Dissertations / Theses on the topic 'Semi-empirical'

Kohn-Sham density functional theory (DFT) is the most widely-used method for quantum chemical calculations. For most chemical properties it offers relatively accurate results for a relatively low computational cost. This accuracy is governed by the quality of the exchange-correlation functional used. The development and assessment of new functionals is a vital aspect of DFT research, and is the focus of this thesis. In Chapter 1, the theory of traditional wavefunction-based quantum chemistry methods and of DFT is outlined, and the two approaches compared and contrasted. Chapter 2 considers the relatively poor performance of conventional DFT functionals for NMR shielding constants. A simple generalised gradient approximation (GGA) functional, denoted KTl, is developed, which improves this performance significantly. A more flexible functional fitted to experimental energetic data, denoted KT2, is also presented. In Chapter 3, KTl and KT2 are assessed for other magnetic properties, such as chemical shifts, magnetisabilities, and indirect spin-spin coupling constants. Chapter 4 details the development of a third GGA denoted KT3, which is designed to address the shortcomings of KT2 for non-magnetic properties. In Chapter 5, the more flexible functional form of KT3 is shown to give results competitive with the best GGAs for a wide range of chemical properties and for solid state calculations. In Chapter 6, we attempt to improve performance for classical chemical reaction barriers, for which KT3 is relatively poor. This requires a more flexible form in the resulting GGA functional, denoted KT4. A hybrid functional, B97- 3, is also developed with a similar emphasis on reaction barriers. Chapter 7 presents an extensive chemical assessment for KT4 and B97-3. For the systems considered, B97-3 is shown to be the most accurate semi-empirical functional developed to date. Concluding remarks are presented in Chapter 8.

The k . p perturbation method, initially developed for bulk systems has subsequently been generalised to model heterostructures using the envelope function approximation. This semi-empirical modelling technique provides vital information on the electronic and optical properties of complicated material systems that form heterostructures. It is known that k . p theory can be formulated in two ways; either through use of single or double group basis functions, with the implication that spin orbit interaction is either treated as a perturbation in parallel with the k . p term, or as part of the unperturbed Hamiltonian. The critical difference between the two approaches is that under the former, single group selection rules are considered in the evaluation of the k-dependent Hamiltonian, and the subsequent treatment of spin orbit interaction as a perturbation places restrictions on the adapted double group bases. Under the latter approach, double group selection rules are considered, resulting in an explicit change in the k-dependent Hamiltonian for multiband models of 14-band models or higher, and implicit changes to material parameters describing lower band models. A key result, is the ability of the double group formulated k . π theory to properly account for the experimentally measured spin orbit band and conduction band effective masses. This in particular leads to a change in the bulk valence band dispersion relation. In heterostructures, double group-effective mass equations result in changes to the operator ordered Hamiltonian, and the use of double group material parameters impacts the confinement energies and in-plane dispersion of subbands in a quantum well. An investigation is made into the impact of these changes on the electronic properties of Ge/SiGe heterostructures, which have applications as optical modulator devices.

The tire is one of the most important components of the vehicle. It has many functions, such as supporting the load of the vehicle, transmitting the forces which drive, brake and guide the vehicle, and acting as the secondary suspension to absorb the effect of road irregularities before transmitting the forces to the vehicle suspension. A tire is a complex reinforced rubber composite air container. The structure of the tire is very complex. It consists of several layers of synthetic polymer, many flexible filaments of high modulus cord, and glass fiber, which are bonded to a matrix of low modulus polymeric material. As the tire is the only component of the vehicle which makes contact with the road surface, almost all forces and moments acting on the vehicle must be transferred by the tire. To predict the dynamics of the vehicle, we need to know these forces and moments generated at the tire contact patch. Therefore, tire models that accurately describe this dynamic behavior are needed for vehicle dynamic simulation. Many researchers developed tire models for vehicle dynamic simulations; however, most of the development in tire modeling has been limited to deterministic steady-state on-road tire models. The research conducted in this study is concerned with the development of semi-empirical transient tire models for on-road and off-road vehicle simulations. The semi-empirical transient tire model is developed based on existed tire models, analytical tire structure mechanics analysis, and experimental data collected by various researchers. The tire models were developed for vehicle traction, handling and ride analysis. The theoretical mechanics analysis of the tire model focused on the determination of tire and terrain deformation. Then, the results are used together with empirical data to calculate the force response and the moment response. Moreover, the influence of parametric uncertainties in tire parameters on the tire-terrain interaction is investigated. The parametric uncertainties are quantified and propagated through the tire models using a polynomial chaos theory with a collocation approach. To illustrate the capabilities of the tire models developed, both deterministic and stochastic tire models are simulated for various scenarios and maneuvers. Numerically simulated results are analyzed from the perspective of vehicle dynamics. Such an analysis can be used in tire and vehicle development and design.
Ph. D.

Neste trabalho aplica-se um método semi-empírico que utiliza uma técnica de otimização não linear para determinação das eficiências volumétrica e combinada do compressor hermético alternativo. Relações para estimar aproximadamente o fluxo de massa e a potência elétrica do compressor também são propostas. Todas estas características do compressor são calculadas através das relações físicas do modelo, empregadas nos cálculos de otimização. O método é implementado no software EES (Engineering Equation Solver) e baseia-se nos trabalhos de Jahing (1999) e Jahing et al. (2000). No presente método, cinco medições experimentais do fluxo de massa e potência elétrica são suficientes para determinar os parâmetros de ajuste do modelo. Este procedimento permite a geração de mapas de compressores satisfatórios sem a necessidade de um maior número de dados experimentais como no caso da norma ARI 540. Estes resultados obtidos com o modelo podem ser usados para o projeto de novos compressores.
In the present work is applied a semi-empirical method that uses a non-linear optimization technique for determination of the volumetric and combined efficiencies of hermetic reciprocating compressor. Relations to approximately estimate the mass flow and the electric power of the compressor are also proposed. All these compressor characteristics are calculated through physical model relations, used in the optimization calculations. The method is implemented in the EES (Engineering Equation Solver) software and is based on the works of Jahing (1999) and Jahing et al. (2000). In the method, four experimental measurements of the mass flow and electric power are enough to determine the fitting parameters of the model. This procedure allows the generation of satisfactory compressor maps without the necessity of a higher number of experimental data, as in the case of norm ARI 540 application. The results obtained with the model can be used for the design of new compressors.

In the early ship design process a quick overview of which shipdesign that could be the optimal choice for the intended usage needsto be investigated. Therefore the feasibility and accuracy ofinterpolating between measurement data from model resistance serieswhen estimating unknown hulls were conducted. A parametric study wasundertaken in order to investigate which parameters carry the mostimportance in regard to calm water resistance for semi-displacinghulls. In order to asses the whole estimation process one semidisplacing ship (FDS-5) and one bulk carrier with a bulbous bow (JBC)were estimated in regard to calm water resistance by using semiempirical methods and were later compared with CFD results. The CFDresults came from a in part parallel conducted work. The resultsshowed that it is possible to estimate the total resistance withsemi-empirical methods to an unknown hull by linear interpolationwith an accuracy of below 5% in the designed speed interval both forFDS-5 and JBC. The CFD simulations achieved a lower accuracy comparedto the semi-empirical approach, however by furhter calibrating themodels, the accuracy could potentially be improved. Linearinterpolation between two hulls in order to estimate an unknown hull,is only advised when the hulls are nearly identical. Meaning that thehulls must be of the same ship type and that only one parameter isallowed to differ compared to the unknown hull. The parametric studyresulted in parameter importance in falling order: Slenderness ratio,length-beam ratio, longitudinal prismatic coefficient, blockcoefficient and beam-draught ratio. Even though the CFD approach notyet is completely reliable, it could still be a useful complement tothe semi-empirical approach by calculating parameters such as adynamic wetted surface, resistance due to appendages or airresistance of the full-scale ship. Simply by incrementally increasingthe accuracy of individual resistance components an overallimprovement could potentially be achieved.

In this thesis, a semi-empirical model for the infrared emission of dust around star-forming sites in galaxies is developed and then applied to fitting a variety of observations. A simple model of radiative transport in dust clouds is combined with a state-of-the-art model of the microscopic optical properties of interstellar dust grains. In combination with the STARBURST99 stellar spectral synthesis package, this framework is able to produce synthetic spectra for galaxies which extend from the Lyman limit through to the far-infrared. Models of radiative transport in dusty media and of the optical properties of dust grains both have potential to be computationally time-consuming. This has restricted previous semi-empirical models to include detailed considerations of only one of these. In this thesis, a minimal set of simplifications are adopted in the treatment of radiative transport, such that the use of a state-of-the-art model of dust grain energetics is computationally tractable. Following an initial exploration of the predictions of the model, it is applied to fitting the spectra of M82, Arp220 and NGC 6381. M82 and Arp220 are chosen for study because they are nearby starburst galaxies, and test the ability of our model to fit extreme systems. In both cases, we need to remove some of the smallest grains from our model to fit their mid-infrared spectra, but achieve an excellent fit after doing so. NGC 6381 is chosen because it is the only NGC or UGC galaxy within the xFLS field. From our model fit, we infer a flat star formation history over the past (150±50)Myr with star-formation rate (4.69 ± 0.37) M_⊙ yr^-1, and that these stars are surrounded by a column density (6 ± 1) x 10²⁵ Hm^-2  of material and an old stellar population of mass (95 ± 5) x 10⁹ M_⊙^.

