De nos jours, il n'existe encore aucune théorie capable de proposer une description précise et quantitative du transfert de proton en solution. En effet, ce problème est complexe du fait de la grande diversité des interactions existant dans l'eau liquide, à savoir: des interactions non liantes de type Van der Waals, des liaisons faiblement covalentes et des liaisons hydrogènes remarquablement fortes. Ces dernières sont d'ailleurs à l'origine des nombreuses propriétés fascinantes de l'eau à l'échelle macroscopique. À cela s'ajoutent les effets quantiques nucléaires dus à la faible masse de l'hydrogène, qui modifient profondément la nature de la surface d'énergie potentielle décrivant le transfert de proton le long de sa coordonnée de réaction. Nous proposons dans cette thèse une approche tout quantique basée sur une description quasi exacte de la fonction d'onde du système par l'utilisation de méthodes stochastiques de type Monte Carlo Quantique. Cette technique, combinée avec le formalisme des équations de Langevin et des intégrales de chemin de Feynman, permet de simuler à un niveau de précision inédit, n'importe quel système chimique en phase gaz ou en solution. Nous appliquons cette méthodologie à des agrégats d'eau neutres ou protonés pour apporter de nouveaux éclaircissements sur les phénomènes microscopiques régissant la diffusion du proton hydraté dans de tels systèmes. Il est mis en évidence que la mobilité du proton est optimale pour des températures proches des conditions ambiantes, du fait de la compétition subtile entre les effets thermiques et quantiques nucléaires. / There is no theory up to now able to provide an accurate and quantitative description of the proton transfer (PT) yet. Indeed, the complexity of the problem stems from the large diversity of the existing interactions in liquid water, namely: non bonding Van der Waals interactions, weakly covalent bonds and remarkably strong H-bonds. The latter ones are at the origin of the numerous fascinating properties of water at the macroscopic scale. In addition to such interactions, the nuclear quantum effects arising from the hydrogen light mass deeply modify the potential energy surface, and must be taken into account. In this thesis, we propose a fully quantum approach based on an almost exact description of the electronic wave function by means of Quantum Monte Carlo (QMC) methods. Our novel technique combines QMC with a Langevin-based Molecular Dynamics and the Feynman's path integral formalism. This allows one to perform fully quantum simulations of systems in gas or condensed phase, at an unprecedented level of accuracy,. We apply our approach to neutral or charged protonated water clusters to shed light on the microscopic phenomena driving the proton diffusion in such systems. We discovered that the proton hopping is optimal for temperatures close to ambient conditions, due to the subtle competition between thermal and nuclear quantum effects. This is highly suggestive of the importance of quantum nuclear effects to make PT processes - relevant for life - most efficient at room temperature.

Path integral Monte Carlo (PIMC) is a method suitable for quantum liquid simulations at finite temperature. We present in this thesis a study of PIMC dealing with the theory and algorithms related to it, and then two applications of PIMC to current research problems of quantum fluids in the Bolzmann regime. The first part encompasses a study of the different ingredients of a PIMC code: action, sampling and physical property estimators. Particular attention has been paid to Li-Broughton's higher order approximation to the action. Regarding sampling, several collective movement methods have been derived, including the bisection algorithm, that has been thoroughly tested. We also include a study of estimators for different physical properties, such as, the energy (through the thermodynamic and virial estimators), the pair distribution function, the structure factor, and the momentum distribution. In relation to the momentum distribution, we have developed a novel algorithm for its estimation, the trail method. It surmounts some of the problems exposed by previous approaches, such as the open chain method or McMillan's algorithm.The Richardson extrapolation used within PIMC simulations, is another contribution of this thesis. Up until now, this extrapolation has not been used in this context. We present studies of the energy dependence on the number of "beads", along with the betterment provide by the Richardson extrapolation. Inasmuch as our goal is to perform research of quantum liquids at finite temperature, we have produced a library of codes, written from scratch, that implement most of the features theoretically developed. The most elaborated parts of these codes are included in some of the appendixes.The second part shows two different applications of the algorithms coded. We present results of a PIMC calculation of the momentum distribution of Ne and normal 4He at low temperatures. In the range of temperatures analysed, exchanges can be disregarded and both systems are considered Boltzmann quantum liquids. Their quantum character is well reflected in their momentum distributions witch show clear departures from the classical limit. The PIMC momentum distributions which show clear departures from the classical limit. The PIMC momentum distributions are sampled using the trail method. Kinetic energies of both systems, as a function of temperature and at a fixed density, are also reported. Finally, the solid-liquid neon phase transition along the 35 K isotherm has been characterized.While thermodynamic properties of the solid phase are well known the behaviour of some properties, such as the energy or the dessity, during the trasition presen6 some uncertainties For example, experimental data for the place diagram, which determines solid and liquid boundaries, present sizeable differences. The temperature chosen is high enough so that Bose or Fermi statistics corrections are small, although the system is strongly quantum mechanical. The results obtained show a discontinuity in the kinetic energy during the transition.

