Studies on some metal monothiobenzoates

Monothiobenzoate (MTB) (Chemical Equation Presented) complexes with the molecular formulas Cr(MTB)3, [Ni(MTB)2]n, [Zn(MTB)2]n, [Cd(MTB)2]n, [Hg(MTB)2]n, [Cu(MTB)]n, and [Ag(MTB)]n have been prepared and studied. All the complexes are nonionic in acetonitrile. Only the chromium complex is soluble in nitrobenzene and found to be monomeric cryoscopically. The thiobenzoate ligand appears to be asymmetrically chelated in Cr(III) and Cd(II) complexes, with stronger oxygen and sulfur coordination, respectively, while practically symmetrically coordinated in Ni(II) and Zn(II) complexes. These four complexes are assigned distorted octahedral structures around the metal ion. The coordination in Hg(II), Cu(I), and Ag(I) complexes is mainly through sulfur indicating the monodentate nature of the thiobenzoate ligand in these complexes. The coordination of monothiobenzoate ion in the complexes has been rationalized in terms of "hard" and "soft" acid-base concept.

Stability of systems with power-law non-linearities

It is shown that a sufficient condition for the asymptotic stability-in-the-large of an autonomous system containing a linear part with transfer function G(jω) and a non-linearity belonging to a class of power-law non-linearities with slope restriction [0, K] in cascade in a negative feedback loop is ReZ(jω)[G(jω) + 1 K] ≥ 0 for all ω where the multiplier is given by, Z(jω) = 1 + αjω + Y(jω) - Y(-jω) with a real, y(t) = 0 for t < 0 and ∫ 0 ∞ |y(t)|dt < 1 2c2, c2 being a constant associated with the class of non-linearity. Any allowable multiplier can be converted to the above form and this form leads to lesser restrictions on the parameters in many cases. Criteria for the case of odd monotonic non-linearities and of linear gains are obtained as limiting cases of the criterion developed. A striking feature of the present result is that in the linear case it reduces to the necessary and sufficient conditions corresponding to the Nyquist criterion. An inequality of the type |R(T) - R(- T)| ≤ 2c2R(0) where R(T) is the input-output cross-correlation function of the non-linearity, is used in deriving the results.

Equivalent constitutive model-based design of wave-absorbing material system and controller

A design methodology for wave-absorbing active material system is reported. The design enforces equivalence between an assumed material model having wave-absorbing behavior and a set of target feedback controllers for an array of microelectro-mechanical transducers which are integral part of the active material system. The proposed methodology is applicable to problems involving the control of acoustic waves in passive-active material system with complex constitutive behavior at different length-scales. A stress relaxation type one-dimensional constitutive model involving viscous damping mechanism is considered, which shows asymmetric wave dispersion characteristics about the half-line. The acoustic power flow and asymptotic stability of such material system are studied. A single sensor non-collocated linear feedback control system in a one-dimensional finite waveguide, which is a representative volume element in an active material system, is considered. Equivalence between the exact dynamic equilibrium of these two systems is imposed. It results in the solution space of the design variables, namely the equivalent damping coefficient, the wavelength(s) to be controlled and the location of the sensor. The characteristics of the controller transfer functions and their pole-placement problem are studied. (c) 2005 Elsevier Ltd. All rights reserved.

Asymtotic solution of the Frieman and Book equation for the pair-correlation function

Using Thomé's procedure, the asymptotic solutions of the Frieman and Book equation for the two-particle correlation in a plasma have been obtained in a complete form. The solution is interpreted in terms of the Lorentz distance. The exact expressions for the internal energy and pressure are evaluated and they are found to be a generalization of the result obtained earlier by others.

Topics in Spatial Econometrics - With Applications to House Prices

Topics in Spatial Econometrics — With Applications to House Prices Spatial effects in data occur when geographical closeness of observations influences the relation between the observations. When two points on a map are close to each other, the observed values on a variable at those points tend to be similar. The further away the two points are from each other, the less similar the observed values tend to be. Recent technical developments, geographical information systems (GIS) and global positioning systems (GPS) have brought about a renewed interest in spatial matters. For instance, it is possible to observe the exact location of an observation and combine it with other characteristics. Spatial econometrics integrates spatial aspects into econometric models and analysis. The thesis concentrates mainly on methodological issues, but the findings are illustrated by empirical studies on house price data. The thesis consists of an introductory chapter and four essays. The introductory chapter presents an overview of topics and problems in spatial econometrics. It discusses spatial effects, spatial weights matrices, especially k-nearest neighbours weights matrices, and various spatial econometric models, as well as estimation methods and inference. Further, the problem of omitted variables, a few computational and empirical aspects, the bootstrap procedure and the spatial J-test are presented. In addition, a discussion on hedonic house price models is included. In the first essay a comparison is made between spatial econometrics and time series analysis. By restricting the attention to unilateral spatial autoregressive processes, it is shown that a unilateral spatial autoregression, which enjoys similar properties as an autoregression with time series, can be defined. By an empirical study on house price data the second essay shows that it is possible to form coordinate-based, spatially autoregressive variables, which are at least to some extent able to replace the spatial structure in a spatial econometric model. In the third essay a strategy for specifying a k-nearest neighbours weights matrix by applying the spatial J-test is suggested, studied and demonstrated. In the final fourth essay the properties of the asymptotic spatial J-test are further examined. A simulation study shows that the spatial J-test can be used for distinguishing between general spatial models with different k-nearest neighbours weights matrices. A bootstrap spatial J-test is suggested to correct the size of the asymptotic test in small samples.

