Modern Computational Chemistry Methods for Prediction of Ground- and Excited-State Properties in Open-Shell Systems

The main goal of the research presented in this work is to provide some important insights about computational modeling of open-shell species. Such projects are: the investigation of the size-extensivity error in Equation-of-Motion Coupled Cluster methods, the analysis of the Long-Range corrected scheme in predicting UV-Vis spectra of Cu(II) complexes with the 4-imidazole acetate and its ethylated derivative, and the exploration of the importance of choosing a proper basis set for the description of systems such as the lithium monoxide anion. The most significant findings of this research are: (i) The contribution of the left operator to the size-extensivity error of the CR-EOMCC(2,3) approach, (ii) The cause of d-d shifts when varying the range-separation parameter and the amount of the exact exchange arising from the imbalanced treatment of localized vs. delocalized orbitals via the "tuned" CAM-B3LYP* functional, (iii) The proper acidity trend of the first-row hydrides and their lithiated analogs that may be reversed if the basis sets are not correctly selected.

Rapid Determination of Water-Soluble and Fat-Soluble Vitamins in Commercial Formulations by MEEKC

Microemulsion electrokinetic capillary chromatography has been successfully applied to the separation and determination of water-soluble vitamins (thiamine hydrochloride, riboflavin, niacin, pyridoxine hydrochloride, folic acid, cobalamin, ascorbic acid) and a fat-soluble vitamin (alpha-tocopherol acetate). The optimal microemulsion buffer contained sodium dodecylsulfate (SDS) as surfactant, butan-1-ol as the co-surfactant, ethyl acetate as the oil and pH 9.2 tetraborate buffer, modified with 15% (v/v) 2-propanol. UV detection at 214 nm gave adequate sensitivity without interference from sample excipients. Under the optimized conditions, the vitamins were baseline separated in less than 7 min. Analytical curves of peak area versus concentration presented coefficients of determination (R (2) ) > 0.99, acceptable limits of quantification between 8.40 and 16.23 mu g mL(-1) were obtained. Vitamin levels in liquid formulation were quantified with intra-day precision better than 0.99% RSD for migration time and 1.19% RSD for peak area ratio. Recoveries ranged between 98.7 and 101.7%. The method was considered appropriate for rapid and routine analysis.

Squeezing-induced complete transparency in two-level systems

The modification of the statistical properties of vacuum fluctuations, via quadrature squeezing, can dramatically reduce the absorptive and dispersive properties of two-level atoms. We show that for some range of parameter values the system exhibits zero absorption accompanied by zero dispersion of the probe field. This complete transparency is attributed to the coherent population oscillations induced by the squeezed vacuum.

Implications of the LHC two-photon signal for two-Higgs-doublet models

We study the implications for two-Higgs-doublet models of the recent announcement at the LHC giving a tantalizing hint for a Higgs boson of mass 125 GeV decaying into two photons. We require that the experimental result be within a factor of 2 of the theoretical standard model prediction, and analyze the type I and type II models as well as the lepton-specific and flipped models, subject to this requirement. It is assumed that there is no new physics other than two Higgs doublets. In all of the models, we display the allowed region of parameter space taking the recent LHC announcement at face value, and we analyze the W+W-, ZZ, (b) over barb, and tau(+)tau(-) expectations in these allowed regions. Throughout the entire range of parameter space allowed by the gamma gamma constraint, the numbers of events for Higgs decays into WW, ZZ, and b (b) over bar are not changed from the standard model by more than a factor of 2. In contrast, in the lepton-specific model, decays to tau(+)tau(-) are very sensitive across the entire gamma gamma-allowed region.

Multi-product firms and product variety

The goal of this paper is to study the role of multi-product firms in the market provision of product variety. The analysis is conducted using the spokes model of non-localized competition proposed by Chen and Riordan (2007). Firstly, we show that multi-product firms are at a competitive disadvantage vis-a-vis single-product firms and can only emerge if economies of scope are sufficiently strong. Secondly, under duopoly product variety may be higher or lower with respect to both the first best and the monopolistically competitive equilibrium. However, within a relevant range of parameter values duopolists drastically restrict their product range in order to relax price competition, and as a result product variety is far below the efficient level.