Made available in DSpace on 2015-05-14T12:14:12Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 3660633 bytes, checksum: 7309d28729d29dd071bc87f7c5609ebc (MD5) Previous issue date: 2013-11-20 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / The non-linear science is a central topic covering several investigation areas, such as biology, chemistry, mathematics and physics. In the first part of this thesis, we studied the non-linearity in the scope of classical field theory. The discussions are based on static solutions in (1, 1) space-time dimensions, and they are focused on kinks and lumps defects. In the related procedures, we show several techniques which allowed us to determine new models with their respective analytical solutions. The main mathematical tool to obtain these results is the so called deformation method, which was also an essential piece in the construction of a new extension method. This method presents the determination of new two scalar fields models from the coupling between two one scalar field systems. The method was analyzed carefully, as well as the linear stability, the zero modes, the total energy and the superpotentials, related with the new families of potentials. Furthermore, in the second part we presented the basics concepts about the Brownian Motion, where we analised the features of the solution of the Langevin Equation, and we also introduced a path integral approach to this problem in a quantum field theory way. / A ciência não-linear é tema central de diversas linhas de investigação, cobrindo áreas como a biologia, a física, a matemática e a química. Nossa primeira vertente de trabalho nesta tese, consiste no estudo de não-linearidades via abordagem de teoria clássica de campos. As discussões estão baseadas em soluções estáticas em (1, 1) dimensões, com destaque para o chamados defeitos tipo kink e lump. Nos procedimentos relatados, discorremos a respeito de diversas técnicas para a determinação de novos modelos com suas respectivas soluções analíticas. Um ferramental fundamental para a obtenção desses resultados é o chamado método de deformação, o qual também foi parte essencial para a criação de um método de extensão de modelos, onde visamos a construção de modelos de dois campos reais a partir do acoplamento entre dois modelos de um campo. Tal método também foi exposto em detalhes, bem como as análises sobre estabilidade linear, cálculo de modos zeros, determinação da energia total e dos superpotenciais, relativos às novas famílias de potenciais. Já a segunda linha de pesquisa, refere-se aos conceitos básicos do movimento browniano, onde analisamos as propriedades da solução da equação de Langevin, e na introdução de uma abordagem via integrais de trajetória para descrevê-lo nos moldes de teoria de quântica de campos.

