Nature of Cl center dot center dot center dot Cl Intermolecular Interactions via Experimental and Theoretical Charge Density Analysis:Correlation of Polar Flattening Effects with Geometry

The experimental charge density distribution in three compounds, 2-chloro-3-quinolinyl methanol, 2-chloro-3-hydroxypyridine, and 2-chloro-3-chloromethyl-8-methylquinoline, has been obtained using high-resolution X-ray diffraction data collected at 100 K based on the aspherical multipole modeling of electron density. These compounds represent type I (cis), type I (trans), and type II geometries, respectively, as defined for short Cl center dot center dot center dot Cl interactions. The experimental results are compared with the theoretical charge densities using theoretical structure factors obtained from a periodic quantum calculation at the B3LYP/6-31G** level. The topological features derived from the Bader's theory of atoms in molecules (AIM) approach unequivocally suggest that both cis and trans type I geometries show decreased repulsion, whereas type II geometry is attractive based on the nature of polar flattening of the electron density around the Cl atom.

Evolution of and preconditions for generation of corrugations on a plane surface in rolling contact

A hard roller under normal load is driven by the flat surface of a soft disc. Corrugations are generated on the disc when certain surface morphological, load, speed and mechanical property-oriented conditions are met. The evolutionary process of corrugation generation and the preconditions necessary for it are investigated morphologically and mechanically for four disc materials: mild steel, brass, PTFE and PMMA.

Observations on transition in plane bubble plumes

Flow visualization studies of plane laminar bubble plumes have been conducted to yield quantitative data on transition height, wavelength and wave velocity of the most unstable disturbance leading to transition. These are believed to be the first results of this kind. Most earlier studies are restricted to turbulent bubble plumes. In the present study, the bubble plumes were generated by electrolysis of water and hence very fine control over bubble size distribution and gas flow rate was possible to enable studies with laminar bubble plumes. Present observations show that (a) the dominant mode of instability in plane bubble plumes is the sinuous mode, (b) transition height and wavelength are related linearly with the proportionality constant being about 4, (c) wave velocity is about 40 % of the mean plume velocity, and (d) normalized transition height data correlate very well with a source Grashof number. Some agreement and some differences in transition characteristics of bubble plumes have been observed compared to those for similar single-phase flows.

Dense granular flow down an inclined plane A comparison between the hard particle model and soft particle simulations

The granular flow down an inclined plane is simulated using the discrete element (DE) technique to examine the extent to which the dynamics of an unconfined dense granular flow can be well described by a hard particle model First, we examine the average coordination number for the particles in the flow down an inclined plane using the DE technique using the linear contact model with and without friction, and the Hertzian contact model with friction The simulations show that the average coordination number decreases below 1 for values of the spring stiffness corresponding to real materials, such as sand and glass, even when the angle of inclination is only 10 larger than the angle of repose Additional measures of correlations in the system, such as the fraction of particles with multibody contact, the force ratio (average ratio of the magnitudes of the largest and the second largest force on a particle), and the angle between the two largest forces on the particle, show no evidence of force chains or other correlated motions in the system An analysis of the bond-orientational order parameter indicates that the flow is in the random state, as in event-driven (ED) simulations V Kumaran, J Fluid Mech 632, 107 (2009), J Fluid Mech 632, 145 (2009)] The results of the two simulation techniques for the Bagnold coefficients (ratio of stress and square of the strain rate) and the granular temperature (mean square of the fluctuating velocity) are compared with the theory V Kumaran, J Fluid Mech 632, 107 (2009), J Fluid Mech 632, 145 (2009)] and are found to be in quantitative agreement In addition, we also conduct a comparison of the collision frequency and the distribution of the precollisional relative velocities of particles in contact The strong correlation effects exhibited by these two quantities in event-driven simulations V Kumaran, J Fluid Mech 632, 145 (2009)] are also found in the DE simulations (C) 2010 American Institute of Physics doi 10 1063/1 3504660]

Growth temperature induced effects in non-polar a-plane GaN on r-plane sapphire substrate by RF-MBE

Non-polar a-plane GaN films were grown on an r-plane sapphire substrate by plasma assisted molecular beam epitaxy (PAMBE). The effect of growth temperature on structural, morphological and optical properties has been studied. The growth of non-polar a-plane (1 1 - 2 0) orientation of the GaN epilayers were confirmed by high resolution X-ray diffraction (HRXRD) study. The X-ray rocking curve (XRC) full width at half maximum of the (1 1 - 2 0) reflection shows in-plane anisotropic behavior and found to decrease with increase in growth temperature. The atomic force micrograph (AFM) shows island-like growth for the film grown at a lower temperature. Surface roughness has been decreased with increase in growth temperature. Room temperature photoluminescence shows near band edge emission at 3.434-3.442 eV. The film grown at 800 degrees C shows emission at 2.2 eV, which is attributed to yellow luminescence along with near band edge emission. (C) 2010 Elsevier B.V. All rights reserved.