Denoising signals corrupted by chaotic noise

We consider the problem of signal estimation where the observed time series is modeled as y(i) = x(i) + s(i) with {x(i)} being an orbit of a chaotic self-map on a compact subset of R-d and {s(i)} a sequence in R-d converging to zero. This model is motivated by experimental results in the literature where the ocean ambient noise and the ocean clutter are found to be chaotic. Making use of observations up to time n, we propose an estimate of s(i) for i < n and show that it approaches s(i) as n -> infinity for typical asymptotic behaviors of orbits. (C) 2010 Elsevier B.V. All rights reserved.

Bootstrap and Fast Double Bootstrap Tests of Cointegration Rank with Financial Time Series

The likelihood ratio test of cointegration rank is the most widely used test for cointegration. Many studies have shown that its finite sample distribution is not well approximated by the limiting distribution. The article introduces and evaluates by Monte Carlo simulation experiments bootstrap and fast double bootstrap (FDB) algorithms for the likelihood ratio test. It finds that the performance of the bootstrap test is very good. The more sophisticated FDB produces a further improvement in cases where the performance of the asymptotic test is very unsatisfactory and the ordinary bootstrap does not work as well as it might. Furthermore, the Monte Carlo simulations provide a number of guidelines on when the bootstrap and FDB tests can be expected to work well. Finally, the tests are applied to US interest rates and international stock prices series. It is found that the asymptotic test tends to overestimate the cointegration rank, while the bootstrap and FDB tests choose the correct cointegration rank.

Stability of scheduled message communication over degraded broadcast channels

We develop a multi-class discrete-time processor-sharing queueing model for scheduled message communication over a discrete memoryless degraded broadcast channel. The framework we consider here models both the random message arrivals and the subsequent reliable communication by suitably combining techniques from queueing theory and information theory. Requests for message transmissions are assumed to arrive according to i.i.d. arrival processes. Then, (i) we derive an outer bound to the stability region of message arrival rate vectors achievable by the class of stationary scheduling policies, (ii) we show for any message arrival rate vector that satisfies the outer bound, that there exists a stationary "state-independent" policy that results in a stable system for the corresponding message arrival processes, and (iii) under an asymptotic regime, we show that the stability region of information arrival rate vectors is the information-theoretic capacity region of a degraded broadcast channel.

SPSA algorithms with measurement reuse

Four algorithms, all variants of Simultaneous Perturbation Stochastic Approximation (SPSA), are proposed. The original one-measurement SPSA uses an estimate of the gradient of objective function L containing an additional bias term not seen in two-measurement SPSA. As a result, the asymptotic covariance matrix of the iterate convergence process has a bias term. We propose a one-measurement algorithm that eliminates this bias, and has asymptotic convergence properties making for easier comparison with the two-measurement SPSA. The algorithm, under certain conditions, outperforms both forms of SPSA with the only overhead being the storage of a single measurement. We also propose a similar algorithm that uses perturbations obtained from normalized Hadamard matrices. The convergence w.p. 1 of both algorithms is established. We extend measurement reuse to design two second-order SPSA algorithms and sketch the convergence analysis. Finally, we present simulation results on an illustrative minimization problem.

The Power of Bootstrap Tests of Cointegration Rank with Financial Time Series

Bootstrap likelihood ratio tests of cointegration rank are commonly used because they tend to have rejection probabilities that are closer to the nominal level than the rejection probabilities of the correspond- ing asymptotic tests. The e¤ect of bootstrapping the test on its power is largely unknown. We show that a new computationally inexpensive procedure can be applied to the estimation of the power function of the bootstrap test of cointegration rank. The bootstrap test is found to have a power function close to that of the level-adjusted asymp- totic test. The bootstrap test estimates the level-adjusted power of the asymptotic test highly accurately. The bootstrap test may have low power to reject the null hypothesis of cointegration rank zero, or underestimate the cointegration rank. An empirical application to Euribor interest rates is provided as an illustration of the findings.

Robust multivariable controllers for a tublar ammonia reactor

The specific objective of this paper is to develop multivariable controllers that would achieve asymptotic regulation in the presence of parameter variations and disturbance inputs for a tubular reactor used in ammonia synthesis. A ninth order state space model with three control inputs and two disturbance inputs is generated from the nonlinear distributed model using linearization and lumping approximations. Using this model, an approach for control system design is developed keeping in view the imperfections of the model and the measurability of the state variables. Specifically, the design of feedforward and robust integral controllers using state and output feedback is considered. Also, the design of robust multiloop proportional integral controllers is presented. Finally the performance of these controllers is evaluated through simulation.