L’étude des propriétés d’équilibre d’un système Coulombien quantique à plusieurs composantes présente un intérêt théorique fondamental, au-delà de ses nombreuses applications. Le mélange hydrogène-hélium est omniprésent dans la nébuleuse interstellaire ou les planètes géantes, et c’est aussi le constituant majoritaire du Soleil, où les interactions entre électrons et noyaux sont purement électrostatiques en première approximation.Ce travail est dévolu à l’équation d’état de ce mélange vu comme un plasma quantique constitué de protons, de noyaux d’Hélium et d’électrons. Dans ce cadre, nous développons des méthodes numériques pour estimer des intégrales de chemin représentant des ingrédients essentiels. En outre, nous construisons une nouvelle version de la diagrammatique à la Mayer resommée bien adaptée à nos objectifs.Tout d’abord, nous améliorons le double développement basse température et basse densité, dit SLT, pour l’hydrogène pur, grâce à de meilleures estimations des termes à trois corps, les résultats étant par ailleurs comparés à la fameuse équation d’état OPAL. Les densités plus élevées sont atteintes de manière non-perturbative, en utilisant des fonctions de partition d’entités recombinées suffisamment précises. Ainsi l’ionisation par pression est décrite sur une base théorique robuste. Nous étudions également d’autres quantités d’équilibre, comme l’énergie interne et la vitesse du son. Dans la dernière partie, nous calculons l’équation d’état du mélange hydrogène-hélium en incluant les effets d’écran associés aux ions He+, ainsi que des corrections à la Debye déterminées de manière auto-cohérente. Nos résultats nous permettent de comprendre le contenu physique d’approches ad-hoc et de déterminer leurs régimes de validité. Nous obtenons aussi une description plus fiable du mélange, qui devrait être précise le long de l'adiabate du Soleil. / The study of the thermodynamic properties of a multi-component quantum Coulomb system is of fundamental theoretical interest and has, beyond that, a wide range of applications. The Hydrogen-Helium mixture can be found in the interstellar nebulae and giant planets, however the most prominent example is the Sun. Here the interaction between the electrons and the nuclei is almost purely electrostatic.In this work we study the equation of state of the Hydrogen-Helium mixture starting from first principles, meaning the fundamental Coulomb interaction of its constituting particles. In this context we develop numerical methods to study the few-particle clusters appearing in the theory by using the path integral language. To capture the effects of the long-range Coulomb interaction between the fundamental particles, we construct a new version of Mayer-diagrammatic, which is appropriate for our purposes. In a first step, we ameliorate the scaled-low-temperature (SLT) equation of state, valid in the limit of low density and low temperature, by taking three-body terms into account and we compare the predictions to the well-established OPAL equation of state. Higher densities are accessed by direct inversion of the density equations and by the use of cluster functions that include screening effects. These cluster functions put the influence of screening on the ionization, unto now treated ad-hoc, on a theoretically well-grounded basis. We also inspect other equilibrium quantities such as the speed of sound and the inner energy. In the last part we calculate the equation of state of the Hydrogen-Helium mixture including the charged He+ ions in the screening process. Our work gives insights in the physical content of previous phenomenological descriptions and helps to better determine their range of validity. The equation of state derived in this thesis is expected to be very precise as well as reliable for conditions found in the Sun.

Path integral approaches have been widely used for long in both quantum mechanics as well as statistical mechanics. In addition to being a tool for obtaining the probability distributions of interest(wave functions in the case of quantum mechanics),these methods are very instructive and offer great insights into the problem. In this thesis, path integrals are extensively employed to study some very interesting problems in both equilibrium and non-equilibrium statistical mechanics. In the non-equilibrium regime, we have studied, using a path integral approach, a very interesting class of anomalous diffusion, viz. the L´evy flights. In equilibrium statistical mechanics, we have evaluated the partition function for a class of molecules referred to as the hindered rotors which have a barrier for internal rotation. Also, we have evaluated the exact quantum statistical mechanical propagator for a harmonic potential with a time-dependent force constant, valid under certain conditions. Diffusion processes have attracted a great amount of scientific attention because of their presence in a wide range of phenomena. Brownian motion is the most widely known class of diffusion which is usually driven by thermal noise. However ,there are other classes of diffusion which cannot be classified as Brownian motion and therefore, fall under the category of Anomalous diffusion. As the name suggests, the properties of this class of diffusion are very different from those for usual Brownian motion. We are interested in a particular class of anomalous diffusion referred to as L´evy flights in which the step sizes taken by the particle during the random walk are obtained from what is known as a L´evy distribution. The diverging mean square displacement is a very typical feature for L´evy flights as opposed to a finite mean square displacement with a linear dependence on time in the case of Brownian motion. L´evy distributions are characterized by an index α where 0 <α ≤ 2. When α =2, the distribution becomes a Gaussian and when α=1, it reduces to a Cauchy/Lorentzian distribution. In the overdamped limit of friction, the probability density or the propagator associated with L´evy flights can be described by a position space fractional Fokker-Planck equation(FFPE)[1–3]. Jespersen et al. [4]have solved the FFPE in the Fourier domain to obtain the propagator for free L´evy flight(absence of an external potential) and L´evy flights in linear and harmonic