Uma contribuição para o estudo da estrutura de bandas de energia em filmes finos de 'SNO IND.2'

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

First-principle studies of intermolecular and intramolecular catalysis of protonated cocaine

We have performed a series of first-principles electronic structure calculations to examine the reaction pathways and the corresponding free energy barriers for the ester hydrolysis of protonated cocaine in its chair and boat conformations. The calculated free energy barriers for the benzoyl ester hydrolysis of protonated chair cocaine are close to the corresponding barriers calculated for the benzoyl ester hydrolysis of neutral cocaine. However, the free energy barrier calculated for the methyl ester hydrolysis of protonated cocaine in its chair conformation is significantly lower than for the methyl ester hydrolysis of neutral cocaine and for the dominant pathway of the benzoyl ester hydrolysis of protonated cocaine. The significant decrease of the free energy barrier, ∼4 kcal/mol, is attributed to the intramolecular acid catalysis of the methyl ester hydrolysis of protonated cocaine, because the transition state structure is stabilized by the strong hydrogen bond between the carbonyl oxygen of the methyl ester moiety and the protonated tropane N. The relative magnitudes of the free energy barriers calculated for different pathways of the ester hydrolysis of protonated chair cocaine are consistent with the experimental kinetic data for cocaine hydrolysis under physiologic conditions. Similar intramolecular acid catalysis also occurs for the benzoyl ester hydrolysis of (protonated) boat cocaine in the physiologic condition, although the contribution of the intramolecular hydrogen bonding to transition state stabilization is negligible. Nonetheless, the predictability of the intramolecular hydrogen bonding could be useful in generating antibody-based catalysts that recruit cocaine to the boat conformation and an analog that elicited antibodies to approximate the protonated tropane N and the benzoyl O more closely than the natural boat conformer might increase the contribution from hydrogen bonding. Such a stable analog of the transition state for intramolecular catalysis of cocaine benzoyl-ester hydrolysis was synthesized and used to successfully elicit a number of anticocaine catalytic antibodies.

Treatment planning aspects and Monte Carlo methods in proton therapy

Over the last years, the interest in proton radiotherapy is rapidly increasing. Protons provide superior physical properties compared with conventional radiotherapy using photons. These properties result in depth dose curves with a large dose peak at the end of the proton track and the finite proton range allows sparing the distally located healthy tissue. These properties offer an increased flexibility in proton radiotherapy, but also increase the demand in accurate dose estimations. To carry out accurate dose calculations, first an accurate and detailed characterization of the physical proton beam exiting the treatment head is necessary for both currently available delivery techniques: scattered and scanned proton beams. Since Monte Carlo (MC) methods follow the particle track simulating the interactions from first principles, this technique is perfectly suited to accurately model the treatment head. Nevertheless, careful validation of these MC models is necessary. While for the dose estimation pencil beam algorithms provide the advantage of fast computations, they are limited in accuracy. In contrast, MC dose calculation algorithms overcome these limitations and due to recent improvements in efficiency, these algorithms are expected to improve the accuracy of the calculated dose distributions and to be introduced in clinical routine in the near future.