Evolution and decay of cylindrical and spherical nonlinear acoustic waves generated by a sinusoidal source

The present work gives a comprehensive numerical study of the evolution and decay of cylindrical and spherical nonlinear acoustic waves generated by a sinusoidal source. Using pseudospectral and predictor–corrector implicit finite difference methods, we first reproduced the known analytic results of the plane harmonic problem to a high degree of accuracy. The non-planar harmonic problems, for which the amplitude decay is faster than that for the planar case, are then treated. The results are correlated with the known asymptotic results of Scott (1981) and Enflo (1985). The constant in the old-age formula for the cylindrical canonical problem is found to be 1.85 which is rather close to 2, ‘estimated’ analytically by Enflo. The old-age solutions exhibiting strict symmetry about the maximum are recovered; these provide an excellent analytic check on the numerical solutions. The evolution of the waves for different source geometries is depicted graphically.

Novel phase-transition behavior in an aqueous electrolyte solution

We have investigated the near-critical behavior of the susceptibility of a ternary liquid mixture of 3-methylpyridine. water, and sodium bromide as a function of the salt concentration. The susceptibility was determined from light-scattering measurements performed at a scattering angle of 90 degrees in the one-phase region near the locus of lower consolute points. A sharp crossover from asymptotic Ising behavior to mean-field behavior has been observed at concentrations ranging from 8 to 16.5 mass% NaBr. The range of asymptotic Ising behavior shrinks with increasing salt concentration and vanishes at a NaBr concentration of about 17 mass%. where complete mean-field-like behavior of the susceptibility is observed. A simultaneous pronounced increase in the background scattering at concentrations above 15 mass%, as well as a dip in the critical locus at 17 mass % NaBr, suggests that this phenomenon can be interpreted as mean-field tricritical behavior associated with the formation of a microheterogeneous phase due to clustering of the molecules and ions. An analogy with tri critical behavior observed in polymer solutions as well as the possibility of a charge-density-wave phase is also discussed. In addition, we, have observed a third soap-like phase an the liquid-liquid interface in several binary and ternary liquid mixtures.

The hard-particle model for a dense granular flow down an inclined plane

Perfectly hard particles are those which experience an infinite repulsive force when they overlap, and no force when they do not overlap. In the hard-particle model, the only static state is the isostatic state where the forces between particles are statically determinate. In the flowing state, the interactions between particles are instantaneous because the time of contact approaches zero in the limit of infinite particle stiffness. Here, we discuss the development of a hard particle model for a realistic granular flow down an inclined plane, and examine its utility for predicting the salient features both qualitatively and quantitatively. We first discuss Discrete Element simulations, that even very dense flows of sand or glass beads with volume fraction between 0.5 and 0.58 are in the rapid flow regime, due to the very high particle stiffness. An important length scale in the shear flow of inelastic particles is the `conduction length' delta = (d/(1 - e(2))(1/2)), where d is the particle diameter and e is the coefficient of restitution. When the macroscopic scale h (height of the flowing layer) is larger than the conduction length, the rates of shear production and inelastic dissipation are nearly equal in the bulk of the flow, while the rate of conduction of energy is O((delta/h)(2)) smaller than the rate of dissipation of energy. Energy conduction is important in boundary layers of thickness delta at the top and bottom. The flow in the boundary layer at the top and bottom is examined using asymptotic analysis. We derive an exact relationship showing that the a boundary layer solution exists only if the volume fraction in the bulk decreases as the angle of inclination is increased. In the opposite case, where the volume fraction increases as the angle of inclination is increased, there is no boundary layer solution. The boundary layer theory also provides us with a way of understanding the cessation of flow when at a given angle of inclination when the height of the layer is decreased below a value h(stop), which is a function of the angle of inclination. There is dissipation of energy due to particle collisions in the flow as well as due to particle collisions with the base, and the fraction of energy dissipation in the base increases as the thickness decreases. When the shear production in the flow cannot compensate for the additional energy drawn out of the flow due to the wall collisions, the temperature decreases to zero and the flow stops. Scaling relations can be derived for h(stop) as a function of angle of inclination.

Invariant-preserving Petri net reduction and conditions for invariant-existence

The use of invariants is an important tool for analysis of distributed and concurrent systems modeled by Petri nets. For a large practical system, the computation of desired invariants by the existing techniques is a time-consuming task. This paper proposes a theoretical foundation for simplified computation of desired invariants. We provide invariant-preserving Petri net reduction rules followed by the conditions for the existence of invariants in various well-structured nets. If an invariant exists, it can be found directly from the net structure using the formulas derived, or by applying the existing techniques on the reduced net.