potentials. We use a path integral technique to study L´evy flights. L´evy distributions rarely have a compact analytical expression in the position space. However, their Fourier transformations are rather simple and are given by e−D │p│α where D determines the width of the distribution. Due to the absence of a simple analytical expression, attempts in the past to study L´evy flights using path integrals in the position space [5, 6] have not been very successful. In our approach, we have tried to make use of the elegant representation of the L´evy distribution in the Fourier space and therefore, we write the propagator in terms of a two-dimensional path integral –one over paths in the position space(x)and the other over paths in the Fourier space(p). We shall refer to this space as the ‘phase space’. Such a representation is similar to the Hamiltonian path integral of quantum mechanics which was introduced by Garrod[7]. If we try to perform the path integral over Fourier variables first, then what remains is the usual position space path integral for L´evy flights which is rather difficult to solve. Instead, we perform the position space path integral first which results in expressions which are rather simple to handle. Using this approach, we have obtained the propagators for free L´evy flight and L´evy flights in linear and harmonic potentials in the over damped limit [8]. The results obtained by this method are in complete agreement with those obtained by Jesepersen et al. [4]. In addition to these results, we were also able to obtain the exact propagator for L´evy flights in a harmonic potential with a time-dependent force constant which has not been reported in the literature. Another interesting problem that we have considered in the over damped limit is to obtain the probability distribution for the area under the trajectory of a L´evy particle. The distributions, again, were obtained for free L´evy flight and for L´evy flights subjected to linear and harmonic potentials. In the harmonic potential, we have considered situations where the force constant is time-dependent as well as time-independent. Like in the case of the over damped limit, the probability distribution for L´evy flights in the under damped limit of friction can also be described using a fractional Fokker-Planck equation, although in the full phase space. However, this has not yet been solved for any general value of α to obtain the complete propagator in terms of both position and velocity. Using our path integral approach, the exact full phase space propagators have been obtained for all values of α for free L´evy flights as well as in the presence of linear and harmonic potentials[8]. The results that we obtain are all exact when the potential is at the most harmonic. If the potential is higher than harmonic, like the cubic potential, we have used a semi classical evaluation where, we extremize the action using an optimal path and further, account for fluctuations around this optimal path. Such potentials are very useful in describing the problem of escape of a particle over a barrier. The barrier crossing problem is very extensively studied for Brownian motion (Kramers problem) and the associated rate constant has been calculated in a variety of methods, including the path integral approach. We are interested in its L´evy analogue where we consider the escape of a particle driven by a L´evy noise over a barrier. On extremizing the action which depends both on phase space variables, we arrived at optimal paths in both the position space as well as the space of the conjugate variable, p. The paths form an infinite hierarchy of instant on paths, all of which have to be accounted for in order to obtain the correct rate constant. Care has to be taken while accounting for fluctuations around the optimal path since these fluctuations should be independent of the time-translational mode of the instant on paths. We arrived at an ‘orthogonalization’ scheme to perform the same. Our procedure is valid in the limit when the barrier height is large(or when the diffusion constant is very small), which would ensure that there is small but a steady flux of particles over the barrier even at very large times. Unlike the traditional Kramers rate expression, the rate constant for barrier crossing assisted by L´evy noise does not have an exponential dependence on the barrier height. The rate constant for wide range of α, other than for those very close to α = 2, are proportional to Dμ where, µ ≈ 1 and D is the diffusion constant. These observations are consistent with the simulation results obtained by Chechkin et al. [9]. In addition, our approach when applied to Brownian motion, gives the correct dependence on D. In equilibrium statistical mechanics we have considered two problems. In the first one, we have evaluated the imaginary time propagator for a harmonic oscillator with a time-dependent force constant(ω2(t))exactly, when ω2(t) is of the form λ2(t) - λ˙(t)where λ(t) is any arbitrary function of t. We have made use of Hamiltonian path integrals for this. The second problem that we considered was the evaluation of the partition function for hindered rotors. Hindered rotors are molecules which have a barrier for internal rotation. The molecule behaves like free rotor when the barrier is very small in comparison with the thermal energy, and when the barrier is very high compared to thermal energy, it behaves like a harmonic oscillator. Many methods have been developed in order to obtain the partition function for a hindered rotor. However, most of them are some what ad-hoc since they interpolate between free-rotor and the harmonic oscillator limits. We have obtained the approximate partition function by writing it as the trace of the density matrix and performing a harmonic approximation around each point of the potential[10]. The density matrix for a harmonic potential is in turn obtained from a path integral approach[11]. The results that we obtain using this method are very close to the exact results for the problem obtained numerically. Also, we have devised a proper method to take the indistinguishability of particles into account in internal rotation which becomes very crucial while calculating the partition function at low temperatures.

