Lanthanides have several specific properties which cannot be found for other elements in the periodic table. Among various applications of lanthanides, complexes of LnIII ions are used in medicine, e.g., as contrast agents in MRI, as luminescent probes or as radiopharmaceuticals, where their specific properties are important. These complexes must be kinetically inert to prevent release of highly toxic "free" LnIII ions. This requirement is fulfilled with pre-organized ligands such as analogues of H4dota (1,4,7,10- tetraazacyclododecane-1,4,7,10-tetraacetic acid). Many of important properties of LnIII complexes of H4dota, such as relaxivity, isomerism and fluxionality, depend on the solution dynamics of the complexes. However, the knowledge of this solution dynamics is limited for LnIII complexes of H4dota derivatives with phosphonate or phosphinate pendant arms. Recently, a new dynamical process where phosphonate oxygen atoms interchange through a bidentate phosphonate intermediate ("a phosphonate rotation") has been proposed by DFT calculations but unconfirmed experimentally. To prove the process experimentally, solution dynamics of LnIII complexes of monophosphonate and monophosphinate derivatives of H4dota was investigated. Especially, to examine the "P-rotation", 17 O NMR spectroscopy was used...

[pt] O presente trabalho se propôs a efetuar uma investigação resumida do mercado de mineração de criptomoedas no Brasil e analisar a viabilidade econômica da implantação de uma fazenda de mineração de Bitcoins em território brasileiro. O estudo foi realizado em três etapas, onde foram abordadas análises determinísticas baseadas em possíveis cenários, observação da sensibilidade do investimento em relação as principais variáveis do problema e por último a utilização de métodos estocásticos visando estimar o risco do investimento, em razão do ambiente de incerteza. Os resultados demonstram que este é um investimento de altíssimo risco e que não existe viabilidade econômica em minerar Bitcoin no Brasil, com cotação do abaixo de US$ 10.065. O estudo aponta o custo da energia elétrica como o mais expressivo, seguido do investimento nos equipamentos de mineração e sugere que a operação seja estabelecida em países com menor custo de eletricidade, clima mais baixo e menores taxas de importação e de imposto de renda. / [en] This work carries out a brief investigation of cryptocurrencies mining market in Brazil and to analyze the economic viability of the investment in a Bitcoin mining farm in Brazil. The study was carried out in three stages, where deterministic analyzes were based on possible scenarios, observation of the sensitivity of the investment relative to the main variables of the problem and finally the use of stochastic methods to estimate the investment risk under uncertainty. The study points to the cost of electricity as the most significant, followed by investment in mining equipment and suggests that the operation be established in countries with lower electricity costs, lower climate and lower import and income tax rates.

<p>This thesis is a numerical investigation of two-dimensional steady flows past a circular obstacle. In the fluid dynamics research there are few computational results concerning the structure of the steady wake flows at Reynolds numbers larger than 100, and the state-of-the-art results go back to the work of Fornberg (1980) Fornberg (1985). The radial velocity component approaches its asymptotic value relatively slowly if the solution is ``physically reasonable''. This presents a difficulty when using the standard approach such as domain truncation. To get around this problem, in the present research we will develop a spectral technique for the solution of the steady Navier-Stokes system. We introduce the ``bootstrap" method which is motivated by the mathematical fact that solutions of the Oseen system have the same asymptotic structure at infinity as the solutions of the steady Navier-Stokes system with the same boundary conditions. Thus, in the ``bootstrap" method, the streamfunction is calculated as a perturbation to the solution to the Oseen system. Solutions are calculated for a range of Reynolds number and we also investigate the solutions behaviour when the Reynolds number goes to infinity. The thesis compares the numerical results obtained using the proposed spectral ``bootstrap" method and a finite--difference approach for unbounded domains against previous results. For Reynolds numbers lower than 100, the wake is slender and similar to the flow hypothesized by Kirchoff (1869) and Levi-Civita (1907). For large Reynolds numbers the wake becomes wider and appears more similar to the Prandtl-Batchelor flow, see Batchelor (1956).</p> / Doctor of Science (PhD)