This thesis describes an empirical evaluation of semi-supervised and active learning individually, and in combination for the naïve Bayes classifier. Active learning aims to minimise the amount of labelled data required to train the classifier by using the model to direct the labelling of the most informative unlabelled examples. The key difficulty with active learning is that the initial model often gives a poor direction for labelling the unlabelled data in the early stages. However, using both labelled and unlabelled data with semi-supervised learning might be achieve a better initial model because the limited labelled data are augmented by the information in the unlabelled data. In this thesis, a suite of benchmark datasets is used to evaluate the benefit of semi-supervised learning and presents the learning curves for experiments to compare the performance of each approach. First, we will show that the semi-supervised naïve Bayes does not significantly improve the performance of the naïve Bayes classifier. Subsequently, a down-weighting technique is used to control the influence of the unlabelled data, but again this does not improve performance. In the next experiment, a novel algorithm is proposed by using a sigmoid transformation to recalibrate the overly confident naïve Bayes classifier. This algorithm does not significantly improve on the naïve Bayes classifier, but at least does improve the semi-supervised naïve Bayes classifier. In the final experiment we investigate the effectiveness of the combination of active and semi-supervised learning and empirically illustrate when the combination does work, and when does not.

Ab initiocalculation based on density function theory (DFT) is an accu-rate and efficient method for modelling material properties. It is performedby solving the Shrödinger equations with a few assumptions to obtain thephysical properties of the system. It is very computational demanding whendealing with large systems or long-time simulations. Developing empiricalpotentials on the basis ofab initiocalculations on smaller systems is a possi-ble way to solve this problem. The empirical potentials will benefit from theaccuracy ofab initiosimulations and can facilitate applications to large sys-tems and long-time simulations. In this thesis, we have performed two studiesregarding fitting empirical potentials: one is fitting an empirical Sutton-Chenpotential based onab initiosimulations for iron under extreme conditionsand the other one is fitting an improved Finnis-Sinclair potential for ternaryV-Ti-Cr alloy.In the first part, we focus on fitting a Sutton-Chen potential for solid Feunder the Earth’s inner core condition. Based onab initiomolecular dynam-ics (MD) simulation results, the Sutton-Chen potential is fitted to energies ofthe configurations obtained fromab initioMD simulations at the pressure of360 GPa and temperature of 6000 K. The method applied for the fitting isthe Particle Swarm Optimization (PSO) algorithm. The Sutton-Chen poten-tial can reproduce theab initioenergies with an error of 6.2 meV/atom. Setas the same withab initioMD simulations, classical MD using Sutton-Chenpotential can obtain the consistent results with those fromab initioMD sim-ulations at the pressure of 360 GPa and temperature of 6000 K. In order toexplore the size effect on the results, we extend the classical MD to large-sizesystems (from 1024 atoms to 65536 atoms). We also extend the temperaturerange to see the temperature effect on the results.In the second part, we develop an improved Finnis-Sinclair (IFS) potentialfor ternary V-Ti-Cr alloys. The interaction parameters of V-V, Ti-Ti andCr-Cr are fitted to the experimental lattice constants, cohesive energies andelastic constants. The binary alloy potential parameters are obtained byconstructing 3 binary alloy models (V15Ti, V15Cr, V8Ti8) and fitting to theirtheoretical lattice constants, cohesive energies and elastic constants. Finally,the IFS potential is successfully used to calculate mechanical properties andthe monovacancy formation energy in V-Ti-Cr alloy. It is also applied toinvestigate the composition effect on the mechanical properties of ternaryV-Ti-Cr alloys.

QC 20160815

Molecular modeling, using both ab initio and semi-empirical methods has been undertaken for a series of dirhodium complexes in order to improve the understanding of the nature of the chemical bonding in this class of homogeneous catalysts. These complexes, with carboxylamidate and carboxylate ligands, are extremely functional metal catalysts used in the synthesis of pharmaceuticals and agrochemicals. The X-ray crystallography shows anomalies in the bond angles that have potential impact on understanding the catalysis. To resolve these issues, minimum energy structures of several examples (e.g. Rh2(NHCOCH3)4, Rh2(NHCOCH3)4NC, Rh2(CO2CH3)4, Rh2(CO2CH3)4NC, Rh2(CHO2)4, and Rh2(CHO2)4NC) were calculated using Hatree-Fock and Density Functional Theory/B3LYP with the LANL2DZ ECP (Rh), and cc-pVDZ (all other atoms) basis sets.

The receiver operating characteristic (ROC) curve is one of the most commonly used methods to compare the diagnostic performances of two or more laboratory or diagnostic tests. In this thesis, we propose semi-empirical likelihood based confidence intervals for ROC curves of two populations, where one population is parametric while the other one is non-parametric and both populations have missing data. After imputing missing values, we derive the semi-empirical likelihood ratio statistic and the corresponding likelihood equations. It has been shown that the log-semi-empirical likelihood ratio statistic is asymptotically chi-square distributed. The estimating equations are solved simultaneously to obtain the estimated lower and upper bounds of semi-empirical likelihood confidence intervals. Simulation studies are conducted to evaluate the finite sample performance of the proposed empirical likelihood confidence intervals with various sample sizes and different missing rates.

Due to space limitations in urban areas, underground construction has become a common practice worldwide. When using deep excavations, excessive lateral movements are a major concern because they can lead to significant displacements and rotations in adjacent structures. Therefore, accurate predictions of lateral wall deflections and surface settlements are important design criteria in the analysis and design of excavation support systems. This research shows that the current design methods, based on plane strain analyses, are not accurate for designing excavation support systems and that fully three-dimensional (3D) analyses including wall installation effects are needed. A complete 3D finite element simulation of the wall installation at the Chicago and State Street excavation case history is carried out to show the effects of modeling: (i) the installation sequence of the supporting wall, (ii) the excavation method for the wall, and (iii) existing adjacent infrastructure. This model is the starting point of a series of parametric analyses that show the effects of the system stiffness on the resulting excavation-related ground movements. Furthermore, a deformation-based methodology for the analysis and design of excavation support systems is proposed in order to guide the engineer in the different stages of the design. The methodology is condensed in comprehensive flow charts that allow the designer to size the wall and supports, given the allowable soil distortion of adjacent structures or predict ground movements, given data about the soil and support system.

A critical issue in the development of gas condensate reservoirs is accurate prediction of well deliverability. In this investigation a procedure has been developed for accurate prediction of well production rates using semi-empirical approach. The use of state of the art fine grid numerical simulation is time consuming and computationally demanding, therefore not suitable for real time rapid production management decisions required on site. Development of accurate fit-for-purpose correlations for fluid property prediction below the saturation pressure was a major consideration to properly allow for retrograde condensation, complications of multiphase flow and mobility issues. Previous works are limited to use of experimentally measured pressure, volume, temperature (PVT) property data, together with static relative permeability correlations for simulation of well deliverability. To overcome the above limitations appropriate fluid property correlations required for prediction of well deliverability and dynamic three phase relative permeability correlation have been developed to enable forecasting of these properties at all the desired reservoir conditions The developed correlations include; condensate hybrid compressibility factor, viscosity, density, compositional pseudo-pressure, and dynamic three phase relative permeability. The study made use of published data bases of experimentally measured gas condensate PVT properties and three phase relative permeability data. The developed correlations have been implemented in both vertical and horizontal well models and parametric studies have been performed to determine the critical parameters that control productivity in gas condensate reservoirs, using specific case studies. The improved correlations showed superior performance over existing correlations on validation. The investigation has built on relevant literature to present an approach that modifies the black oil model for accurate well deliverability prediction for condensate reservoirs at conditions normally ignored by the conventional approach. The original contribution to knowledge and practice includes (i) the improved property correlations equations, (4.44, 4.47, 4.66, 4.69, 4.75, 5.21) and (ii) extension of gas rate equations, for condensate rate prediction in both vertical and horizontal wells. Standard industry software, the Eclipse compositional model, E-300 has been used to validate the procedure. The results show higher well performance compared with the industry standard. The new procedure is able to model well deliverability with limited PVT and rock property data which is not possible with most available methods. It also makes possible evaluation of various enhanced hydrocarbon recovery techniques and optimisation of gas condensate recovery.

Buoyancy driven underwater gliders, which locomote by modulating their buoyancy and their attitude with moving mass actuators and inflatable bladders, are proving their worth as efficient long-distance, long-duration ocean sampling platforms. Gliders have the capability to travel thousands of kilometers without a need to stop or recharge. There is a need for the development of methods for hydrodynamic modeling. This thesis aims to determine the hydrodynamic parameters for the governing equations of motion for three autonomous underwater vehicles. This approach is two fold, using data obtained from computational flight tests and using a semi-empirical approach. The three vehicles which this thesis focuses on are two gliders (Slocum and XRay/Liberdade), and a third vehicle, the Virginia Tech Miniature autonomous underwater vehicle.
Master of Science

In the drive to more sustainable energy production, polymer electrolyte fuel cells (PEFC) have been at the pinnacle of global research. One of the major drawbacks of PEFCs is therequirement for expensive noble metal catalysts (platinum and ruthenium). Furthermore 75% of the overpotential losses at the cathode are due to the activation of the oxygen reduction reaction (ORR). To reduce the platinum content requirements and understand the cause of the large overpotential of the ORR, a fundamental understanding of the reaction mechanism and the manner in which it proceeds under different operatingconditions is required. Presently, there still remains a large debate in literature around the mechanism followed by the ORR.This study developed a kinetic model from conventional kinetic isotherms and it is proposed that an associative adsorption mechanism occurs at a low overpotential resulting in the dissociation of the hydroperoxyl species determining the rate of the ORR at the cathode of the PEFC. In order to explain the above phenomena a kinetic model was developed, based on the Eley-Rideal mechanism. Furthermore, experiments were conducted at different oxygen partial pressures and low potentials whereby the associative mechanism is believed to dominate. Under these conditions linear sweep voltammograms were recorded. Regression of the derived kinetic model, by using the values for oxygen partial pressure, applied overpotential and kinetic current allowed for the determination of the kinetic constant of a polycrystalline platinum catalyst for ORR.

