Sign Of The Order Parameter In Oriented Systems And Its Utility In The Study Of The Dynamic Properties Of Molecules

Novel one and two dimensional NMR techniques are proposed and utilized for the determination of the signs of the order parameters used for the study of the mobility of the fatty acid chains. The experiments designed to extract this information involve the use of the intensities of the side bands in the spectra of oriented systems spinning at the magic angle. Advantages of the two dimensional technique over the one dimensional method are discussed. The utility of the method in the study of the dynamic properties of membranes and model systems is pointed out.

Radiative interactions in boundary layers

A detailed description of radiative interactions in laminar compressible boundary layers for moderate Mach numbers is presented by way of asymptotic analysis and supporting solutions. The radiation field is described by the differential approximation. While the asymptotic analysis is valid for large N (the ratio of photon mean free path to molecular mean free path) and arbitrary Boltzmann number, Bo (the ratio of convective heat flux to radiation heat flux), the solutions are obtained for Bo [double less-than sign] 1, the case of strong radiative interactions. The asymptotic analysis shows the existence of an optically thin boundary layer for large N and all Bo. For Bo [double less-than sign] 1, two outer regions are observed — one optically thin (at short distances from the leading edge) and the other optically thick (at large distances from the leading edge). An interesting feature not pointed out in the previous literature is the existence of a wall layer at large distances from the leading edge where convective heat flux can be ignored to the leading order of approximation. The radiation field in all cases can be very well approximated by a one-dimensional description. The solutions have been constructed using the ideas of matched asymptotic expansions by approximate analytical procedures and numerical methods. It is shown that, to the leading order of approximation, the radiation slip method yields exactly the same result as the more complicated matching procedure. Both the cases of linear and nonlinear radiation have been considered, the former being of interest in developing approximate methods which are subsequently generalized to handle the nonlinear problem. Detailed results are presented for both cases.

Synthetic, spectroscopic, magnetic, and x-ray structural studies on a vitamin B6-amino acid Schiff base complex, aqua(5'-phosphopyridoxylidenetyrosinato)copper(II) tetrahydrate

A Schiff base metal complex, [Cu(II)(PLP-DL-tyrosinato)(H2O)].4H2O (PLP = pyridoxal phosphate), with the molecular formula CuC17O13N2H27P has been prepared and characterized by magnetic, spectral, and X-ray structural studies. The compound crystallizes in the triclinic space group P1BAR with a = 8.616 (2) angstrom, b = 11.843 (3) angstrom, c = 12.177 (3) angstrom, alpha = 103.40 (2)degrees, beta = 112.32 (2)degrees, gamma = 76.50 (1)degrees, and Z = 2. The structure was solved by the heavy-atom method and refined by least-squares techniques to a final R value of 0.057 for 3132 independent reflections. The coordination geometry around Cu(II) is distorted square pyramidal with phenolic oxygen, imino nitrogen, and carboxylate oxygen from the Schiff base ligand and water oxygen as basal donor atoms. The axial site is occupied by a phosphate oxygen from a neighboring molecule, thus resulting in a one-dimensional polymer. The structure reveals pi-pi interaction of the aromatic side chain of the amino acid with the pyridoxal pi system. A comparative study is made of this complex with similar Schiff base complexes. The variable-temperature magnetic behavior of this compound shows a weak antiferromagnetic interaction.

Spectral element approach to wave propagation in uncertain beam structures

This paper presents a study on the uncertainty in material parameters of wave propagation responses in metallic beam structures. Special effort is made to quantify the effect of uncertainty in the wave propagation responses at high frequencies. Both the modulus of elasticity and the density are considered uncertain. The analysis is performed using a Monte Carlo simulation (MCS) under the spectral finite element method (SEM). The randomness in the material properties is characterized by three different distributions, the normal, Weibull and extreme value distributions. Their effect on wave propagation in beams is investigated. The numerical study shows that the CPU time taken for MCS under SEM is about 48 times less than for MCS under a conventional one-dimensional finite element environment for 50 kHz loading. The numerical results presented investigate effects of material uncertainties on high frequency modes. A study is performed on the usage of different beam theories and their uncertain responses due to dynamic impulse load. These studies show that even for a small coefficient of variation, significant changes in the above parameters are noticed. A number of interesting results are presented, showing the true effects of uncertainty response due to dynamic impulse load.