In this thesis, we investigate supersymmetric quantum mechanics (SUSYQM) and its relation to index theorems and equivariant cohomology. We define some basic constructions on super vector spaces in order to set the language for the rest of the thesis. The path integral in quantum mechanics is reviewed together with some related calculational methods and we give a path integral expression for the Witten index. Thereafter, we discuss the structure of SUSYQM in general. One shows that the Witten index can be taken to be the difference in dimension of the bosonic and fermionic zero energy eigenspaces. In the subsequent section, we derive index theorems. The models investigated are the supersymmetric non-linear sigma models with one or two supercharges. The former produces the index theorem for the spin-complex and the latter the Chern-Gauss-Bonnet Theorem. We then generalise to the case when a group action (by a compact connected Lie group) is included and want to consider the orbit space as the underlying space, in which case equivariant cohomology is introduced. In particular, the Weil and Cartan models are investigated and SUSYQM Lagrangians are derived using the obtained differentials. The goal was to relate this to gauge quantum mechanics, which was unfortunately not successful. However, what was shown was that the Euler characteristics of a closed oriented manifold and its homotopy quotient by U(1)n coincide.

La théorie des bifurcations est utilisée pour étudier certains aspects des systèmes dynamiques qui intervient lorsqu'un petit changement d'un paramètre physique produit un changement majeur dans l'organisation du système. Ces phénomènes ont lieu dans les systèmes physiques, chimiques, biologiques, écologiques, économiques et sociaux. Cette idée unificatrice a été appliquée pour modéliser et explorer à la fois tant les systèmes sociaux que les systèmes physiques. Dans la première partie de cette thèse, nous appliquons les outils de la physique statistique et de la théorie des bifurcations pour modéliser le problème des décisions binaires dans les sciences sociales. Nous avons mis au point un schéma permettant de prédire l’apparition de sauts extrêmes dans ces systèmes en se basant sur la notion de précurseurs, utilisés comme signal d'alerte d'apparition de ces événements catastrophiques. Nous avons également résolu un modèle mathématique d’effondrement social fondé sur une équation de "régression logistique" utilisée pour décrire la croissance d’une population et la façon dont celle-ci peut être influencée par des ressources limitées. Ce modèle présente des bifurcations sous-critiques et nous avons étudié sa relation avec le phénomène social du « sunk-cost effect » (effet de coût irrécupérable). Ce dernier phénomène explique l’influence des investissements passés sur les décisions présentes, et la combinaison de ces deux phénomènes est utilisé comme modèle pour expliquer la désintégration de certaines sociétés anciennes (basés sur des témoignages archéologiques). Dans la deuxième partie de cette thèse, nous étudions les systèmes macroscopiques décrits par des équations différentielles stochastiques multidimensionnelles ou, de manière équivalente, par les équations multidimensionnelles de Fokker-Planck. Afin de calculer la fonction de distribution de probabilité (PDF), nous avons introduit un nouveau schéma alternatif de calcul basé sur les intégrales de chemin (« Path Integral ») lié aux processus stochastiques. Les calculs basés sur les intégrales de chemin sont effectués sur des systèmes uni et bidimensionnels et successivement comparés avec certains modèles dont on connaît la solution pour confirmer la validité de notre méthode. Nous avons également étendu ce schéma pour estimer le temps d’activation moyen (« Mean Exit Time »), ce qui a donné lieu à une nouvelle expression de calcul pour les systèmes à dimension arbitraire. A` noter que pour le cas des systèmes dynamiques à deux dimensions, les calculs de la fonction de distribution de probabilité ainsi que du temps de sortie moyen ont validé le schéma des intégrales du chemin. Ça vaut la peine de souligner que la perspective de poursuivre cette ligne de recherche repose sur le fait que cette méthode est valable pour les « non gradient systems » assujettis à des bruits d'intensité arbitraires. Cela ouvre la possibilité d'analyser des situations plus complexes où, à l'heure actuelle, il n'existe aucune méthode permettant de calculer les PDFs et/ou les METs. / Bifurcations in continuous dynamical systems, i.e., those described by ordinary differential equations, are found in a multitude of models such as those used to study phenomena related to physical, chemical, biological, ecological, economic and social systems. Using this concept as a unifying idea, in this thesis, we apply it to model and explore both Social as well as Physical systems. In the first part of this