Finite amplitude perturbations in compressible media are ubiquitous in scientific and engineering applications such as gas-turbine engines, rocket propulsion systems, combustion instabilities, inhomogeneous solids, and traffic flow prediction models, to name a few. Small amplitude waves in compressible fluids propagate as sound and are very well described by linear theory. On the other hand, the theory of nonlinear acoustics, concerning high-amplitude wave propagation (Mach<2) is relatively underdeveloped. Most of the theoretical development in nonlinear acoustics has focused on wave steepening and has been centered around the Burgers' equation, which can be extended to nonlinear acoustics only for purely one-way traveling waves. In this dissertation, theoretical and computational developments are discussed with the objective of advancing the multi-fidelity modeling of nonlinear acoustics, ranging from quasi one-dimensional high-amplitude waves to combustion-induced detonation waves. <br> <br> We begin with the theoretical study of spectral energy cascade due to the propagation of high amplitude sound in the absence of thermal sources. To this end, a first-principles-based system of governing equations, correct up to second order in perturbation variables is derived. The exact energy corollary of such second-order system of equations is then formulated and used to elucidate the spectral energy dynamics of nonlinear acoustic waves. We then extend this analysis to thermoacoustically unstable waves -- i.e. amplified as a result of thermoacoustic instability. We drive such instability up until the generation of shock waves. We further study the nonlinear wave propagation in geometrically complex case of waves induced by the spark plasma between the electrodes. This case adds the geometrical complexity of a curved, three-dimensional shock, yielding vorticity production due to baroclinic torque. Finally, detonation waves are simulated by using a low-order approach, in a periodic setup subjected to high pressure inlet and exhaust of combustible gaseous mixture. An order adaptive fully compressible and unstructured Navier Stokes solver is currently under development to enable higher fidelity studies of both the spark plasma and detonation wave problem in the future. <br>

Die vorliegende Arbeit beschäftigt sich mit einer Klasse von Variationsproblemen, die im Kontext des Ferromagnetismus entstehen. Es soll hierbei ein numerischer und analytischer Hintergrund zur Behandlung von harten magnetischen dünnen Filmen mit senkrechter Anisotropie gegeben werden. Bei magnetischen dünnen Filmen handelt es sich um Schichten von magnetischen Materialien mit Dicken von wenigen Mikrometern bis hin zu einigen Nanometern. Ausgangspunkt der Betrachtungen ist ein Modell von Landau und Lifshitz, das die Grundzustände der Magnetisierung in einem dreidimensionalen Körpers mit den Minimierer eines nichtkonvexen und nichtlokalen Energiefunktionals, der sogenannten mikromagnetischen Energie, verbindet. Unter der Annahme sehr kleiner Filmdicken wird aus dem betrachteten Modell ein zwei-dimensionales Modell hergeleitet. Anschließend wird mit Hilfe der Gamma-Konvergenz die Konvergenz zu einem Sharp-Interface-Modell gezeigt. Das resultierende Energiefunktional besteht aus konkurrierenden Interface- und Dipolenergieanteilen. Der zweite Teil der Arbeit beschäftigt sich mit der Analyse einer numerischen Methode, die die Lösungen des vorher hergeleiteten Modells approximiert. Hierbei stützen sich die Betrachtungen auf ein relaxiertes Modell, in dem der Interfaceenergiebeitrag durch seine Modica-Mortola Approximation ersetzt und dann der entsprechende L^2 Gradientenfluß betrachtet wird. Die daraus resultierende nichtlineare und nichtlokale parabolische Gleichung wird anschließend durch ein Crank-Nicolson-Verfahren in der Zeitvariablen und einem Fourieransatz für die Raumvariablen diskretisiert. Wir beweisen die Existenz und Eindeutigkeit von Lösungen des numerischen Verfahrens, sowie deren Konvergenz zu Lösungen des anfänglich betrachteten stetigen Modells. Ferner werden auch a priori Fehlerabschätzungen für die numerische Methode hergeleitet. Abschließend werden die analytischen Resultate anhand numerischer Experimente illustriert. / This thesis is concerned with the study of a class of variational problems arising in the context of ferromagnetism. More precisely, it aims at providing a numerical and analytical background to the study of hard magnetic thin films with perpendicular anisotropy. Magnetic thin films are sheets of magnetic materials with thicknesses of a few micrometers down to a few nanometers used mainly in electronic industry, for example as magnetic data storage media for computers. Our initial considerations are based on a model of Landau and Lifshitz that associates the ground states of the magnetization within a three-dimensional body to the minimizers of a nonconvex and nonlocal energy functional, the so-called micromagnetic energy. Under film thickness considerations (thin film regime), we first reduce the aforementioned model to two dimensions and then carry out a Gamma-limit for a sharp-interface model. The resulting energy functional features a competition between an interfacial and a dipolar energy contribution. The second part of the thesis is concerned with the analysis of a numerical method to approximate solutions of the previously derived sharp-interface model. We base our considerations on a relaxed model in which we replace the interfacial energy contribution by its Modica-Mortola approximation, and then study the associated L^2 gradient flow. The resulting evolution equation, a nonlinear and nonlocal parabolic equation, is discretized by a Crank-Nicolson approximation for the time variable and a Fourier collocation method for the space variable. We prove the existence and uniqueness of the solutions of the numerical scheme, the convergence of these solutions towards solutions of the initial continuous model and also derive a-priori error estimates for the numerical method. Finally, we illustrate the analytical results by a series of numerical experiments.

