrete steps using switches in the controller. The inverse system gain is 4.15 electrons DN-1 at the gain setting of 9.2, and the readout noise approximately 8 electrons.

Large-Signal Model for Independent DG MOSFET

In this paper, we show the limitations of the traditional charge linearization techniques for modeling terminal charges of the independent double-gate metal-oxide-semiconductor field-effect transistors. Based on our recent computationally efficient Poisson solution for independent double gate transistors, we propose a new charge linearization technique to model the terminal charges and transcapacitances. We report two different types of quasistatic large-signal models for the long-channel device. In the first type, the terminal charges are expressed as closed-form functions of the source- and drain-end inversion charge densities and found to be accurate when the potential distribution at source end of the channel is hyperbolic in nature. The second type, which is found to be accurate in all regimes of operations, is based on the quadratic spline collocation technique and requires the input voltage equation to be solved two more times, apart from the source and drain ends.

Coupled electrostatic-elastic analysis for topology optimization using material interpolation

In this paper, we present a novel analytical formulation for the coupled partial differential equations governing electrostatically actuated constrained elastic structures of inhomogeneous material composition. We also present a computationally efficient numerical framework for solving the coupled equations over a reference domain with a fixed finite-element mesh. This serves two purposes: (i) a series of problems with varying geometries and piece-wise homogeneous and/or inhomogeneous material distribution can be solved with a single pre-processing step, (ii) topology optimization methods can be easily implemented by interpolating the material at each point in the reference domain from a void to a dielectric or a conductor. This is attained by considering the steady-state electrical current conduction equation with a `leaky capacitor' model instead of the usual electrostatic equation. This formulation is amenable for both static and transient problems in the elastic domain coupled with the quasi-electrostatic electric field. The procedure is numerically implemented on the COMSOL Multiphysics (R) platform using the weak variational form of the governing equations. Examples have been presented to show the accuracy and versatility of the scheme. The accuracy of the scheme is validated for the special case of piece-wise homogeneous material in the limit of the leaky-capacitor model approaching the ideal case.

Charge-transfer interaction of picolines with iodine and pi-accepters- A spectroscopic study

The interaction of 2-amino-6-methylpyridine, 2-picoline and 4-picoline as donors with iodine, 7,7',8,8'-tetracyanoquinodimethane,2,3-dichloro-5,6-dicyano-1,4-benzoquinone, p-chloranil, o-chloranil, 2,4,7-trinitro-9-fluorenone and 2,4,5,7-tetranitro-9-fluorenone as acceptors has been studied by measuring visible and ultraviolet spectra. Infrared, electron paramagnetic and nuclear magnetic resonance spectra have also been obtained. Kinetic parameters have been derived. The results indicate that the charge transfer interaction occurs through the formation of free radicals which is followed by a slow reaction to give a diamagnetic product. However, with iodine, the charge transfer complex formation occurs without the formation of free radicals. The donor site is inferred to be the lone pair of electrons of the amino nitrogen of 2-amino-6-methylpridine whereas for 2- and 4-picolines, the preferred site is lone pair of electrons on the pyridine nitrogen.

Impedance peaks of sealed nickel/cadmium cells at low states-of-charge

The impedance of sealed nickel/cadmium cells is measured at low states-of-charge that correspond to a cell e.m.f. range of 0.0 to 1.3 V. The results show that the impedance exhibits a pronounced maximum between 0.3 and 0.45 V. It is concluded that the impedance maxima are due to physicochemical processes taking place at the nickel oxide electrode. The impedance of the nickel oxide electrode is dominated by three different phenomena: (i) a Ni(II)/Ni(III) reaction between 1.3 and 0.8 V; (ii) a double-layer impedance between 0.8 and 0.3 V; (iii) a hydrogen evolution reaction between 0.3 and 0.0 V.

Hydrodynamics of R-charged D1-branes

We study the hydrodynamic properties of strongly coupled SU(N) Yang-Mills theory of the D1-brane at finite temperature and at a non-zero density of R-charge in the framework of gauge/gravity duality. The gravity dual description involves a charged black hole solution of an Einstein-Maxwell-dilaton system in 3 dimensions which is obtained by a consistent truncation of the spinning D1-brane in 10 dimensions. We evaluate thermal and electrical conductivity as well as the bulk viscosity as a function of the chemical potential conjugate to the R-charges of the D1-brane. We show that the ratio of bulk viscosity to entropy density is independent of the chemical potential and is equal to 1/4 pi. The thermal conductivity and bulk viscosity obey a relationship similar to the Wiedemann-Franz law. We show that at the boundary of thermodynamic stability, the charge diffusion mode becomes unstable and the transport coefficients exhibit critical behaviour. Our method for evaluating the transport coefficients relies on expressing the second order differential equations in terms of a first order equation which dictates the radial evolution of the transport coefficient. The radial evolution equations can be solved exactly for the transport coefficients of our interest. We observe that transport coefficients of the D1-brane theory are related to that of the M2-brane by an overall proportionality constant which sets the dimensions.

Distribution of ionic charge carriers and migration barriers in binary alkali silicate glasses

Likely spatial distributions of network-modifying (and mobile) cations in (oxide) glasses are discussed here. At very low modifier concentrations, the ions form dipoles with non-bridging oxygen centres while, at higher levels of modification, the cations tend to order as a result of Coulombic interactions. Activation energies for cation migration are calculated, assuming that the ions occupy (face-sharing) octahedral sites. It is found that conductivity activation energy decreases markedly with increasing modifier content, in agreement with experiment.