With the variability in performance of the multitude of parallel environments available today, the conceptual overhead created by the need to anticipate runtime information to make design-time decisions has become overwhelming. Performance-critical applications and libraries carry implicit assumptions based on incidental metrics that are not portable to emerging computational platforms or even alternative contemporary architectures. Furthermore, the significance of runtime concerns such as makespan, energy efficiency and fault tolerance depends on the situational context. This thesis presents a case study in the application of both Mattson’s prescriptive pattern-oriented approach and the more principled structured parallelism formalism to the computational simulation of inelastic neutron scattering spectra on hybrid CPU/GPU platforms. The original ad hoc implementation as well as new patternbased and structured implementations are evaluated for relative performance and scalability. Two new structural abstractions are introduced to facilitate adaptation by lazy optimisation and runtime feedback. A deferred-choice abstraction represents a unified space of alternative structural program variants, allowing static adaptation through model-specific exhaustive calibration with regards to the extrafunctional concerns of runtime, average instantaneous power and total energy usage. Instrumented queues serve as mechanism for structural composition and provide a representation of extrafunctional state that allows realisation of a market-based decentralised coordination heuristic for competitive resource allocation and the Lyapunov drift algorithm for cooperative scheduling.

The importance of ionic channels is due to the passage of ions across the cell membrane which is based on electrochemical gradients. The structure of ionic channels often includes one or several central cores which makes up the pore. The direct electron transfer between the enzyme and unmodified electrode is usually prohibited due to shielding of the redox active sites by the protein shells. In this paper, we have studies the stability of C60-amino acids clusters using by semi-empirical method and investigation of vi-brational frequencies and electrical properties. When you are citing the document, use the following link http://essuir.sumdu.edu.ua/handle/123456789/35428

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Neste trabalho investigamos os efeitos decorrentes da presença de heteroátomos numa folha de “supercoroneno” (molécula C58H18 utilizada como uma primeira aproximação para o grafeno). Mais especificamente, utilizando método semi-empírico PM6, implementado no pacote computacional MOPAC2012®, estudamos as diferentes curvas de energia (calor de formação). As curvas estudadas foram obtidas pela passagem de um átomo de carbono sobre uma folha de supercoroneno na qual existe um heteroátomo (foram utilizadas três diferentes estruturas: C57H18Si, C57H18Ge e C57H18Sn). Nesse contexto, estudamos também o efeito destes heteroátomos sobre a densidade eletrônica e os orbitais HOMO e LUMO das diferentes estruturas.
In this work we investigate the effects of the presence of heteroatoms on a “supercoronene” sheet (C58H18 molecule used as a molecular model for graphene). Specifically, we used the semiempirical method PM6 as implemented in MOPAC2012® software to study several (formation) energy curves. The energy curves were obtained by positioning a carbon atom over a “supercoronene” sheet in which there is a heteroatom (this was done for three different structures: C57H18Si, C57H18Ge and C57H18Sn). In this context, the effect of these heteroatoms on the electronic density distributions, as well as their effect on HOMO and LUMO orbitals were also investigated.

This thesis is concerned with soil erosion from hillslopes in semi-arid Spain. It approaches the problem f rom three related angles which are reflected in its structure: Part 1: The literature is evaluated to determine the current conceptual understanding of the processes of soil erosion, and the organisation of those concepts and evidence from field and laboratory studies into predictive models of the major processes of erosion - rainfall dynamics, rainsplash, infiltration and runoff generation, runoff routing and wash erosion mechanics. Part 2: A field study of the major factors of erosion and their results is conducted over two field seasons for four experimental hilislope sites in southern Spain, and provides detailed information on the spatial and temporal patterns of erosion and their controls. Four main contextual variables are analysed - topography, vegetation cover, surface sediments (soil and coarse fraction) and micro-topographic roughness. The results from four process experiments are presented - infiltration from ponded and simulated rainfall experiments; runoff generation and soil loss from fifty microplot rainfall simulations; natural storm runoff and erosion losses from sub-site plots situated at the midpoint and base of each site; and seasonal and annual patterns of ground surface change derived from soil pin data. Part 3: Concern is with the development of selected erosion process simulation models. These include - the stochastic generation of a temporally nested rainfall series (yield, intensity, duration of wet and dry periods) for the annual/seasonal distribution of daily rainfall, and, subject to threshold criteria, the hourly pattern of storms within a day; an infiltration-runoff generation model based on a modified Green and Ampt (1911) infiltration equation, which predicts time to runoff, volume of pre-saturation soil storage, and runoff volumes. The latter are routed across plots according to an algorithm which determines potential flow lines in three dimensional space. A finite difference kinematic flow model using the Manning flow equation is developed and calibrated from microplot data; finally an erosion model developed from the prototype of Meyer and Wischmeier (1969) predicts spatial and temporal variability of erosion from hillslopes. Major changes to the original model include three-dimensional space and contour curvature, dynamic modelling of flow generation and routing, and physically based detachment and transport mechanics of overland flow. The thesis is divided into two volumes - Volume I comprises the text arranged into three parts. Volume II, for ease of reference, presents supporting and background material, which may be read in parallel with Volume I, and includes Appendices of raw data, results of data analysis, computer programs and simulation results; a list of symbols by chapter; a set of photographic plates, and a full bibliography.