Pattern formation of parametrically driven surface waves induced by vibration

Esta tesis se centra en la generación de ondas superficiales subarmónicas en fluidos sometidos a vibración forzada en el régimen gravitatorio capilar con líquidos de baja viscosidad. Tres problemas diferentes han sido estudiados: un contenedor rectangular con vibración horizontal, la misma geometría pero con una combinación de vibración vertical y horizontal y un obstáculo completamente sumergido vibrado verticalmente en un contenedor grande. Se deriva una ecuación de amplitud desde primeros principios para describir las ondas subarmónicas con forzamiento parámetrico inducido por la vibración. La ecuación es bidimensional mientras que el problema original es tridimensional y admite un forzamiento espacial no uniforme. Usando esta ecuación los tres sistemas han sido analizados, centrándose en calcular la amplitud crítica, la orientación de los patrones y el carácter temporal de los patrones espaciotemporales, que pueden ser estrictamente subarmónicos o cuasiperiodicos con una frecuencia de modulación temporal. La dependencia con los parámetros adimensionales también se considera. La teoría será comparada con los experimentos disponibles en la literatura. Abstract This thesis focus on the generation of subharmonic surface waves on fluids subject to forced vibration in the gravity-capillary regime with liquids of small viscosity. Three different problems have been considered: a rectangular container under horizontal vibration; the same geometry but under a combination of horizontal and vertical vibration; and a fully submerged vertically vibrated obstacle in a large container. An amplitude equation is derived from first principles that fairly precisely describes the subharmonic surfaces waves parametrically driven by vibration. That equation is two dimensional while the underlying problem is three-dimensional and permits spatially nonuniform forcing. Using this equation, the three systems have been analyzed, focusing on the calculation of the threshold amplitude, the pattern orientation, and the temporal character of the spatio-temporal patterns, which can be either strictly subharmonic or quasi-periodic, showing an additional modulation frequency. Dependence on the non-dimensional parameters is also considered. The theory is compared with the experiments available in the literature.

Understanding the structure of the first atomic contact in gold

We have studied experimentally jump-to-contact (JC) and jump-out-of-contact (JOC) phenomena in gold electrodes. JC can be observed at first contact when two metals approach each other, while JOC occurs in the last contact before breaking. When the indentation depth between the electrodes is limited to a certain value of conductance, a highly reproducible behaviour in the evolution of the conductance can be obtained for hundreds of cycles of formation and rupture. Molecular dynamics simulations of this process show how the two metallic electrodes are shaped into tips of a well-defined crystallographic structure formed through a mechanical annealing mechanism. We report a detailed analysis of the atomic configurations obtained before contact and rupture of these stable structures and obtained their conductance using first-principles quantum transport calculations. These results help us understand the values of conductance obtained experimentally in the JC and JOC phenomena and improve our understanding of atomic-sized contacts and the evolution of their structural characteristics.

Analytical first order comparison of amplitude and phase noise in single and dual Mach-Zehnder interferometer detection schemes for DQPSK transmission systems

An analytical first order calculation of the impact of Gaussian white noise on a novel single Mach-Zehnder Interferometer demodulation scheme for DQPSK reveals a constant Q factor ratio to the conventional scheme.

Bubble Growth From First Principals

We consider the simplest relevant problem in the foaming of molten plastics, the growth of a single bubble in a sea of highly viscous Newtonian fluid, and without interference from other bubbles. This simplest problem has defied accurate solution from first principles. Despite plenty of research on foaming, classical approaches from first principles have neglected the temperature rise in the surrounding fluid, and we find that this oversimplification greatly accelerates bubble growth prediction. We use a transport phenomena approach to analyze the growth of a solitary bubble, expanding under its own pressure. We consider a bubble of ideal gas growing without the accelerating contribution from mass transfer into the bubble. We explore the roles of viscous forces, fluid inertia, and viscous dissipation. We find that bubble growth depends upon the nucleus radius and nucleus pressure. We begin with a detailed examination of the classical approaches (thermodynamics without viscous heating). Our failure to fit experimental data with these classical approaches, sets up the second part of our paper, a novel exploration of the essential decelerating role of viscous heating. We explore both isothermal and adiabatic bubble expansion, and also the decelerating role of surface tension. The adiabatic analysis accounts for the slight deceleration due to the cooling of the expanding gas, which depends on gas polyatomicity. We also explore the pressure profile, and the components of the extra stress tensor, in the fluid surrounding the growing bubble. These stresses can eventually be frozen into foamed plastics. We find that our new theory compares well with measured bubble behavior.