Lattice-gas model of particles with orientational and positional degrees of freedom: Mean-field treatment

We consider a lattice-gas model of particles with internal orientational degrees of freedom. In addition to antiferromagnetic nearest-neighbor (NN) and next-nearest-neighbor (NNN) positional interactions we also consider NN and NNN interactions arising from the internal state of the particles. The system then shows positional and orientational ordering modes with associated phase transitions at Tp and To temperatures at which long-range positional and orientational ordering are, respectively, lost. We use mean-field techniques to obtain a general approach to the study of these systems. By considering particular forms of the orientational interaction function we study coupling effects between both phase transitions arising from the interplay between orientational and positional degrees of freedom. In mean-field approximation coupling effects appear only for the phase transition taking place at lower temperatures. The strength of the coupling depends on the value of the long-range order parameter that remains finite at that temperature.

Caracterização de escamas do peixe piau (Leporinus elongatus) e sua aplicação na remoção de Cu(II) de meio aquoso

Characterization of fish scales of Leporinus elongatus and their application in the removal of Cu(II) from aqueous solutions are described. It was observed that the scales are mainly formed by hydroxyapatite and type I collagen. Adsorption of Cu(II) was performed using batch experiments at 25 0C. The ANOVA statistical results have shown that the Langmuir model was successful applied to determine the maximum adsorption capacity of 2.686 x10-4 mol g-1 and the Langmuir equilibrium parameter (b) of 168.8 L mol-1. The Langmuir separation parameter, R L, has shown favorable adsorption of Cu(II) on the scales.

Epäsuoran kysyntätiedon hyödyntäminen verkkokaupan tuotevalikoima- ja hinnoittelupäätöksissä

Tässä diplomityössä tutkitaan, miten verkkokaupan kävijävirran käyttäytymistä analysoimalla voidaan tehdä perusteltuja, tarkoituksenmukaisiin nimikkeisiin ja niiden parametreihin kohdistuvia päätöksiä tilanteessa, jossa laajamittaisemmat historiatiedot toteutuneesta myynnistä puuttuvat. Teoriakatsauksen perusteella muodostettiin ratkaisumalli, joka perustuu potentiaalisten kysyntäajurien muodostamiseen ja testaamiseen. Testisarjan perusteella valittavaa ajuria käytetään estimoimaan nimikkeiden kysyntää, jolloin sitä voidaan käyttää toteutuneen myynnin sijasta esimerkiksi Pareto-analyysissä. Näin huomio on mahdollista keskittää rajattuun määrään merkitykseltään suuria nimikkeitä ja niiden yksityiskohtaisiin parametreihin, joilla on merkitystä asiakkaan ostopäätöstilanteissa. Lisäksi voidaan tunnistaa nimikkeitä, joiden ongelmana on joko huono verkkonäkyvyys tai yhteensopimattomuus asiakastarpeiden kanssa. Ajurien testaamisperiaatteena käytetään kertymäfunktioiden yhdenmukaisuustarkastelua, joka rakentuu kolmesta peräkkäisestä vaiheesta; visuaalisesta tarkastelusta, kahden otoksen 2-suuntaisesta Kolmogorov-Smirnov-yhteensopivuustestistä ja Pearsonin korrelaatiotestistä. Mallia ja sen avulla tuotettua kysynnän ajuria testattiin veneilyalan kuluttaja-asiakkaille suunnatussa verkkokaupassa, jossa sillä tunnistettiin Pareto-jakauman alkupäästä runsaasti nimikkeitä, joiden parametreissa oli myynnin kannalta epäedullisia tekijöitä. Jakauman toisessa päässä tunnistettiin satoja nimikkeitä, joiden ongelmana on ilmeisesti joko huono verkkonäkyvyys tai nimikkeiden yhteensopimattomuus asiakastarpeiden kanssa.

High-Speed Semiconductor Lasers based on Low-Dimensional Active Materials for Optical Telecommunication