Thesis (MSc)--Stellenbosch University, 2013.
ENGLISH ABSTRACT: This work focussed on a local multiple chamber falling film evaporator (FFE). The FFE is currently under operator control and experiencing large amounts of lost production time due to excessive fouling. Furthermore, the product milk dry mass fraction (WP) is constantly off specification, negatively influencing product quality, while the first effect temperature (TE1) runs higher than the recommended 70°C (this is a main cause of fouling). A two month period of historical data were received with the aim to develop a controller that could outperform the operators by keeping both control variables, WP and TE1, at desired set points while also increasing throughput and maintaining product quality. Access to the local plant was not possible and as such available process data were cleaned and used to identify two data based models, transfer function and autoregressive with exogenous inputs (ARX) models, as well as a semi-empirical-model. The ARX model proved inadequate to predict TE1 trends, with an average TE1 correlation to historical data of 0.36, compared to 0.59 and 0.74 for the transfer function and semi-empirical-models respectively. Product dry mass correlations were similar between the models with the average correlations of 0.47, 0.53 and 0.51 for the semi-empirical, transfer function and ARX models respectively. Although the semi-empirical showed the lowest WP correlation, it was offset by the TE1 prediction advantage. Therefore, the semi-empirical model was selected for controller development and comparisons. The success of the semi-empirical model was in accordance with previous research [1] [2] [3], yet other studies have concluded that ARX modelling was more suited to FFE modelling [4]. Three controllers were developed, namely: a proportional and integral (PI) controller as base case, a linear quadratic regulator (LQR) as an optimal state space alternative and finally, to make full use of process knowledge, a predictive fuzzy logic controller (PFC). The PI controller was able to offer zero offset set point tracking, but could not adequately reject a feed dry mass (WF) disturbance (as proposed and reported by Winchester [5]). The LQR was combined with a Kalman estimator and used pre-delay states. In order to offer increased disturbance rejection, the feedback gains of the disturbance states were tuned individually. The altered LQR and PFC solutions proved to adequately reject all modelled disturbances and outperform a cascade controller designed by Bakker [6]. The maximum deviation in WP was a fractional increase of 0.007 for LQR and 0.005 for FPC, compared to 0.012 for PI and 0.0075 for the cascade controller [6] (WF disturbance fractional increase of 0.01). All the designed controllers managed to reduce the standard deviation of operator controlled WP and TE1 by at least 700% and 450%, respectively. The same level of reduction was seen for maximum control variable deviations (370%), the integral of the absolute error (300%) and the mean squared error (900%). All these performance metrics point to the controllers performing better than the operator based control. In order to prevent manipulated variable saturation and optimise the feed flow rate (F1), a fuzzy feed optimiser (FFO) was developed. The FFO focussed on maximising the available evaporative capacity of the FFE by optimising the motive steam pressure (PS), which supplied heat to the effects. By using the FFO for each controller the average feed flow rate was increased by 4.8% (±500kg/h) compared to the operator control. In addition to flow rate gain, the controllers kept TE1 below 70°C and WP on specification. As such, the overall product quality also increased as well as decreasing the down time due to less fouling.
AFRIKAANSE OPSOMMING: Hierdie projek het op ‘n vallende film verdamper (VFV) gefokus. Die VFV word tans beheer deur operateurs en ondervind groot hoeveelhede verlore produksie tyd a.g.v oormatige aangroeisels. Die vorming van aangroeisels is grootliks te danke aan die eerste effek temperatuur (TE1) wat gereeld 70°C oorskrei. Die produk droë massa fraksie (WP) is ook telkens nie op die gewenste vlak nie, wat produk kwaliteit negatief beinvloed. Data, wat oor ‘n twee maand periode strek, was verkry met die doelstelling om ‘n beheerder te ontwerp wat beter sou vaar as die operateurs, deur beide WP en TE2 om ‘n nou stelpunt te beheer. Ter selfde tyd moet die ontwerpte beheerder die produksie tempo en produk kwaliteit verhoog. Geen toegang tot die plaaslikke VFV was moontlik nie, dus was die data skoongemaak en gebruik om twee data gebasseerde modelle te identifiseer, nl. oordragsfunksie en outoregressiwe met eksogene insette (ORX) modelle, asook ‘n semi-empiriese model. Die ORX model kon nie TE1 goed voorspel nie, met ‘n korrelasie faktor (tot die historiese data) van 0.36, vergeleke met die 0.59 en 0.74 van die oordragsfunksie en semi-empiriese modelle onderskeidelik. WP korrelasie faktore was meer konstant tussen die modelle, met waardes van 0.47, 0.53 en 0.51 vir die semi-empiriese, oordragsfunskie en ORX modelle onderskeidelik. Alhoewel die semi-empiriese model die laagste WP korrelasie vertoon het, was die tekortkoming vergoed deur die beter TE1 voorspelling. Gevolglik was die semi-empiriese model gebruik vir beheerder ontwerp en vergelyking. Die sukses van die semiempiriese model stem ooreen met vorige studies [1] [2] [3], tog het ander studies al bevind dat die ORX model beter gepas is vir die VFV proses [4]. Drie beheerders was ontwikkel, nl. ‘n proporsionele en integreerder (PI) beheerder as basis geval, ‘n liniêre kwadratiese reguleerder (LKR) as optimale toestands beheer alternatief en laastens ‘n voorspellende wasige logika beheerder (VWB) om volle gebruik van proseskennis te maak. Die PI beheerder kon foutlose volging van die stelpunte lewer, maar kon nie ‘n inset voer droë massa fraksie (WF) versteuring (soos voorgestel en weergegee deur Winchester [5]) na wense verwerp nie. Die LKR was saamgevoeg met ‘n Kalman afskatter en het gebruik gemaak van onvertraagde toestande. Die versteuringstoestande was individueel verstel om beter versteurings verweping te weeg te bring. Die aangepaste LKR en VWB kon beide die WF versteuring verwerp en het beter gevaar as ‘n kaskade beheer oplossing wat deur Bakker [6] ontwerp was. Die WP afwyking is beperk tot ‘n fraksie droë masse verandering van 0.007 vir LKR en 0.005 vir VWB, vergeleke met die afwykings van 0.012 vir die PI beheerder asook die 0.0075 van die kaskade beheerder [6]. Die ontwerpte beheerder kon ook die standaard afwyking van beide WP en TE1 met ten minste 700% en 450% onderskeidelik verminder. Soortgelyke verbeterings was gesien vir die maksimum beheer veranderlikke afwyking (370%), die integraal van die absolute fout (300%) en die gemiddelde fout (900%). Dus het die ontwerpte beheerders wesenlik verbeter op die operateur beheer. Ten einde om gemanipuleerde veranderlikke versadiging te voorkom, asook die voer vloei (V1) te optimiseer, was ‘n wasige logika optimiseerder (WVO) ontwerp. Die WVO het die beskikbare verdampingskapasiteit ten volle benut deur te sorg dat die stoom druk (PS), wat energie verskaf vir verdamping, ge-optimiseerd bly. ‘n Gemiddelde V1 stygging van 4.8% (±500kg/uur), vergeleke met operateur beheer, is waargeneem. Al die beheerders kon steeds die WP en TE1 stelpunte volg en dus TE1 onder 70°C hou (wat verminderde vormasie van aangroeisels tot gevolg gehad het). Daarom het die produk kwailiteit verhoog en die verlore produksie tyd verminder.

This thesis is a summary of studies that were carried out as part of candidacy for aPhD degree. The purpose of these studies was to evaluate some factors in shipdesign that are intended for navigating in ice using numerical simulations. A semiempiricalnumerical procedure was developed by combining mathematical modelsthat describe the various elements of the continuous-mode icebreaking process inlevel ice. The numerical procedure was calibrated and validated using full- andmodel-scale measurements. The validated numerical model was in turn used toinvestigate and clarify issues that have not been previously considered.An icebreaker typically breaks ice by its power, its weight and a strengthened bowwith low stem angle. The continuous icebreaking process involves heave and pitchmotions that may not be negligible. The numerical procedure was formulated toaccount for all of the possible combinations of motions for six degrees of freedom(DOFs). The effects of the motion(s) for certain DOF(s) were investigated bycomparing simulations in which the relevant motion(s) were first constrained andthen relieved.In the continuous-mode icebreaking process, a ship interacts with an icebreakingpattern consisting of a sequence of individual icebreaking events. The interactionsamong the key characteristics of the icebreaking process, i.e., the icebreakingpattern, ship motions, and ice resistance, were studied using the numericalprocedure in which the ship motions and excitation forces were solved for in thetime domain and the ice edge geometry was simultaneously updated.Observations at various test scales have shown that the crushing pressure arisingfrom the ice–hull interaction depends on the contact area involved. A parametricstudy was carried out on the numerical procedure to investigate the effect of thecontact pressure on icebreaking.The loading rates associated with the ship’s forward speed have been anticipatedto play an important role in determining the bending failure loads, in view of thedynamic water flow underneath the ship and the inertia of the ice. The dynamicbending behavior of ice could also explain the speed dependence of the icebreakingresistance component. A dynamic bending failure criterion for ice was derived,incorporated into the numerical procedure and then validated using full-scale data.The results obtained using the dynamic and static bending failure criteria werecompared to each other.In addition, the effect of the propeller flow on the hull resistance for ships runningpropeller first in level ice was investigated by applying the information obtainedfrom model tests to the numerical procedure. The thrust deduction in ice wasdiscussed.

In many parts of the world, and particularly in semi-arid and arid regions, shallow foundations are located above the ground water table where the soil is typically in a state of unsaturated conditions. The capillary stresses (i.e., matric suction or negative pore water pressure) above the ground water table contribute significantly towards the bearing capacity of unsaturated soils. However, the bearing capacity contribution due to the capillary stresses is routinely ignored in the conventional engineering design of shallow foundations. The bearing capacity of unsaturated soil is also estimated using conventional approaches that are used for saturated soils ignoring the influence of matric suction. This is a conservative approach used in the design of shallow foundations for unsaturated soils. For this reason, it is important to understand the influence of matric suction on the bearing capacity of unsaturated soils. In addition, a framework to interpret the bearing capacity of unsaturated soils that takes account of the influence of matric suction will be useful. In the present research program, an extensive experimental study is undertaken to investigate the bearing capacity of a compacted coarse-grained soil under both saturated and unsaturated conditions. Two different series of tests were carried out in a bearing capacity tank using two different sizes of square shaped model footings (i.e. 100 mm x 100 mm and 150 mm x 150 mm). The bearing capacity tank of the size 900 mm x 900 mm and 750 mm height was specially designed and fabricated in the University of Ottawa, Faculty of Engineering Student Workshop to undertake the present research program. The first series of tests were conducted to determine the bearing capacity of the compacted sand in the tank under fully saturated conditions. The second series of tests were conducted to study the influence of matric suction on the bearing capacity of compacted sand under different unsaturated conditions. The ground water table level in the bearing capacity tank was varied using the drainage valves to achieve different values of matric suction below the model footings. The variation of the matric suction with respect to depth below the model footing was measured using four commercial Tensiometers. These Tensiometers were located at different depths in the proximity of the expected stress bulb (i.e., 1.5 times the width of the footing) below the loaded footing. In addition, piezometers were also placed in the tank to monitor the ground water table levels. The model footings were loaded using a loading frame until failure to measure the bearing capacity. The sand used in the bearing capacity tank was compacted to achieve a density index value of approximately equal to 65% such that the failure of the footing will be in accordance with the general shear failure criteria. The experimental results of the test program demonstrated that the bearing capacity of unsaturated soils is approximately 5 to 7 times higher than the bearing capacity of the same soil under saturated conditions. As expected, there was a non-linear increase in the bearing capacity of the compacted sand with an increase in the matric suction under the model footings. In addition, it was also observed that there is a relationship between the soil-water retention curve (SWRC) and the bearing capacity of unsaturated soils. Terzaghi's bearing capacity theory for saturated soils was extended to interpret the bearing capacity of unsaturated soils using the saturated shear strength parameters and taking account of the influence of the matric suction. In addition, a simple technique was proposed for predicting the variation of the bearing the capacity of unsaturated soils using the soil-water retention curve (SWRC) and the saturated shear strength parameters. The proposed prediction procedure was similar to the procedure used for predicting the shear strength of unsaturated soils by Vanapalli et al. (1996). The procedure proposed for predicting the bearing capacity of unsaturated soils was extended for another four soils, of which two of them were coarse-grained and the other two were fine-grained in nature. The data for the four soils was obtained from the literature. The results of the study suggest that the variation of the bearing capacity of unsaturated soils can be reasonably well predicted using the SWRC and the saturated shear strength parameters. The framework of the research program developed based on the studies undertaken on model footings shows considerable promise for extending it to field studies.