thesis we apply tools of statistical physics and bifurcation theory to model a problem of binary decision in Social Sciences. We find an scheme to predict the appearance of extreme jumps in these systems based on the notion of precursors which act as a kind of warning signal for the upcoming appearance of these catastrophic events. We also solve a mathematical model of social collapse based on a logistic re-growing equation used to model population grow and how limited resources change grow patterns. This model exhibits subcritical bifurcations and its relation to the social phenomenon of sunk-cost effect is studied. This last phenomenon explains how past investments affect current decisions and the combination of both phenomena is used as a model to explain the disintegration of some ancient societies, based on evidence from archeological records. In the second part of this thesis, we study macroscopic systems described by multidimensional stochastic differential equations or equivalently by their deterministic counterpart, the multidimensional FokkerPlanck equation. A new and alternative scheme of computation based on Path Integrals, related to stochastic processes is introduced in order to calculate the Probability Distribution Function. The computations based on this Path Integral scheme are performed on systems in one and two dimensions and contrasted to some soluble models completely validating this method. We also extended this scheme to the case of computation of Mean Exit Time, finding a new expression for each computation in systems in arbitrary dimensions. It is worth noting that in case of two-dimensional dynamical systems, the computations of both the probability distribution function as well as of the mean exit time validated the Path Integral scheme and the perspective for continuing this line of work are based on the fact that this method is valid for both arbitrary non gradient systems and noise intensities. This opens the possibility to explore new cases, for which no methods are known to obtain them.

No description available.

Robotics is an interdisciplinary field that integrates computer science, electrical engineering, mechanical engineering, control engineering and other related fields. As the quick development of these fields, people have been building more complex robots with more advanced control strategies in order to solve more challenging tasks. In addition, it is always a target for researchers to achieve autonomous operation of robots so that the manpower can be saved and the robot can work in harsh environment like on Mars. In this project, I focus on the trajectory planning problem of a unicycle model running in 2D environment. I choose Path Integral Policy Improvement (PI2) control algorithm in this project as the main study object. And Model Predictive Control (MPC) is chosen as a reference in order to be compared with PI2 to evaluate the performance of PI2. In order to simulate the tasks that the robot needs to handle in practice, I use obstacles to represent the complex environment and I use Signal Temporal Logic (STL) to represent the complex tasks. Furthermore, I also incorporate the deep dynamics model in the project so that the the method put forward in this project is able to handle complex robot models and complex working environments. To evaluate the performances of PI2 and MPC, five criteria are put forward in this project. Finally, based on the evaluation results, possible improvement and future research are proposed. / Robotics är ett tvärvetenskapligt område som integrerar datavetenskap, elektroteknik, maskinteknik, styrteknik och andra relaterade områden. Som den snabba utvecklingen av dessa fält har människor byggt mer komplexa robotar med mer avancerade kontrollstrategier för att lösa mer utmanande uppgifter. Dessutom är det alltid ett mål för forskare att uppnå autonom drift av robotar så att arbetskraften kan sparas och roboten kan arbeta i tuffa miljöer som på Mars. I det här projektet fokuserar jag på banplaneringsproblemet för en enhjulingsmodell som körs i 2D-miljö. Jag väljer Path Integral Policy Improvement (PI2) kontrollalgoritm i detta projekt som huvudstudieobjekt. Och Model Predictive Control (MPC) väljs som referens för att kunna jämföras med PI2 för att utvärdera prestandan för PI2. För att simulera de uppgifter som roboten behöver hantera i praktiken använder jag hinder för att representera den komplexa miljön och jag använder Signal Temporal Logic (STL) för att representera de komplexa uppgifterna. Dessutom införlivar jag också den djupa dynamikmodellen i projektet så att metoden som läggs fram i detta projekt kan hantera komplexa robotmodeller och komplexa arbetsmiljöer. För att utvärdera prestanda för PI2 och MPC presenteras fem kriterier i detta projekt. Slutligen, baserat på utvärderingsresultaten, föreslås möjliga förbättringar och framtida forskning.