The Poiseuille Flow is the flow of a viscous incompressible fluid in a channel between two infinite parallel plates. The behaviour of flow is properly described by the well-known Navier-Stokes Equations. The fact that Navier-Stokes equations are partial differential equations makes their solution difficult. They can rarely be solved in closed form. On the other hand, numerical techniques can be applied successfully to the well-posed partial differential equations. In the present study pseudo-spectral method is implemented to analyze the Poiseuille Flow. The pseudo-spectral method is a high-accuracy numerical modelling technique. It is an optimum choice for the Poiseuille flow analysis due to the flows simple geometry. The method makes use of Fourier Transform and by handling operations in the Fourier space reduces the difficulty in the solution. Fewer terms are required in a pseudo-spectral orthogonal expansion to achieve the same accuracy as a lower order method. Karhunen-Lo&egrave / ve (KL) decomposition is widely used in computational fluid dynamics to achieve reduced storage requirements or construction of relatively low-dimensional models. In this study the KL basis is extracted from the flow field obtained from the direct numerical simulation of the Poiseuille flow.

Numerical study of transition in the Rayleigh-B&#039 / enard problem of thermal convection between rigid plates heated from below under the influence of gravity with and without rotation is presented. The first numerical approach uses spectral element method with Fourier expansion for horizontal extent and Legendre polynomal for vertical extent for the purpose of generating a database for the subsequent analysis by using Karhunen-Lo&#039 / eve (KL) decomposition. KL decompositions is a statistical tool to decompose the dynamics underlying a database representing a physical phenomena to its basic components in the form of an orthogonal KL basis. The KL basis satisfies all the spatial constraints such as the boundary conditions and the solenoidal (divergence-free) character of the underlying flow field as much as carried by the flow database. The optimally representative character of the orthogonal basis is used to investigate the convective flow for different parameters, such as Rayleigh and Prandtl numbers. The second numerical approach uses divergence free basis functions that by construction satisfy the continuity equation and the boundary conditions in an expansion of the velocity flow field. The expansion bases for the thermal field are constructed to satisfy the boundary conditions. Both bases are based on the Legendre polynomials in the vertical direction in order to simplify the Galerkin projection procedure, while Fourier representation is used in the horizontal directions due to the horizontal extent of the computational domain taken as periodic. Dual bases are employed to reduce the governing Boussinesq equations to a dynamical system for the time dependent expansion coefficients. The dual bases are selected so that the pressure term is eliminated in the projection procedure. The resulting dynamical system is used to study the transitional regimes numerically. The main difference between the two approaches is the accuracy with which the solenoidal character of the flow is satisfied. The first approach needs a numerically or experimentally generated database for the generation of the divergence-free KL basis. The degree of the accuracy for the KL basis in satisfying the solenoidal character of the flow is limited to that of the database and in turn to the numerical technique used. This is a major challenge in most numerical simulation techniques for incompressible flow in literature. It is also dependent on the parameter values at which the underlying flow field is generated. However the second approach is parameter independent and it is based on analytically solenoidal basis that produces an almost exactly divergence-free flow field. This level of accuracy is especially important for the transition studies that explores the regions sensitive to parameter and flow perturbations.