In this thesis a new computer code is developed to perform non-equilibrium Green’s function based calculations of electronic transmission, using a Hamiltonian computed from self consistent extended Hückle theory as input. Individual elements of this code are tested to ensure correctness. To evaluate its usefulness, the code is tested on porphyrin based systems against the more traditional density functional theory methods of generating the required Hamiltonian. It is then used on more complex porphyrin systems, and comments are made on the use of porphyrin in molecular electronics. Finally it is used on DNA based systems too large to be dealt with efficiently via density functional theory to provide predictions of the effects of DNA structure on its conductance.

Thesis (PhD)--University of Stellenbosch, 2004.
388 leaves printed on single pages, preliminary pages i- xv and numbered pages 1-371. Includes bibliography, list of tables and figures.
Digitized at 330 dpi black and white and 330 dpi color PDF format (OCR), using KODAK i 1220 PLUS scanner.
ENGLISH ABSTRACT: Bath type furnaces have become an established technology for the intensive smelting, converting and refining of primary and secondary raw materials. Since these furnaces normally have large inventories, long time constants and complex metallurgies, a dynamic model-based prediction strategy is the only feasible approach to operator decision support and process control. This dissertation presents a semi-empirical approach to the stochastic modelling of bath-type pyrometallurgical reactors, which leads to a generic model type called the Equilib-ARMAX model. The modelling approach is applied to three case studies: • A nickel-copper matte converting operation using a submerged lance injection reactor • A chromite smelting operation to produce high carbon ferrochrome using a direct current (DC) plasma smelting furnace • An ilmenite smelting operation to produce high titania slag and pig iron, using a direct current (DC) plasma smelting furnace. In each case, the industrial operations were analysed with regard to the practical and technological constraints which influence the type and quality of the process data. The fundamental process phenomena associated with each operation have been analysed to ascertain which fundamental variables should be included within the overall semi-empirical approach, without sacrificing model transparency, simplicity, accuracy and calculation time. It was considered that an overly complex model would be inappropriate given that data from industrial smelting operations show significant random variance. The thermochemistry and phase equilibria associated with each operation are discussed in detail, as they become the fundamental backbone of the semi-empirical models. The equilibria have been modelled with software that uses non-ideal solutions models and Gibbs free energy minimisation to predict the phase and chemical equilibria that could be expected for a given feed recipe and operating temperature. As the thermodynamic modelling software is not stable within an industrial environment, an artificial intelligent mapping technique has been developed to map process inputs to equilibrium outputs. A multi-layer perceptron neural network has been used as the convenient mapping method to represent equilibrium. The neural networks were trained using tens of thousands of feed recipes, where the feed component ratios were varied based on a 3N factorial design. The amounts and chemistries of all equilibrium phases could be calculated with high accuracies (R2 > 0.95) in all cases. Further stochastic analysis and modelling require additional information about the property distributions associated with each measurement. The homogeneities of the furnace products (slag, alloy and flue dust) critically influence the level of confidence that one can associate with plant measurements. The homogeneities were characterised for the DC plasma arc furnaces and they were benchmarked against a submerged arc furnace. It was found that the homogeneity varied per element, with silicon and sulphur tending to show highest variations in the alloy melts. The observation that the variation in these two elements are both high can partially be attributed to the fact that SiS evaporates from the bath surface, especially in regions close to the arc attachment zone. A significant negative correlation was found between the relative standard deviation per tap (using silicon) and the degree of superheat / subcooling of the alloy, indicating that the homogeneity can be strongly influenced by the changes in rheology due to subcooling below the liquidus (which leads to the precipitation of solid phases and increases the observed melt viscosity). Mixedness or homogeneity and data uncertainty are therefore inseparably linked. The relative standard deviations associated with the homogeneity characterisation, as well as known sampling and assaying variances were used to develop reconciled material balances based on measured plant data. Material balance closure was therefore obtained within the inherent uncertainties of the plant data. Biases in the plant data were identified simultaneously with data reconciliation. Moreover, it was shown using Fast Fourier Power Spectra and statespace analysis that the data reconciliation was a good low-pass filter, as it extracted the major process trends components in the noisy data and it also improved the overall dynamic behaviour characteristics of the data. Finally systems identification techniques were used to develop dynamic transfer function models that were linear in the parameters to be estimated. These systems models were based on the reconciled plant data and equilibrium predictions. The final systems models are therefore equilibrium-autoregressive-moving-average models with exogenous variables (Equilib-ARMAX). The model parameters can be estimated recursively using a simple least squares method. The final models could dynamically predict the metallurgy of the subsequent tap 4-6 hours in advance, based on a given suite of set-points, within the inherent accuracy of the data. These models may be used to suggest the optimal operating conditions through an operator guidance system, or more simply, the models are simple enough to be used in a spreadsheet on a manager's desk.
AFRIKAANSE OPSOMMING: Bad-tipe oonde is reeds 'n gevestigde tegnologie wat algemeen gebruik word vir die intensiewe smelting, omsetting en raffinering van primere en sekondere roumateriale. Aangesien hierdie oonde normaalweg groot inventarisse, lang tydkonstantes en komplekse metallurgiee het, is dinamiese, modelgebaseerde voorspelling die enigste uitvoerbare benadering tot operateur besluitnemingsteunstelsels en prosesbeheer. Hierdie proefskrif stel 'n nuwe generiese, semi-empiriese benadering voor om die bad-tipe oonde stogasties te modelleer en lei tot die sogenaamde Equilib-ARMAX model. Die modelleringsbenadering word geevalueer deur drie gevallestudies: • 'n Nikkel-koper swawelsteen omsettingsproses in 'n dompel-Ians inspuit reaktor • 'n Chromiet smeltingsproses om hoe-koolstof ferrochroom te produseer in 'n gelykstroom (GS) plasmaboogoond • 'n Ilmeniet smeltingsproses om hoe titania slak en ruyster te produseer in 'n gelykstroom (GS) plasmaboogoond. In elke geval is die industriele prosesse ontleed met betrekking tot die praktiese en tegnologiese beperkings wat die tipe en die gehalte van die prosesdata beinvloed. Die fundamentele prosesgedrag van elke proses is ontleed om te bepaal welke fundamentele veranderlikes ingesluit moet word in die semi-empiriese benadering, sonder om model deursigtigheid, eenvoud, akkuraatheid en berekeningstyd in te boet. Die ontwikkeling van oor-komplekse modelle is beskou as ongepas, gegewe dat die data van industriele smeltingsprosesse beduidende onsekerhede toon. Die termochemiese en fase-ewewigte geassosieer met elke proses word breedvoerig bespreek, aangesien dit die fundamente1e grondslag van die semi-empiriese modelle verskaf. Die ewewigte is gemodelleer met rekenaar simulasie-programmatuur wat nie-ideale oplossingsmodelle en Gibbs vrye-energie minimering gebruik om die fase en chemiese ewewigte, wat verwag kan word vir 'n gegewe toevoerresep en bedryfstemperatuur, te voorspel. Aangesien termodinamiese modelleringsprogrammatuur normaalweg nie stabiele gedrag toon in 'n intydse industriele omgewing nie, word kunsmatig intelligente projeksietegnieke gebruik om prosesinsette te projekteer na die ekwavilente ewewigsvoorspellings. 'n Multilaag perseptron neurale netwerk is gebruik as 'n eenvoudige metode om hierdie ewewigsprojeksies voor te stel. Die neurale netwerke is afgerig deur van tienduisende toevoer resepte gebruik te maak. Die verhoudings van die komponente in die voer is gewissel gebaseer op 'n 3N faktoriaalontwerp. Die hoeveelhede en samestelling van al die ewewigsfases kon in alle gevalle bereken word met hoe akkuraatheid (R2 > 0.95). Verdere stogastiese analise en modellering is slegs moontlik met kennis oor die eienskapsverspreidings geassosieer met elke komponent. Die homogeniteite van die oondprodukte (slak, legering en vlieg-as) bepaal, tot 'n groot mate, die betroubaarheidsvlak van die aanlegmetings. Homogeniteite is gekarakteriseer vir die GS-plasmaboogoonde en is vergelyk met die homogeniteite wat in dompelboogoonde gevind word. Die homogeniteite het gevarieer per komponent. Silikon en swawel neig om die grootste ruimtelike variasies te toon in die legerings wat bestudeer is. 'n Beduidende negatiewe korrelasie is gevind tussen die relatiewe standaardafwyking per tap (gebaseer op silikon) en die graad van superverhitting / onderverkoeling van die legering. Dit dui aan dat die homogeniteit sterk beinvloed word deur veranderinge in die smelt reologie. Vermenging, reologie, homogeniteit en data onsekerheid (integriteit) is daarom ten nouste gekoppel. Die relatiewe standaardafwykings geassosieer met die homogeniteitsbepaling, asook die monsternemings- en ontledingsvariansies, is gebruik om die aanlegdata te rekonsilieer onderhewig aan die behoud van die komponent en totale stroom massabalanse. Die massabalanse is dus gesluit deur aanpassings aan die metings te maak binne die inherente onsekerhede in die data. Sistematiese foute in die data is gelyktydig met die rekonsiliasie geidentifiseer. Verder is deur diskrete Fourier energiespektra en toestand-ruimte analises getoon dat massabalans-rekonsiliasie dien as 'n goeie seinfilter om hoe-frekwensie geraas te verminder en tergelykertyd die dinamiese gedragseienskappe van die data te verbeter. Stelsel-identifikasietegnieke is gebruik om dinamiese oordragsfunksiemodelle te ontwikkel wat linieer is met betrekking tot die modelparameters. Hierdie stelselmodelle is gebaseer op gerekonsilieerde data, eksogene prosesdata en ewewigsberekeninge, en word vervolgens ewewigs-autoregressiewe-lopende-gemiddelde modelle met eksogene veranderlikes (Equilib ARMAX) genoem. Die modelparameters kan deur gewone kleinste-kwadrate metodes beraam word. Die finale modelle kan die metallurgie van toekomstige tappe 4-6 uur voortydig voorspel, gebaseer op beskikbare stelpunte en binne die inherente presisie van die data. Hierdie modelle kan gebruik word om optimale bedryfskondisies vir prosesbeheer te identifiseer, en is eenvoudig genoeg om in sigbladformaat op 'n aanlegbetuurder se rekenaar gebruik te kan word.