Estimation of soil hydraulic properties and their uncertainty: comparison between laboratory and field experiment

Often the soil hydraulic parameters are obtained by the inversion of measured data (e.g. soil moisture, pressure head, and cumulative infiltration, etc.). However, the inverse problem in unsaturated zone is ill-posed due to various reasons, and hence the parameters become non-unique. The presence of multiple soil layers brings the additional complexities in the inverse modelling. The generalized likelihood uncertainty estimate (GLUE) is a useful approach to estimate the parameters and their uncertainty when dealing with soil moisture dynamics which is a highly non-linear problem. Because the estimated parameters depend on the modelling scale, inverse modelling carried out on laboratory data and field data may provide independent estimates. The objective of this paper is to compare the parameters and their uncertainty estimated through experiments in the laboratory and in the field and to assess which of the soil hydraulic parameters are independent of the experiment. The first two layers in the field site are characterized by Loamy sand and Loamy. The mean soil moisture and pressure head at three depths are measured with an interval of half hour for a period of 1 week using the evaporation method for the laboratory experiment, whereas soil moisture at three different depths (60, 110, and 200 cm) is measured with an interval of 1 h for 2 years for the field experiment. A one-dimensional soil moisture model on the basis of the finite difference method was used. The calibration and validation are approximately for 1 year each. The model performance was found to be good with root mean square error (RMSE) varying from 2 to 4 cm(3) cm(-3). It is found from the two experiments that mean and uncertainty in the saturated soil moisture (theta(s)) and shape parameter (n) of van Genuchten equations are similar for both the soil types. Copyright (C) 2010 John Wiley & Sons, Ltd.

A Series of Cu-II-Azide Polymers of Cu-6 Building Units and the Role of Chelating Diamine in Controlling their Dimensionality: Synthesis, Structures, and Magnetic Behavior

Four new neutral copper-azido polymers Cu-6(N-3)(12)(aem)(2)](n)(1), Cu-6(N-3)(12)(dmeen)(2)(H2O)(2)](n) (2), Cu-6(N-3)(12)(N,N'-dmen)(2)](n) (3), and Cu-6(N-3)(12)(hmpz)(2)](n) (4) aem = 4-(2-aminoethyl)morpholine; dmeen = N,N-dimethyl-N'-ethylethylenediamine; N,N'-dmen = N,N'-dimethylethylenediamine and hmpz = homopiperazine] have been synthesized by using 0.33 mol equiv of the chelating diamine ligands with Cu(NO3)(2)center dot 3H(2)O/CuCl2 center dot 2H(2)O and an excess of NaN3. Single crystal X-ray structures show that the basic unit of these complexes, especially 1-3, contains very similar Cu-6(II) building blocks. But the overall structures of these complexes vary widely in dimensionality. While 1 is three-dimensional (3D) in nature, 2 and 3 have a two-dimensional (2D) arrangement (with different connectivity) and 4 has a one-dimensional (1D) structure. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in all the four complexes. The experimental susceptibility data have been analyzed by some theoretical model equations.

Demixing of severely overlapped H-1 NMR resonances and interpretation of anomalous intensity pattern of dipolar coupled A(3) spins in a weakly aligning medium

We report a single C-13 spin edited selective proton-proton correlation experiment to decipher overcrowded 13C coupled proton NMR spectra of weakly dipolar coupled spin systems. The experiment unravels the masked C-13 satellites in proton spectrum and permits the measurement of one bond carbon-proton residual dipolar couplings in I3S and for each diastereotopic proton in I2S groups. It also provides all the possible homonuclear proton-proton residual couplings which are otherwise difficult to extract from the broad and featureless one dimensional H-1 spectrum, in addition to enantiodifferentiation in a chiral molecule. Employment of heteronuclear (C-13) decoupling in the evolution period results in complete demixing of overlapped signals from enantiomers. The observed anomalous intensity pattern in strongly dipolar coupled methyl protons in methyl selective correlation experiment has been interpreted using polarization operator formalism. (C) 2010 Elsevier Inc. All rights reserved.

Theory of the effects of destruction of localization by inelastic scattering in the resistivity of pure thin potassium wires