Fluid mechanics of blood can be well approximated by a mixture model of a Newtonian fluid and deformable particles representing the red blood cells. Experimental and theoretical evidence suggests that the deformation and rheology of red blood cells is similar to that of phospholipid vesicles. Vesicles and red blood cells are both area preserving closed membranes that resist bending. Beyond red blood cells, vesicles can be used to investigate the behavior of cell membranes, intracellular organelles, and viral particles. Given the importance of vesicle flows, in this thesis we focus in efficient numerical methods for such problems: we present computationally scalable algorithms for the simulation of dilute suspension of deformable vesicles in two and three dimensions. Our method is based on the boundary integral formulation of Stokes flow. We present new schemes for simulating the three-dimensional hydrodynamic interactions of large number of vesicles with viscosity contrast. The algorithms incorporate a stable time-stepping scheme, high-order spatiotemporal discretizations, spectral preconditioners, and a reparametrization scheme capable of resolving extreme mesh distortions in dynamic simulations. The associated linear systems are solved in optimal time using spectral preconditioners. The highlights of our numerical scheme are that (i) the physics of vesicles is faithfully represented by using nonlinear solid mechanics to capture the deformations of each cell, (ii) the long-range, N-body, hydrodynamic interactions between vesicles are accurately resolved using the fast multipole method (FMM), and (iii) our time stepping scheme is unconditionally stable for the flow of single and multiple vesicles with viscosity contrast and its computational cost-per-simulation-unit-time is comparable to or less than that of an explicit scheme. We report scaling of our algorithms to simulations with millions of vesicles on thousands of computational cores.

In this thesis, a survey on pseudospectral methods for differential equations is presented. Properties of the classical orthogonal polynomials required in this context are reviewed. Differentiation matrices corresponding to Jacobi, Laguerre,and Hermite cases are constructed. A fairly detailed investigation is made for the Hermite spectral methods, which is applied to the Schr&ouml / dinger eigenvalue equation with several potentials. A discussion of the numerical results and comparison with other methods are then introduced to deduce the effciency of the method.

This thesis presents new numerical methods for solving differential equations with periodicity. Spectral methods for solving linear and nonlinear ODEs, linear ODE eigenvalue problems and linear time-dependent PDEs on a periodic interval are reviewed, and a novel approach for computing multiplication matrices is presented. Choreographies, periodic solutions of the n-body problem that share a common orbit, are computed for the first time to high accuracy using an algorithm based on approximation by trigonometric polynomials and optimization techniques with exact gradient and exact Hessian matrix. New choreographies in spaces of constant curvature are found. Exponential integrators for solving periodic semilinear stiff PDEs in 1D, 2D and 3D periodic domains are reviewed, and 30 exponential integrators are compared on 11 PDEs. It is shown that the complicated fifth-, sixth- and seventh-order methods do not really outperform one of the simplest exponential integrators, the fourth-order ETDRK4 scheme of Cox and Matthews. Finally, algorithms for solving semilinear stiff PDEs on the sphere with spectral accuracy in space and fourth-order accuracy in time are proposed. These are based on a new variant of the double Fourier sphere method in coefficient space and standard implicit-explicit time-stepping schemes. A comparison is made against exponential integrators and it is found that implicit-explicit schemes perform better. The algorithms described in each chapter of this thesis have been implemented in MATLAB and made available as part of Chebfun.