The development of the semi-empirical atomistic potential called the embedded atom method (EAM) has allowed for the efficient modeling of solid-state environments, at a lower computational cost than afforded by density functional theory (DFT). This offers the capability of EAM to model the energetics of solid-state phases of varying coordination, including defects, such as vacancies and self-interstitials. This dissertation highlights the development and application of two EAMs: a Ti potential constructed with the multi-state modified embedded atom method (MS-MEAM), and a Ni potential constructed with the fragment Hamiltonian (FH) method. Both potentials exhibit flexibility in the description of different solid-states phases and applications. This dissertation also outlines two applications of DFT. First, a study of structure and stability for solid-state forms of NixCy (in which x and y are integers) is investigated using plane-wave DFT. A ground state phase for Ni2C is elucidated and compared to known and hypothesized forms of NixCy. Also, a set of correlation consistent basis sets, previously constructed using the B3LYP and BLYP density functionals, are studied. They are compared to the well-known to the correlation consistent basis sets that were constructed with higher-level ab initio methodologies through computations of enthalpies of formation and combustion enthalpies. The computational accuracy with regard to experiment is reported.

The environmental and human impacts of wildfires have grown considerably in recent years due to an increase in their frequency and coverage. Effective wildfire management and suppression requires real-time data to locate fire fronts, model their propagation and assess the impact of biomass burning. Existing empirical wildfire models are based on fuel properties and meteorological data with inadequate spatial or temporal sampling. A geosynchronous space platform with the proposed set of high resolution infrared detectors provides a unique capability to monitor fires at improved spatial and temporal resolutions. The proposed system is feasible with state-of-the-art hardware and software for high sensitivity fire detection at saturation levels exceeding active flame temperatures. Ground resolutions of 100 meters per pixel can be achieved with repeat cycles less than one minute. Atmospheric transmission in the presence of clouds and smoke is considered. Modeling results suggest fire detection is possible through thin clouds and smoke. A semi-empirical cellular automata model based on theoretical elliptical spread shapes is introduced to predict wildfire propagation using detected fire front location and spread rate. Model accuracy compares favorably with real fire events and correlates within 2% of theoretical ellipse shapes. This propagation modeling approach could replace existing operational systems based on complex partial differential equations. The baseline geosynchronous fire detection system supplemented with a discrete-based propagation model has the potential to save lives and property in the otherwise uncertain and complex field of fire management.

With new tests being developed and marketed, the comparison of the diagnostic accuracy of two continuous-scale diagnostic tests are of great importance. Comparing the partial areas under the receiver operating characteristic curves (pAUC) is an effective method to evaluate the accuracy of two diagnostic tests. In this thesis, we study the semi-parametric inference for the difference between two pAUCs. A normal approximation for the distribution of the difference between two pAUCs has been derived. The empirical likelihood ratio for the difference between two pAUCs is defined and its asymptotic distribution is shown to be a scaled chi-quare distribution. Bootstrap and empirical likelihood based inferential methods for the difference are proposed. We construct five confidence intervals for the difference between two pAUCs. Simulation studies are conducted to compare the finite sample performance of these intervals. We also use a real example as an application of our recommended intervals.

The term microvibrations generally refers to accelerations in the order of micro-gs and which manifest in a bandwidth from a few Hz up to say 500-1000 Hz. The need to accurately characterise this small disturbances acting on-board modern satellites, thus allowing the design of dedicated minimisation and control systems, is nowadays a major concern for the success of some space missions. The main issues related to microvibrations are the feasibility to analytically describe the microvibration sources using a series of analysis tools and test experiments and the prediction of how the dynamics of the microvibration sources couple with those of the satellite structure. In this thesis, a methodology to facilitate the modelling of these phenomena is described. Two aspects are investigated: the characterisation of the microvibration sources with a semi-empirical procedure which allows derivation of the dynamic mass properties of the source, also including the gyroscopic effect, with a significantly simpler test configuration and lower computational effort compared to traditional approaches; and the modelling of the coupled dynamics when the source is mounted on a representative supporting structure of a spacecraft, including the passive and active effects of the source, which allows prediction of the structure response at any location. The methodology has been defined conducting an extensive study, both experimental and numerical, on a reaction wheel assembly, as this is usually identified as the main contributory factor among all microvibration sources. The contributions to the state-of-the-art made during this work include: i) the development of a cantilever configured reaction wheel analytical model able to reproduce all the configurations in which the mechanism may operate and inclusive of the gyroscopic effect; ii) the reformulation of the coupling theory which allows retrieving the dynamic mass of a microvibration source over a wide range of frequencies and speeds, by means of the experimental data obtained from measurements of the forces generated when the source is rigidly secured on a dynamometric platform and measurements of the accelerations at the source mounting interface in a freefree suspended boundary condition; iii) a practical example of coupling between a reaction wheel and a honeycomb structural panel, where the coupled loads and the panel response have been estimated using the mathematical model and compared with test results, obtained during the physical microvibration testing of the structural panel, showing a good level of agreement when the gyroscopic effect is also taken into account.

Orientador: Paulo Cardieri
Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Elétrica e de Computação
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Resumo: Resultados de campanhas de medição realizadas visando o desenvolvimento de uma fer-ramenta para o projeto, implantação e análise de sistemas de RFID são mostrados nesse traba-lho. Particularmente, a perda de percurso de rádio a partir de um leitor de RFID até um TAG, e de volta para o leitor é caracterizada na banda 915 MHz, para diferentes distâncias de separação leitor-TAG, alturas de TAG e de antena do leitor. Vários cenários de propagação foram considerados, incluindo ambientes exteriores e in-teriores, para os quais foi colhido um extenso número medidas. Os dados de campo são, então, comparados a uma versão melhorada do modelo clássico perda caminho 2-ray, ajustada para incluir também os padrões de radiação da antena não omnidirecionais no leitor. Além disso, foi investigado, por meio da análise de medidas de campo, o efeito da mobi-lidade do TAG no sinal recebido no leitor. Para a coleta das medidas, foi construído um aparato composto de uma esteira de velocidade controlada, onde foram instalados TAGs de teste. Os resultados de medida mostraram que a mobilidade do TAG provoca uma diminuição do valor médio e um aumento da variância do sinal recebido no leitor. Essa atenuação extra e a variância do sinal não são fortemente afetadas pelo valor da velocidade. Por fim, esses efeitos de propagação são incorporados em um modelo matemático, que pode ser utilizado para a simulação e planejamento de sistemas RFID
Abstract: Results of measurement campaigns carried out aiming at the development of a tool for design, deployment, and analysis of RFID systems are shown. Particularly, the radio path loss from an RFID reader towards the test TAG and back to the reader is characterized at the 915 MHz band. The path loss is estimated based on the received signal strength measured at the reader, for different reader¿TAG separation distances and different antenna TAG heights. Several propagation scenarios have been considered, including outdoor and indoor environments for which an extensive number of typical real manufacturing plants have been chosen. The field data are then compared to a proposed novel, improved version of the classical 2-ray path loss model, adjusted to include non-omnidirectional antenna radiation patterns at the reader. In addition, the effect of TAG mobility in the received signal at the reader was also investigated, by means of field measurements. To collect the field measurements, an apparatus was designed and constructed, consisting of a mat of controlled speed, on which test TAGs were installed. The results showed that TAG mobility decreases the average value increases the variance of the received signal at the reader. This extra attenuation and the increased variance of the signal are not strongly affected by the value of speed. Finally, these two effects are incorporated into a mathematical model that can be used for simulation and planning of RFID systems
Doutorado
Telecomunicações e Telemática
Doutor em Engenharia Elétrica

The KTH Maritime Robotics Lab is developing a simulation framework for experimental autonomous underwater vehicles in MATLAB and Simulink. This project has developed a formulation for added mass of the vehicle, to be implemented in this simulation frame-work. The requirements of the solution is that it should require low computational power, be a general formulation applicable on arbitrarily shaped vehicles and be veri-fied against literature. Different existing methods and formulations for primitive bodies have been investigated, and combining these methods has resulted in a simplified but adequate method for calculating the added mass of arbitrarily shaped hulls and control surfaces, that is easy to implement in the existing simulation framework. The method has been verified by calculating added mass coefficients for two existing vehicles, and comparing the values to the coefficients already calculated for the vehicles in question. Some limitations have been identified, such as the interaction effects between compo-nents of the vehicle not being taken into account. To determine the extent of the errors due to this simplification and to fully validate and verify the model, future work in the form of CFD calculations or experiments on added mass measurements need to be con-ducted. There is also an uncertainty in the calculation of the coupled coefficients m26 and m35, and results on these coefficients should be handled with care.