Conception mécaniste-empirique des chaussées non revêtues

Dans le contexte où les routes non revêtues sont susceptibles de subir des charges importantes, une méthode rigoureuse pour la conception de ces chaussées basée sur des principes mécanistes-empiriques et sur le comportement mécanique des sols support est souhaitable. La conception mécaniste combinée à des lois d’endommagement permet l’optimisation des structures de chaussées non revêtues ainsi que la réduction des coûts de construction et d’entretien. Le but de ce projet est donc la mise au point d’une méthode de conception mécaniste-empirique adaptée aux chaussées non revêtues. Il a été question tout d’abord de mettre au point un code de calcul pour la détermination des contraintes et des déformations dans la chaussée. Ensuite, des lois d’endommagement empiriques pour les chaussées non revêtues ont été développées. Enfin, les méthodes de calcul ont permis la création d’abaques de conception. Le développement du code de calcul a consisté en une modélisation de la chaussée par un système élastique multi-couches. La modélisation a été faite en utilisant la transformation d’Odemark et les équations de Boussinesq pour le calcul des déformations sous la charge. L’élaboration des fonctions de transfert empiriques adaptées aux chaussées non revêtues a également été effectuée. Le développement des fonctions de transfert s’est fait en deux étapes. Tout d’abord, l’établissement de valeurs seuil d’orniérage considérant des niveaux jugés raisonnables de conditions fonctionnelle et structurale de la chaussée. Ensuite, le développement de critères de déformation admissible en associant les déformations théoriques calculées à l’aide du code de calcul à l’endommagement observé sur plusieurs routes en service. Les essais ont eu lieu sur des chaussées typiques reconstituées en laboratoire et soumises à un chargement répété par simulateur de charge. Les chaussées ont été instrumentées pour mesurer la déformation au sommet du sol d’infrastructure et les taux d’endommagements ont été mesurés au cours des essais.

Submarine dynamic modelling

This paper discusses the development of a dynamic model for a torpedo shaped sub- marine. Expressions for hydrostatic, added mass, hydrodynamic, control surface and pro- peller forces and moments are derived from first principles. Experimental data obtained from flume tests of the submarine are inserted into the model in order to provide computer simulations of the open loop behavior of the system.

Reliability analysis of transform-based stereo matching techniques, and a new matching constraint

Stereo vision is a method of depth perception, in which depth information is inferred from two (or more) images of a scene, taken from different perspectives. Practical applications for stereo vision include aerial photogrammetry, autonomous vehicle guidance, robotics and industrial automation. The initial motivation behind this work was to produce a stereo vision sensor for mining automation applications. For such applications, the input stereo images would consist of close range scenes of rocks. A fundamental problem faced by matching algorithms is the matching or correspondence problem. This problem involves locating corresponding points or features in two images. For this application, speed, reliability, and the ability to produce a dense depth map are of foremost importance. This work implemented a number of areabased matching algorithms to assess their suitability for this application. Area-based techniques were investigated because of their potential to yield dense depth maps, their amenability to fast hardware implementation, and their suitability to textured scenes such as rocks. In addition, two non-parametric transforms, the rank and census, were also compared. Both the rank and the census transforms were found to result in improved reliability of matching in the presence of radiometric distortion - significant since radiometric distortion is a problem which commonly arises in practice. In addition, they have low computational complexity, making them amenable to fast hardware implementation. Therefore, it was decided that matching algorithms using these transforms would be the subject of the remainder of the thesis. An analytic expression for the process of matching using the rank transform was derived from first principles. This work resulted in a number of important contributions. Firstly, the derivation process resulted in one constraint which must be satisfied for a correct match. This was termed the rank constraint. The theoretical derivation of this constraint is in contrast to the existing matching constraints which have little theoretical basis. Experimental work with actual and contrived stereo pairs has shown that the new constraint is capable of resolving ambiguous matches, thereby improving match reliability. Secondly, a novel matching algorithm incorporating the rank constraint has been proposed. This algorithm was tested using a number of stereo pairs. In all cases, the modified algorithm consistently resulted in an increased proportion of correct matches. Finally, the rank constraint was used to devise a new method for identifying regions of an image where the rank transform, and hence matching, are more susceptible to noise. The rank constraint was also incorporated into a new hybrid matching algorithm, where it was combined a number of other ideas. These included the use of an image pyramid for match prediction, and a method of edge localisation to improve match accuracy in the vicinity of edges. Experimental results obtained from the new algorithm showed that the algorithm is able to remove a large proportion of invalid matches, and improve match accuracy.