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]

Lattice embedding and equilibrium geometry of metal-halogen chains in the two-band extended Hubbard model

Two-band extended Hubbard model studies show that the shift in optical gap of the metal-halogen (MX) chain upon embedding in a crystalline environment depends upon alternation in the site-diagonal electron-lattice interaction parameter (epsilon(M)) and the strength of electron-electron interactions at the metal site (U(M)). The equilibrium geometry studies on isolated chains show that the MX chains tend to distort for alternating epsilon(M) and small U(M) values.

Geometry of proline-containing alpha-helices in proteins

Crystal structure analysis of proline-containing alpha-helices in proteins has been carried out. High resolution crystal structures were selected from the Protein Data Bank. Apart from the standard internal parameters, some parameters which are specifically related to the bend in the helix due to proline have been developed and analyzed. Finally the position and nature of these helices and their interactions with the rest of the protein have been analyzed.

Transverse plane wave analysis of short elliptical chamber mufflers: An analytical approach

Short elliptical chamber mufflers are used often in the modern day automotive exhaust systems. The acoustic analysis of such short chamber mufflers is facilitated by considering a transverse plane wave propagation model along the major axis up to the low frequency limit. The one dimensional differential equation governing the transverse plane wave propagation in such short chambers is solved using the segmentation approaches which are inherently numerical schemes, wherein the transfer matrix relating the upstream state variables to the downstream variables is obtained. Analytical solution of the transverse plane wave model used to analyze such short chambers has not been reported in the literature so far. This present work is thus an attempt to fill up this lacuna, whereby Frobenius solution of the differential equation governing the transverse plane wave propagation is obtained. By taking a sufficient number of terms of the infinite series, an approximate analytical solution so obtained shows good convergence up to about 1300 Hz and also covers most of the range of muffler dimensions used in practice. The transmission loss (TL) performance of the muffler configurations computed by this analytical approach agrees excellently with that computed by the Matrizant approach used earlier by the authors, thereby offering a faster and more elegant alternate method to analyze short elliptical muffler configurations. (C) 2010 Elsevier Ltd. All rights reserved.

Copper( 11) Complexes of Novel Tripodal Ligands containing Phenolate and Benzimidazole/Pyridine Pendants: Synthesis, Structure, Spectra and Electrochemical Behaviour

Mononuclear copper(II) complexes of tri- and tetra-dentate tripodal ligands containing phenolic hydroxyl and benzimidazole or pyridine groups have been isolated. They are of the type (CuL(X)].nH2O, [CuL(H2O)]X.nH2O or [CuL].nH2O where X = Cl-, ClO4-, N3- or NCS- and n = 0-4. The electronic spectra of all the complexes exhibit a broad absorption band around 14000 cm-1 and the polycrystalline as well as the frozen-solution EPR spectra are axial, indicating square-based geometries. The crystal structure of [CuL(Cl)] [HL = (2-hydroxy-5-nitrobenzyl)bis(2-pyridyl-methyl)amine] revealed a square-pyramidal geometry around Cu(II). The mononuclear complex crystallises in the triclinic space group P1BAR with a = 6.938(1), b = 11.782(6), c = 12.678(3) angstrom and alpha = 114.56(3), beta = 92.70(2), gamma = 95.36(2)-degrees. The co-ordination plane is comprised of one tertiary amine and two pyridine nitrogens and a chloride ion. The phenolate ion unusually occupies the axial site, possibly due to the electron-withdrawing p-nitro group. The enhanced pi delocalisation involving the p-nitrophenolate donor elevates the E1/2 values. The spectral and electrochemical results suggest the order of donor strength as nitrophenolate < pyridine < benzimidazole in the tridentate and nitrophenolate < benzimidazole < pyridine in the tetradentate ligand complexes.

On kuhnels 9-vertex complex projective plane

We present an elementary combinatorial proof of the existence and uniqueness of the 9-vertex triangulation of C P2. The original proof of existence, due to Kuhnel, as well as the original proof of uniqueness, due to Kuhnel and Lassmann, were based on extensive computer search. Recently Arnoux and Marin have used cohomology theory to present a computer-free proof. Our proof has the advantage of displaying a canonical copy of the affine plane over the three-element field inside this complex in terms of which the entire complex has a very neat and short description. This explicates the full automorphism group of the Kuhnel complex as a subgroup of the automorphism group of this affine plane. Our method also brings out the rich combinatorial structure inside this complex.

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.

Plane wave analysis of conical and exponential pipes with incompressible mean flow

The general equation for one-dimensional wave propagation at low flow Mach numbers (M less-than-or-equals, slant0·2) is derived and is solved analytically for conical and exponential shapes. The transfer matrices are derived and shown to be self-consistent. Comparison is also made with the relevant data available in the literature. The transmission loss behaviour of conical and exponential pipes, and mufflers involving these shapes, are studied. Analytical expressions of the same are given for the case of a stationary medium. The mufflers involving conical and exponential pipes are shown to be inferior to simple expansion chambers (of similar dimensions) at higher frequencies from the point of view of noise abatement, as was observed earlier experimentally.