Measurements of the electrical resistivity of thin potassium wires at temperatures near 1 K have revealed a minimum in the resistivity as a function of temperature. By proposing that the electrons in these wires have undergone localization, albeit with large localization length, and that inelastic-scattering events destroy the coherence of that state, we can explain both the magnitude and shape of the temperature-dependent resistivity data. Localization of electrons in these wires is to be expected because, due to the high purity of the potassium, the elastic mean free path is comparable to the diameters of the thinnest samples, making the Thouless length lT (or inelastic diffusion length) much larger than the diameter, so that the wire is effectively one dimensional. The inelastic events effectively break the wire into a series of localized segments, whose resistances can be added to obtain the total resistance of the wire. The ensemble-averaged resistance for all possible segmented wires, weighted with a Poisson distribution of inelastic-scattering lengths along the wire, yields a length dependence for the resistance that is proportional to [L3/lin(T)], provided that lin(T)?L, where L is the sample length and lin(T) is some effective temperature-dependent one-dimensional inelastic-scattering length. A more sophisticated approach using a Poisson distribution in inelastic-scattering times, which takes into account the diffusive motion of the electrons along the wire through the Thouless length, yields a length- and temperature-dependent resistivity proportional to (L/lT)4 under appropriate conditions. Inelastic-scattering lifetimes are inferred from the temperature-dependent bulk resistivities (i.e., those of thicker, effectively three-dimensional samples), assuming that a minimum amount of energy must be exchanged for a collision to be effective in destroying the phase coherence of the localized state. If the dominant inelastic mechanism is electron-electron scattering, then our result, given the appropriate choice of the channel number parameter, is consistent with the data. If electron-phason scattering were of comparable importance, then our results would remain consistent. However, the inelastic-scattering lifetime inferred from bulk resistivity data is too short. This is because the electron-phason mechanism dominates in the inelastic-scattering rate, although the two mechanisms may be of comparable importance for the bulk resistivity. Possible reasons why the electron-phason mechanism might be less effective in thin wires than in bulk are discussed.

Structure of the Indian southwesterly pre-monsoon and monsoon boundary layers: Observations and numerical simulation

Characteristics of pre-monsoon and monsoon boundary layer structure and turbulence were studied in New Delhi and Bangalore, India during the summer of 1987. Micrometeorological towers were installed and instrumented at these locations to provide mean and turbulent surface layer measurements, while information on the vertical structure of the atmosphere was obtained using miniradiosondes. Thermal structures of the pre-monsoon and monsoon boundary layers were quite distinct. The daytime, pre-monsoon boundary layer observed over New Delhi was much deeper than that of the monsoon boundary layer observed over Bangalore and at times was characterized by multiple inversions. Surface, turbulent sensible heat fluxes at both sites were approximately the same (235 and 200 Wm−2 for New Delhi and Bangalore, respectively). Diurnal variations in the monsoon boundary layer at Bangalore were more regular compared to those under pre-monsoon conditions at New Delhi. One-dimensional numerical simulations of the pre-monsoon boundary layer using a turbulent energy closure scheme show good agreement with observations.

Performance prediction and loss analysis of low specific speed submersible pumps

A performance prediction procedure is presented for low specific speed submersible pumps with a review of loss models given in the literature. Most of the loss theories discussed in this paper are one dimensional and improvements are made with good empiricism for the prediction to cover the entire range of operation of the low specific speed pumps. Loss correlations, particularly in the low flow range, are discussed. Prediction of the shape of efficiency-capacity and total head-capacity curves agrees well with the experimental results in almost the full range of operating conditions. The approach adopted in the present analysis, of estimating the losses in the individual components of a pump, provides means for improving the performance and identifying the problem areas in existing designs of the pumps. The investigation also provides a basis for selection of parameters for the optimal design of the pumps in which the maximum efficiency is an important design parameter. The scope for improvement in the prediction procedure with the nature of flow phenomena in the low flow region has been discussed in detail.

Influence of strain softening on the fracture of plain concrete beams

Fracture behaviour of notched and un-notched plain concrete slender beams subjected to three-point or four-point bending is analyzed through a one-dimensional model, also called Softening Beam Model. Fundamental equations of equilibrium are used to develop the model. The influence of structural size in altering the fracture mode from brittle fracture to plastic collapse is explained through the stress distribution across the uncracked ligament obtained by varying the strain softening modulus. It is found that at the onset of fracture instability, stress at the crack tip is equal to zero. The maximum load and fracture load are found to be different and a unique value for the fracture load is obtained. It is shown that the length of the fracture process zone depends on the value of the strain softening modulus. Theoretical limits for fracture process zone length are also calculated. Several nonlinear fracture parameters, such as, crack tip opening displacement, crack mouth opening displacement and fracture energy are computed for a wide variety of beam specimens reported in the literature and are found to compare very well with experimental and theoretical results. It is demonstrated that by following a simple procedure, both pre-peak and post-peak portions of load versus crack mouth opening displacement curve can be obtained quite accurately. Further, a simple procedure to calculate the maximum load is also developed. The predicted values of maximum load are found to agree well with the experimental values. The Softening Beam Model (SBM), proposed in this investigation is very simple and is based on rational considerations. It can completely describe the fracture process from the beginning of formation of the fracture process zone till the onset of fracture instability.A l'aide d'un modèle unidimensionnel dit ldquoSoftening Beam Modelrdquo (SBM), on analyse le comportement à rupture de poutres élancées pleines entaillées ou non, soumises en flexion en trois ou quatre points. Des équations fondamentales d'équilibre sont utilisées pour développer le modèle. On explique l'influence de la taille du composant sur l'altération du mode de rupture en rupture fragile et en effondrement plastique par la distribution par la distribution des contraintes sur le ligament non fissuré lorsque varie le module d'adoucissement. On trouve que la contrainte à l'extrémité de la fissure est nulle est nulle au début de l'instabilité de la rupture. La charge maximum et la charge à la rupture sont trouvées différentes, et on obtient une valeur unique de la charge à la rupture. On montre que la longueur de la zone concernée par le processus de rupture d'pend de la valeur du module d'adoucissement. On calcule également les limites théoriques de longueur de cette zone. Divers paramètres de rupture non linéaire sont calculés pour une large gamme d'éprouvettes en poutres reprises dans la littérature; on trouve qu'il existe une bonne concordance avec les résultats expérimentaux et théoriques. On démontre qu'en suivant une procédure simple on peut obtenir avec une bonne précision la courbe reliant les portions avant et après le pic de sollicitation en fonction du COD de la fissure. En outre, on développe une procédure simple pour calculer la charge maximum. Les valeurs prédites sont en bon accord avec les valeurs expérimentales. Le modèle SBM proposé est très simple et est basé sur des considérations rationnelles. Il est susceptible de décrire complètement le processus de rupture depuis le début de la formation de la zone intéressée jusqu'à l'amorçage de la rupture instable.