Monte Carlo modelling of X-ray absorptiometry and its application to body composition studies

This thesis applies Monte Carlo techniques to the study of X-ray absorptiometric methods of bone mineral measurement. These studies seek to obtain information that can be used in efforts to improve the accuracy of the bone mineral measurements. A Monte Carlo computer code for X-ray photon transport at diagnostic energies has been developed from first principles. This development was undertaken as there was no readily available code which included electron binding energy corrections for incoherent scattering and one of the objectives of the project was to study the effects of inclusion of these corrections in Monte Carlo models. The code includes the main Monte Carlo program plus utilities for dealing with input data. A number of geometrical subroutines which can be used to construct complex geometries have also been written. The accuracy of the Monte Carlo code has been evaluated against the predictions of theory and the results of experiments. The results show a high correlation with theoretical predictions. In comparisons of model results with those of direct experimental measurements, agreement to within the model and experimental variances is obtained. The code is an accurate and valid modelling tool. A study of the significance of inclusion of electron binding energy corrections for incoherent scatter in the Monte Carlo code has been made. The results show this significance to be very dependent upon the type of application. The most significant effect is a reduction of low angle scatter flux for high atomic number scatterers. To effectively apply the Monte Carlo code to the study of bone mineral density measurement by photon absorptiometry the results must be considered in the context of a theoretical framework for the extraction of energy dependent information from planar X-ray beams. Such a theoretical framework is developed and the two-dimensional nature of tissue decomposition based on attenuation measurements alone is explained. This theoretical framework forms the basis for analytical models of bone mineral measurement by dual energy X-ray photon absorptiometry techniques. Monte Carlo models of dual energy X-ray absorptiometry (DEXA) have been established. These models have been used to study the contribution of scattered radiation to the measurements. It has been demonstrated that the measurement geometry has a significant effect upon the scatter contribution to the detected signal. For the geometry of the models studied in this work the scatter has no significant effect upon the results of the measurements. The model has also been used to study a proposed technique which involves dual energy X-ray transmission measurements plus a linear measurement of the distance along the ray path. This is designated as the DPA( +) technique. The addition of the linear measurement enables the tissue decomposition to be extended to three components. Bone mineral, fat and lean soft tissue are the components considered here. The results of the model demonstrate that the measurement of bone mineral using this technique is stable over a wide range of soft tissue compositions and hence would indicate the potential to overcome a major problem of the two component DEXA technique. However, the results also show that the accuracy of the DPA( +) technique is highly dependent upon the composition of the non-mineral components of bone and has poorer precision (approximately twice the coefficient of variation) than the standard DEXA measurements. These factors may limit the usefulness of the technique. These studies illustrate the value of Monte Carlo computer modelling of quantitative X-ray measurement techniques. The Monte Carlo models of bone densitometry measurement have:- 1. demonstrated the significant effects of the measurement geometry upon the contribution of scattered radiation to the measurements, 2. demonstrated that the statistical precision of the proposed DPA( +) three tissue component technique is poorer than that of the standard DEXA two tissue component technique, 3. demonstrated that the proposed DPA(+) technique has difficulty providing accurate simultaneous measurement of body composition in terms of a three component model of fat, lean soft tissue and bone mineral,4. and provided a knowledge base for input to decisions about development (or otherwise) of a physical prototype DPA( +) imaging system. The Monte Carlo computer code, data, utilities and associated models represent a set of significant, accurate and valid modelling tools for quantitative studies of physical problems in the fields of diagnostic radiology and radiography.