The scope of this work is the fundamental growth, tailoring and characterization of self-organized indium arsenide quantum dots (QDs) and their exploitation as active region for diode lasers emitting in the 1.55 µm range. This wavelength regime is especially interesting for long-haul telecommunications as optical fibers made from silica glass have the lowest optical absorption. Molecular Beam Epitaxy is utilized as fabrication technique for the quantum dots and laser structures. The results presented in this thesis depict the first experimental work for which this reactor was used at the University of Kassel. Most research in the field of self-organized quantum dots has been conducted in the InAs/GaAs material system. It can be seen as the model system of self-organized quantum dots, but is not suitable for the targeted emission wavelength. Light emission from this system at 1.55 µm is hard to accomplish. To stay as close as possible to existing processing technology, the In(AlGa)As/InP (100) material system is deployed. Depending on the epitaxial growth technique and growth parameters this system has the drawback of producing a wide range of nano species besides quantum dots. Best known are the elongated quantum dashes (QDash). Such structures are preferentially formed, if InAs is deposited on InP. This is related to the low lattice-mismatch of 3.2 %, which is less than half of the value in the InAs/GaAs system. The task of creating round-shaped and uniform QDs is rendered more complex considering exchange effects of arsenic and phosphorus as well as anisotropic effects on the surface that do not need to be dealt with in the InAs/GaAs case. While QDash structures haven been studied fundamentally as well as in laser structures, they do not represent the theoretical ideal case of a zero-dimensional material. Creating round-shaped quantum dots on the InP(100) substrate remains a challenging task. Details of the self-organization process are still unknown and the formation of the QDs is not fully understood yet. In the course of the experimental work a novel growth concept was discovered and analyzed that eases the fabrication of QDs. It is based on different crystal growth and ad-atom diffusion processes under supply of different modifications of the arsenic atmosphere in the MBE reactor. The reactor is equipped with special valved cracking effusion cells for arsenic and phosphorus. It represents an all-solid source configuration that does not rely on toxic gas supply. The cracking effusion cell are able to create different species of arsenic and phosphorus. This constitutes the basis of the growth concept. With this method round-shaped QD ensembles with superior optical properties and record-low photoluminescence linewidth were achieved. By systematically varying the growth parameters and working out a detailed analysis of the experimental data a range of parameter values, for which the formation of QDs is favored, was found. A qualitative explanation of the formation characteristics based on the surface migration of In ad-atoms is developed. Such tailored QDs are finally implemented as active region in a self-designed diode laser structure. A basic characterization of the static and temperature-dependent properties was carried out. The QD lasers exceed a reference quantum well laser in terms of inversion conditions and temperature-dependent characteristics. Pulsed output powers of several hundred milli watt were measured at room temperature. In particular, the lasers feature a high modal gain that even allowed cw-emission at room temperature of a processed ridge wave guide device as short as 340 µm with output powers of 17 mW. Modulation experiments performed at the Israel Institute of Technology (Technion) showed a complex behavior of the QDs in the laser cavity. Despite the fact that the laser structure is not fully optimized for a high-speed device, data transmission capabilities of 15 Gb/s combined with low noise were achieved. To the best of the author`s knowledge, this renders the lasers the fastest QD devices operating at 1.55 µm. The thesis starts with an introductory chapter that pronounces the advantages of optical fiber communication in general. Chapter 2 will introduce the fundamental knowledge that is necessary to understand the importance of the active region`s dimensions for the performance of a diode laser. The novel growth concept and its experimental analysis are presented in chapter 3. Chapter 4 finally contains the work on diode lasers.

Instability of surface-temperature filaments in strain and shear

The effects of uniform straining and shearing on the stability of a surface quasi-geostrophic temperature filament are investigated. Straining is shown to stabilize perturbations for wide filaments but only for a finite time until the filament thins to a critical width, after which some perturbations can grow. No filament can be stabilized in practice, since there are perturbations that can grow large for any strain rate. The optimally growing perturbations, defined as solutions that reach a certain threshold amplitude first, are found numerically for a wide range of parameter values. The radii of the vortices formed through nonlinear roll-up are found to be proportional to θ/s, where θ is the temperature anomaly of the filament and s the strain rate, and are not dependent on the initial size of the filament. Shearing is shown to reduce the normal-mode growth rates, but it cannot stabilize them completely when there are temperature discontinuities in the basic state; smooth filaments can be stabilized completely by shearing and a simple scaling argument provides the shear rate required. Copyright © 2010 Royal Meteorological Society

Multiple stationary solutions of an irradiated slab

A mathematical model describing the heat budget of an irradiated medium is introduced. The one-dimensional form of the equations and boundary conditions are presented and analysed. Heat transport at one face of the slab occurs by absorption (and reflection) of an incoming beam of short-wave radiation with a fraction of this radiation penetrating into the body of the slab, a diffusive heat flux in the slab and a prescribed incoming heat flux term. The other face of the slab is immersed in its own melt and is considered to be a free surface. Here, temperature continuity is prescribed and evolution of the surface is determined by a Stefan condition. These boundary conditions are flexible enough to describe a range of situations such as a laser shining on an opaque medium, or the natural environment of polar sea ice or lake ice. A two-stream radiation model is used which replaces the simple Beer’s law of radiation attenuation frequently used for semi-infinite domains. The stationary solutions of the governing equations are sought and it is found that there exists two possible stationary solutions for a given set of boundary conditions and a range of parameter choices. It is found that the existence of two stationary solutions is a direct result of the model of radiation absorption, due to its effect on the albedo of the medium. A linear stability analysis and numerical calculations indicate that where two stationary solutions exist, the solution corresponding to a larger thickness is always stable and the solution corresponding to a smaller thickness is unstable. Numerical simulations reveal that when there are two solutions, if the slab is thinner than the smaller stationary thickness it will melt completely, whereas if the slab is thicker than the smaller stationary thickness it will evolve toward the larger stationary thickness. These results indicate that other mechanisms (e.g. wave-induced agglomeration of crystals) are necessary to grow a slab from zero initial thickness in the parameter regime that yields two stationary solutions.