Homonuclear NOE in spatially periodic spin systems

The nuclear Overhauser effect equations are solved analytically for a homonuclear group of spins whose sites are periodically arranged, including the special cases where the spins lie at the vertices of a regular polygon and on a one-dimensional lattice. t is shown that, for long correlation times, the equations governing magnetization transfer resemble a diffusion equation. Furthermore the deviation from exact diffusion is quantitatively related to the molecular tumbling correlation time. Equations are derived for the range of magnetization travel subsequent to the perturbation of a single spin in a lattice for both the case of strictly dipolar relaxation and the more general situation where additional T1 mechanisms may be active. The theory given places no restrictions on the delay (or mixing) times, and it includes all the spins in the system. Simulations are presented to confirm the theory.

Exact nonlinear travelling hydromagnetic wave solutions

Exact travelling wave solutions for hydromagnetic waves in an exponentially stratified incompressible medium are obtained. With the help of two integrals it becomes possible to reduce the system of seven nonlinear PDE's to a second order nonlinear ODE which describes an one dimensional harmonic oscillator with a nonlinear friction term. This equation is studied in detail in the phase plane. The travelling waves are periodic only when they propagate either horizontally or vertically. The reduced second order nonlinear differential equation describing the travelling waves in inhomogeneous conducting media has rather ubiquitous nature in that it also appears in other geophysical systems such as internal waves, Rossby waves and topographic Rossby waves in the ocean.

Relaxation system based sub-grid scale modelling for large eddy simulation of Burgers' equation

An implicit sub-grid scale model for large eddy simulation is presented by utilising the concept of a relaxation system for one dimensional Burgers' equation in a novel way. The Burgers' equation is solved for three different unsteady flow situations by varying the ratio of relaxation parameter (epsilon) to time step. The coarse mesh results obtained with a relaxation scheme are compared with the filtered DNS solution of the same problem on a fine mesh using a fourth-order CWENO discretisation in space and third-order TVD Runge-Kutta discretisation in time. The numerical solutions obtained through the relaxation system have the same order of accuracy in space and time and they closely match with the filtered DNS solutions.

A thermodynamic protocol for explaining subcriticality and other subtle features in self-deflagrating solids

A novel universal approach to understand the self-deflagration in solids has been attempted by using basic thermodynamic equation of partial differentiation, where burning mte depends on the initial temperature and pressure of the system. Self-deflagrating solids are rare and are reported only in few compounds like ammonium perchlorate (AP), polystyrene peroxide and tetrazole. This approach has led us to understand the unique characteristics of AP, viz. the existence of low pressure deflagration limit (LPL 20 atm), hitherto not understood sufficiently. This analysis infers that the overall surface activation energy comprises of two components governed by the condensed phase and gas phase processes. The most attractive feature of the model is the identification of a new subcritical regime I' below LPL where AP does not burn. The model is aptly supported by the thermochemical computations and temperature-profile analyses of the combustion train. The thermodynamic model is further corroborated from the kinetic analysis of the high pressure (1-30 atm) DTA thermograms which affords distinct empirical decomposition rate laws in regimes I' and 1 (20-60 atm). Using Fourier-Kirchoff one dimensional heat transfer differential equation, the phase transition thickness and the melt-layer thickness have been computed which conform to the experimental data.