Asset renewal decision modelling with application to the water utility industry

Reliable infrastructure assets impact significantly on quality of life and provide a stable foundation for economic growth and competitiveness. Decisions about the way assets are managed are of utmost importance in achieving this. Timely renewal of infrastructure assets supports reliability and maximum utilisation of infrastructure and enables business and community to grow and prosper. This research initially examined a framework for asset management decisions and then focused on asset renewal optimisation and renewal engineering optimisation in depth. This study had four primary objectives. The first was to develop a new Asset Management Decision Framework (AMDF) for identifying and classifying asset management decisions. The AMDF was developed by applying multi-criteria decision theory, classical management theory and life cycle management. The AMDF is an original and innovative contribution to asset management in that: · it is the first framework to provide guidance for developing asset management decision criteria based on fundamental business objectives; · it is the first framework to provide a decision context identification and analysis process for asset management decisions; and · it is the only comprehensive listing of asset management decision types developed from first principles. The second objective of this research was to develop a novel multi-attribute Asset Renewal Decision Model (ARDM) that takes account of financial, customer service, health and safety, environmental and socio-economic objectives. The unique feature of this ARDM is that it is the only model to optimise timing of asset renewal with respect to fundamental business objectives. The third objective of this research was to develop a novel Renewal Engineering Decision Model (REDM) that uses multiple criteria to determine the optimal timing for renewal engineering. The unique features of this model are that: · it is a novel extension to existing real options valuation models in that it uses overall utility rather than present value of cash flows to model engineering value; and · it is the only REDM that optimises timing of renewal engineering with respect to fundamental business objectives; The final objective was to develop and validate an Asset Renewal Engineering Philosophy (AREP) consisting of three principles of asset renewal engineering. The principles were validated using a novel application of real options theory. The AREP is the only renewal engineering philosophy in existence. The original contributions of this research are expected to enrich the body of knowledge in asset management through effectively addressing the need for an asset management decision framework, asset renewal and renewal engineering optimisation based on fundamental business objectives and a novel renewal engineering philosophy.

Estimating the probability of an invalid match for matching using the rank transform

A fundamental problem faced by stereo matching algorithms is the matching or correspondence problem. A wide range of algorithms have been proposed for the correspondence problem. For all matching algorithms, it would be useful to be able to compute a measure of the probability of correctness, or reliability of a match. This paper focuses in particular on one class for matching algorithms, which are based on the rank transform. The interest in these algorithms for stereo matching stems from their invariance to radiometric distortion, and their amenability to fast hardware implementation. This work differs from previous work in that it derives, from first principles, an expression for the probability of a correct match. This method was based on an enumeration of all possible symbols for matching. The theoretical results for disparity error prediction, obtained using this method, were found to agree well with experimental results. However, disadvantages of the technique developed in this chapter are that it is not easily applicable to real images, and also that it is too computationally expensive for practical window sizes. Nevertheless, the exercise provides an interesting and novel analysis of match reliability.

Spin-polarization and ferromagnetism of graphitic carbon nitride materials

Polymeric graphitic carbon nitride materials have attracted increasing attention in recent years owning to their potential applications in energy conversion, environment protection, and so on. Here, from first-principles calculations, we report the electronic structure modification of graphitic carbon nitride (g-C3N4) in response to carbon doping. We showed that each dopant atom can induce a local magnetic moment of 1.0 μB in non-magnetic g-C3N4. At the doping concentration of 1/14, the local magnetic moments of the most stable doping configuration which has the dopant atom at the center of heptazine unit prefer to align in a parallel way leading to long-range ferromagnetic (FM) ordering. When the joint N atom is replaced by C atom, the system favors an antiferromagnetic (AFM) ordering at unstrained state, but can be tuned to ferromagnetism (FM) by applying biaxial tensile strain. More interestingly, the FM state of the strained system is half-metallic with abundant states at the Fermi level in one spin channel and a band gap of 1.82 eV in another spin channel. The Curie temperature (Tc) was also evaluated using a mean-field theory and Monte Carlo simulations within the Ising model. Such tunable electron spin-polarization and ferromagnetism are quite promising for the applications of graphitic carbon nitride in spintronics.

An efficient algorithm for the detection of Eden

In this paper, a polynomial time algorithm is presented for solving the Eden problem for graph cellular automata. The algorithm is based on our neighborhood elimination operation which removes local neighborhood configurations which cannot be used in a pre-image of a given configuration. This paper presents a detailed derivation of our algorithm from first principles, and a detailed complexity and accuracy analysis is also given. In the case of time complexity, it is shown that the average case time complexity of the algorithm is \Theta(n^2), and the best and worst cases are \Omega(n) and O(n^3) respectively. This represents a vast improvement in the upper bound over current methods, without compromising average case performance.