Sample size considerations in active-control non-inferiority trials with binary data based on the odds ratio

This paper presents an approximate closed form sample size formula for determining non-inferiority in active-control trials with binary data. We use the odds-ratio as the measure of the relative treatment effect, derive the sample size formula based on the score test and compare it with a second, well-known formula based on the Wald test. Both closed form formulae are compared with simulations based on the likelihood ratio test. Within the range of parameter values investigated, the score test closed form formula is reasonably accurate when non-inferiority margins are based on odds-ratios of about 0.5 or above and when the magnitude of the odds ratio under the alternative hypothesis lies between about 1 and 2.5. The accuracy generally decreases as the odds ratio under the alternative hypothesis moves upwards from 1. As the non-inferiority margin odds ratio decreases from 0.5, the score test closed form formula increasingly overestimates the sample size irrespective of the magnitude of the odds ratio under the alternative hypothesis. The Wald test closed form formula is also reasonably accurate in the cases where the score test closed form formula works well. Outside these scenarios, the Wald test closed form formula can either underestimate or overestimate the sample size, depending on the magnitude of the non-inferiority margin odds ratio and the odds ratio under the alternative hypothesis. Although neither approximation is accurate for all cases, both approaches lead to satisfactory sample size calculation for non-inferiority trials with binary data where the odds ratio is the parameter of interest.

Obtaining NiAl intermetallic compound using different milling devices

NiAl intermetallic compound was synthesized by mechanical alloying technique in planetary and attritor mills. The starting powders consisted of elemental mixtures of Ni and Al at Ni50Al50(at%) composition. In the planetary mill, compound formation occurred gradually during mechanical alloying, while the occurrence of a mechanically induced self-propagating reaction (MSR) can be suggested in the attritor mill. The NiAl obtained in both mill types was partially disordered with long-range order parameter not inferior to 0.66. Quantitative phase analysis using the Rietveld method was performed in as-milled samples, and this method was also employed to estimate changes in crystallite size and lattice strain of the NiAl produced during mechanical alloying. (C) 2011 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.

Reliable estimation of dense optical flow fields with large displacements

[EN] In this paper we show that a classic optical flow technique by Nagel and Enkelmann can be regarded as an early anisotropic diffusion method with a diffusion tensor. We introduce three improvements into the model formulation that avoid inconsistencies caused by centering the brightness term and the smoothness term in different images use a linear scale-space focusing strategy from coarse to fine scales for avoiding convergence to physically irrelevant local minima, and create an energy functional that is invariant under linear brightness changes.  Applying a gradient descent method to the resulting energy functional leads to a system of diffusion-reaction equations. We prove that this system has a unique solution under realistic assumptions on the initial data, and we present an efficient linear implicit numerical scheme in detail. Our method creates flow fields with 100% density over the entire image domain, it is robust under a large range of parameter variations, and it can recover displacement fields that are far beyond the typical one-pixel limits which are characteristic for many differential methods for determining optical flow. We show that it performs better than the classic optical flow methods with 100%  density that are evaluated by Barron et al. (1994). Our software is available from the Internet.

PWM Control of a Buck Converter with an Amorphous Core Coil

Pulse-width modulation is widely used to control electronic converters. One of the most topologies used for high DC voltage/low DC voltage conversion is the Buck converter. It is obtained as a second order system with a LC filter between the switching subsystem and the load. The use of a coil with an amorphous magnetic material core instead of air core lets design converters with smaller size. If high switching frequencies are used for obtaining high quality voltage output, the value of the auto inductance L is reduced throughout the time. Then, robust controllers are needed if the accuracy of the converter response must not be affected by auto inductance and load variations. This paper presents a robust controller for a Buck converter based on a state space feedback control system combined with an additional virtual space variable which minimizes the effects of the inductance and load variations when a not-toohigh switching frequency is applied. The system exhibits a null steady-state average error response for the entire range of parameter variations. Simulation results are presented.