Orientador: Douglas Soares Galvão
Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin
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Resumo: As melaninas constituem uma classe de pigmentos biológicos de destaque devido, sobretudo, a sua predominante presença nos tecidos dos mamíferos. Há fortes evidências que sugerem que a pigmentação por melanina tem por objetivo proteger a pele contra efeitos prejudiciais da radiação ultravioleta. Além deste papel de fotoproteção, outras funções biológicas são especuladas em razão da presença do pigmento em regiões não iluminadas do corpo como por exemplo no cérebro em que há uma aparente destruição preferencial das células que contém melanina quando ocorrem doenças como o mal de Parkinson. Apesar de décadas de investigações, nenhuma amostra de melanina foi estruturalmente bem caracterizada. Dentre os diversos obstáculos que são responsáveis pelo lento progresso que marca a pesquisa deste pigmento, o maior deles é que as melaninas naturais são altamente insolúveis e de presumido alto peso molecular. Pesquisas recentes desenvolvem sínteses alternativas para as melaninas utilizando outros solventes e demonstram que até 20 % da estrutura desta pode ser composta por água. Assim, neste trabalho investigamos, por métodos quânticos, a geometria e estrutura eletrônica das moléculas 5,6 indolquinona, suas formas reduzidas (semiquinona e hidroquinona) e 27 dímeros obtidos a partir destas, em seus estados neutros e iônicos ( ± 1 e ± 2), no vácuo e nos solventes DMF(dimetilformamida), DMSO (dimetilsulfóxido) e água. Verificamos como o solvente altera as propriedades eletrônicas e espectroscópicas destas estruturas e como este pode ser fundamental para a determinação de suas geometrias. Utilizamos dois modelos para simular o solvente: um modelo contínuo, COSMO (Conductor-like Screening Model) e um discreto, que considera explicitamente cada molécula do solvente e é baseado em simulações Monte Carlo. Notamos que o solvente altera a propriedade de aceitador de dois elétrons de diversas estruturas, fato até então não observado e de importante consequência biológica, visto as eumelaninas poderem ser base de um mecanismo de defesa celular contra radicais livres. Os picos dos espectros de absorção, de um modo geral, são deslocados para o vermelho e, em alguns casos, tem um alargamento. Isto poderia contribuir para a constrção da larga banda característica das eumelaninas. Diversos outros aspectos importantes, em excelente acordo com dados experimentais, são também apresentados ao se considerar o solvente. Um dos mais relevantes mostra que o solvente tem forte influência na geometria da molécula com o menor custo de dimerização, o que nos leva a concluir que esta pode ser de fato a semente de "nucleação" para a formação do polímero de melanina.
Abstract: Melanins belong to an important class of biological pigments due to its abundant presence in mamal tissues. There are strong evidences that suggest that the pigmentation due to melanin would protect the skin against the biochemical devastation induced by solar exposure. Besides the photo-protection feature, other biological functions have been speculated to melanin due to its presence in non-illuminated areas of the body and the apparent preferential destruction of melanin-containing cells in the substancia nigra of the brain in Parkinsonism. Unfortunately, in what concerns structural and chemical composition, no melanin sample has been fully and unambiguously characterized yet, despite the enormous amount of experimental work done so far. The main difficulty for that is that melanin is insoluble in most organic solvents and has high molecular weight. A new synthetic route for melanins, using organic solvents, has been recently achieved and it was demonstrated that about 20 % of the structure of the pigment is composed by water. In this work we have investigated using quantum methods the geometries and electronic structure of 5,6 indolquinone, their redox forms (semiquinone and hidroquinone) and 27 dimers associated, in their neutral and ionic states ( ± 1 e ± 2). The calculation were carried in vacuum and in the solvents dimethyl sulfoxide (DMSO), N,N-dimethyl formamide (DMF) and water. We study the effect of the solvent on the electronic and spectroscopic properties and its importance to determine eumelanin structure. Two models for solvents were used. The first was a continuum model, COSMO (Conductor-like Screening Model), and the second one (based on Monte Carlo simulations) explicitly considers each molecule of the solvent. The results showed that the solvents affected the electron accepton properties allowing the acceptance of two electrons. These aspects have been not been observed before from vacuum calculations and it is of important biological consequence because the melanins can be the base of mechanism of cellular defense against free radicals. The peaks of absorption spectra of the solvated structure are dislocated from red and broadened. This could contribute to the characteristic broad band of eumelanins. Many others important aspects are in better agreement with experimental data when solvent aspects are explicitly taken into account. One of most important results was the observation that solvent effects can alter the order of the lowest energy dimer configuration in relation to the structures in vacuum. This dimer was suggested to be the nucleation seed for the polymer formation.
Mestrado
Física Atômica e Molecular
Mestre em Física

Esta tesis analiza los métodos estáticos, los cuales comprenden los métodos analíticos y semi empíricos que son utilizados para determinar la capacidad de carga teórica en pilotes, y los compara con las pruebas de carga dinámica, las cuales brindan el resultado real de la capacidad de carga de un pilote. El análisis realizado recopila las teorías de Therzaghi, Hansen, Meyerhof y Bowles, en cuanto a los modelos analíticos, y las teorías de Aoki Velloso, Decourt Quaresma, Pedro Paulo Velloso y Texeira, por parte de las teorías semi empíricas.
This thesis analyzes the static methods, which include the analytical and semi-empirical methods that are used to determine the theoretical load capacity in piles, and compares them with the dynamic load tests, which provide the real result of the load capacity of a pile. The analysis compiles the theories of Therzaghi, Hansen, Meyerhof and Bowles, regarding the analytical models, and the theories of Aoki Velloso, Decourt Quaresma, Pedro Paulo Velloso and Texeira, by the semi-empirical theories.
Tesis

La stratégie la plus utilisée aujourd'hui pour la conception de nouveaux matériaux luminescents est basée sur des méthodes d'essais-erreurs. Cependant, ces méthodes peuvent souvent entraîner une consommation d'argent et de temps. En ce sens, un modèle théorique agissant comme un outil prédictif peut servir comme une stratégie alternative. De tels modèles sont également étudiés et utilisés par des scientifiques du monde entier, mais ils sont pour la plupart difficiles à utiliser. Dans ce travail, deux modèles semi-empiriques conviviaux et faciles à utiliser ont été proposés pour la conception de luminophores intégrés dans le développement de technologies importantes, en particulier dans les éclairages à base de LED et les cellules solaires. Ces modèles sont: 1) le modèle de facteur environnemental (EF) basé sur la théorie diélectrique de la liaison chimique proposée par Philips et 2) le modèle de transfert de charge métal-métal (MMCT) utilisées pour trouver des relations entre les propriétés structurelles d'un matériau et sa luminescence. Le modèle EF a été appliqué à la famille des composés AIBIIPO4 (AI = cation monovalent, BII = cation divalent) dopés à Eu2+. Il était capable d'estimer l'énergie du bord d'excitation et d'identifier les sites de dopage à ± 1000 cm-1. Il peut donc être utilisé pour la conception de nouveaux luminophores appartenant à cette famille. Dans la deuxième partie, les deux modèles ont été utilisés pour identifier la nature de la luminescence dans les oxydes dopés à Bi3+. A cet effet, une méthode combinant les modèles motionnés avec les valeurs de Stokes shift a été trouvé fiable. En outre, la a été jugée utile pour expliquer la modification des propriétés luminescentes de YVO4:Bi3+ sous haute pression. Dans la troisième partie, les deux modèles ont été utilisés pour explorer la luminescence des oxydes dopés à Sb3+ par analogie avec Bi3+. Cependant, les résultats n'étaient pas assez bons pour identifier la nature de la luminescence dans ces matériaux. La raison pourrait être liée à la position décentrée du dopant (Sb3+)
The most used strategy for the design of new luminescent materials today is based on trial-error methods. However, these methods may often result in consummation of money and time. In this sense, a theoretical model acting as a predictive tool can serve as an alternative strategy. Such models are also studied and used by scientists around the world but they are mostly difficult to use. In this work, two friendly and easy to use semi-empirical theoretical models were proposed as a criterion for designing phosphors integrated in the development of important technologies especially in LED-based lightings and solar cells. These models are: 1) the environmental factor model (EF) based on the dielectric theory of chemical bonding proposed by Philips and 2) the metal to metal charge transfer (MMCT) model by Boutinaud that were both used for the purpose of finding relationships between the structural properties of a material and its luminescence. The EF model was applied on the family of AIBIIPO4 (AI= monovalent cation, BII= divalent cation) compounds doped with Eu2+. It was able to estimate the excitation edge energy and to identify the doping sites within uncertainty of ± 1000 cm-1. It can therefore, be used for the design of new phosphors belonging to this family. In a second part, both models were used to identify the nature of luminescence in Bi3+-doped oxides. For this purpose, a method combining the mentioned models along with the values of the Stokes shift was found reliable. In addition, the method was found useful to explain the change in luminescent properties of YVO4:Bi3+ under high pressure. In the third part, the two models were used to explore the luminescence of Sb3+-doped oxides by analogy with Bi3+. However, the results were not good enough to identify the nature of luminescence in these materials. The reason could be related to the off-centered position of the dopant (Sb3+)

Modelling the ice accretion in glaze regime for the supercooled large droplets is one of the most challenging problems in the aircraft icing field. The difficulties are related to the presence of the liquid water film on the surface in the glaze regime and also the phenomena associated with SLD conditions, specifically the splashing and re-impingement. The steady improvement of simulation methods and the increasing demand for highly optimised aircraft performance, make it worthwhile to try to get beyond the current level of modelling accuracy. A semi-empirical method has been presented to characterize the thin water film in the icing problem based on both analytical and experimental approaches. The experiments have been performed at the Cranfield icing facilities. Imaging techniques have been used to observe and measure the features of the thin water film in the different conditions. A series of numerical simulations based on an inviscid VOF model have been performed to characterize the splashing process for different water film to droplet size ratios and impact angles. Based on these numerical simulations and the proposed methods to estimate the thin water film thickness, a framework has been presented to model the effects of the splashing in the icing simulation. These effects are the lost mass from the water film due to the splashing and the re-impingement of the ejected droplets. Finally, a new framework to study the solidification process of the thin water film has been explored. This framework is based on the lattice Boltzmann method and the preliminary results showed the capabilities of the method to model the dynamics, thermodynamics and the solidification of the thin water film.

The Bi-directional Reflectance Distribution Function (BRDF) is a description of the anisotropic scattering of electro-magnetic radiation by a surface. Mathematical models of the BRDF have the potential to provide estimates of various key environmental variables such as Leaf Area Index (LAI) and Earth surface albedo, by inversion against Earth Observation data. A suite of linear semi-empirical kernel-driven BRDF models, known collectively as AM-BRALS, has been devised by NASA for use with data from the TERRA/MODIS sensor. These have yet to be tested in any comprehensive, operational fashion. This thesis examines the potential of the AMBRALS models (specifically the Ross-Thick Li-Sparse kernel combination), to provide information from directional reflectances acquired by the CNES sensor SPOT-4 VEG-ETATION (VGT). VGT is comparable with MODIS in terms of angular sampling and spatial resolution and thus provides an ideal opportunity to test the AMBRALS suite. Potential weaknesses in the pre-processing of VGT are identified and examined in terms of their impact on the inversion of AMBRALS. These were namely; cloud-masking and atmospheric correction. A new cloud-mask is suggested for VGT data that are to be used with BRDF models. Aerosol optical depth is identified as the atmospheric parameter which has the greatest impact on BRDF model inversion. The information content of VGT acquired directional reflectances and resulting BRDF model products are examined statistically. The complementarity of this information with that already provided by the VGT spectral channels is explored.

Current field models for wildfire prediction are mostly based on dry or low-moisture fuel combustion research. To better study live fuel combustion behavior and develop the current semi-empirical bush combustion model, a laminar flow flat-flame burner was used to provide a convection heating source to ignite individual live fuel samples. In this research project, four Utah species were studied: Gambel oak (Quercus gambelii), canyon maple (Acer grandidentatum), big sagebrush (Artemisia tridentata) and Utah juniper (Juniperus osteosperma). Leaf geometrical parameters and time-dependent combustion behavior were recorded. Qualitative results included various combustion phenomena like bursting, brand formation and bending. Quantitative results included determination of best correlations for (a) leaf geometrical properties (individual leaf dry mass (mdry), thickness (Δx), leaf width (W) and leaf length (L)) and (b) combustion characteristics (e.g., time to ignition (tig), time of flame duration (tfd), time to maximum flame height (tfh), time to burnout (tbrn), and maximum flame height (hf,max)). A semi-empirical bush model was expanded to describe the combustion behavior of the three Utah species (Gambel oak, canyon maple and Utah juniper). Leaf placement and bush structure were determined from the statistical model. A new flame area simulation was explored in the semi-empirical bush model in order to improve the bush burning predictions.

Orientador: Bernardo Laks
Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Fisica Gleb Wataghin
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Resumo: Antes da década de 70, todos os materiais poliméricos eram considerados como isolantes e suas aplicações tecnológicas levavam em conta esta característica. De lá para cá, uma nova classe desses materiais, os polímeros conjugados, determinaram uma nova forma de aplicação de sistemas poliméricos baseados em suas propriedades elétricas e de ótica não-linear. Um maior estímulo surgiu a partir do experimento de Mac Diarmid, Heeger e Shirakawa [1] que, expondo o Poliacetileno a agentes oxidantes, demonstraram ser possível obter um sistema no estado metálico. Atualmente encontramos filmes de Poliacetileno com condutividade elétrica da ordem do cobre (105 S/cm). O Poliacetileno, quando no regime metálico, i.e., sob alta dopagem, apresenta algumas características de metal comum: alta condutividade elétrica (cresce 13 ordens de grandeza), susceptibilidade de Pauli finita e absorção no infravermelho. Já outras propriedades como a presença de modos vibracionais localizados no infravermelho e o não comportamento da condutividade com o inverso da temperatura evidenciam ser este um material não usual. Estes polímeros conjugados que apresentam uma extensiva delocalização de elétrons são considerados semicondutores orgânicos com gap de energia relativamente pequeno, da ordem de 1,5 a 2,0 eV. O comportamento semicondutor e as propriedades decorrentes entre os elétrons e a luz têm originado a construção de vários dispositivos semicondutores e optoeletrônicos [2, 7, 3]. Problemas técnicos como estabilidade ao ambiente, processabilidade e solubilidade destes materiais provocaram a produção de uma nova classe de materiais poliméricos que foi obtida por polimerização eletroquímica [57, 58, 59] cuja estrutura molecular trata-se de sistemas que introduzem grupos vinilas (V) entre anéis de tiofeno (T). Experimentos de voltametria cíclica, espectroscopia de absorção ótica e ressonância eletrônica de spin indicam que esses sistemas possuem potencial de ionização e gap de energia menores que o apresentado pelo Politiofeno. Estudos com oligômeros de tiofeno (T) com vinilenos (V) sugerem a possibilidade de escolha desse material como alternativa ao politiofeno. O objetivo deste trabalho foi investigar teoricamente a influência do grupo vinila (V) sobre as propriedades eletrônicas nestes polímeros, reproduzir os resultados experimentais e determinar qual proporção de vinilenos (V) e tiofenos (T) que provoque o menor gap de energia de forma que quando sobre dopagem possibilite uma transição isolante metal. Desta maneira, primeiramente, determinamos as geometrias dos sistemas de interesse utilizando métodos semi-empíricos. Posteriormente investigamos a estrutura eletrônica dos polímeros de tiofeno (T) com vinilenos (V), sendo que estes polímeros foram estudados para o caso neutro e na presença de defeitos conformacionais do tipo pólaron e bipólaron. Finalizamos o estudo investigando as absorções ópticas UV-vis dos sistemas de interesse através de cálculos semi-empíricos utilizando o código ZINDO/S.
Abstract: Before the 1970s, all polymeric materials were considered insulators; therefore their technological applications would take this trait into account. Since then, a new development on these materials, the conjugated polymers, determined new applications for polymeric systems based in their electrical and nonlinear optical properties. Greater interest arose from the experiment by Mac Diarmid, Heeger and Shirakawa [1] who, by using polyacetylene and oxidizing agents, showed that it is possible to obtain a system in the metallic state. Nowadays it is possible to find polyacetylene films with electrical conductivity of the order of copper (10-5 S/cm). Polyacetylene, when in its metallic behavior, i.e., under high dopage, presents some characteristics of real metal: high electrical conductivity (increased by 13 orders of magnitude), finite Pauli susceptibility and infrared absorption. On the other hand, other properties such as the presence of vibrational modes localized on infrared and the odd behavior of conductivity versus the inverse of temperature make clear that this is a unusual material. These conjugated polymers, presenting an extensive delocalization of electrons, are considered organic semiconductors with relatively low energy gap, of the order of 1.5 to 2.0 eV. The semiconductive behavior and the resulting properties of the interaction between electrons and light have been the drive for the manufacturing of several semiconductor and optoelectronic devices [2, 7, 3]. Technical problems, such as environmental stability, processability and solubility of these materials, gave rise to the production of a new kind of polymeric materials that were obtained by electrochemical polymerization [57, 58, 59], in which the molecular structure is a system that introduces vinylene groups (V) between tiophene rings (T). Experiments involving cyclic voltametry, optical absorption spectrometry and spin electronic ressonance indicate that these systems have ionization potential and energy gap smaller than those presented by Polythiophene. Studies with thiopene oligomers (T) with vinylene (V) suggest this material can be chosen as an alternative to Polytiophene. The goal of this work is to theoretically investigate the in uence of the vinyle group (V) on the electronic properties on these polymers, reproduce experimental results and determine what is the vinylene (V) to thiophene (T) rate that causes the smallest energy gap, such that doping will produce a insulator-metal transition. Therefore, we first determine the target systems' geometry using semi-empirical methods. Then we investigate the electronic structure of the tiophene (T) and vinylene (V) polymers both for neutral systems and in the presence of conformational defects of polaron and bipolaron types. We nalized the study by investigating the UV-vis optical absorption of the target systems through semi-empirical calculations using ZINDO/S code.
Doutorado
Estrutura Eletronica de Atomos e Moleculas ; Teoria
Doutor em Ciências