A perda de energia de íons na matéria é um tópico de grande interesse não apenas por suas aplicações diretas em técnicas de análises de materiais bem como nos estudos teóricos das interações íon-átomo. No entanto, o poder de freamento de sólidos para íons pesados é ainda pouco compreendido especialmente para baixas velocidades devido principalmente a complicada dependência nos números atômicos do meio freador e do íon incidente. Neste trabalho são apresentados os dados experimentais para o freamento de Cu em Au na região de velocidades de 2 - 4% da velocidade da luz. Os dados experimentais foram obtidos com uso da técnica de espalhamento elástico, onde um feixe primário de 16O e 28Si, com energias entre 35 - 52 MeV e 49 - 79 MeV respectivamente, foram tilizados para produzir íons de Cu em recuo a partir de um alvo fino ( 160 g/cm2). O feixe primário espalhado é detectado a 60o por um detector de Si, produzindo átomos de Cu do alvo recuando em um ângulo denido pela cinemática da colisão elástica. Os íons em recuo medidos em coincidência temporal com o feixe primário espalhado compõe o feixe secundário de interesse. A perda de energia, em uma folha de Au com espessura em torno de 530 g/cm2, foi obtida medindo-se a energia do feixe secundário com um detector de Si, com e sem a folha de Au interceptando os íons em recuo. Os dados experimentais foram comparados com teorias e modelos semi-empíricos aplicáveis a esse caso. Bom acordo entre a previsão da Aproximação de Convolução Unitária e nossos dados experimentais é observado. / The energy loss of ions in materials is an important issue not only because of its direct applications in analytic techniques of materials but also for studying the basics of ion-atom interactions. Nevertheless, the Stopping Power of heavy ions in solids is still poorly understood which is especially true at low velocities mainly due to the complicated dependence on the atomic numbers of the stopper medium and of the stopping ion. In this work we present new experimental data for Copper ions slowing down in Gold foil in the velocity range of 2 to 4% of the velocity of light. Experimental data were obtained using the elastic scattering technique, where primary beams of 16O and 28Si, with energies from 35 to 52 MeV and 49 to 79 MeV respectively, were used to scatter Cu íons from a thin target ( 160 g/cm2). The scattered primary beam is detected at 60 with a Si detector, producing recoiling atoms of the target in an angle given by the elastic scattering kinematics. The recoiling ions in temporal coincidence with the scattered primary beam will compose the secondary beam. The energy loss, in a gold foil with thickness about 530 g/cm2, was obtained by measuring the energy of the secondary beam with a Si detector, with and without the Au foil intercepting the recoiling ions. Experimental results were compared with theories and semi-empirical models applied to this case. Good agreement between Unitary Convolution Approximation (UCA) prediction and our data is observed.

Ce travail de recherche interroge la notion du développement durable, et la façon dont ce concept se traduit dans le domaine des énergies renouvelables et du « tourisme durable » du niveau international au niveau local. A partir de cette question de départ, nous avons souhaité analyser les enjeux de la « durabilité » des énergies renouvelables par rapport à l’activité touristique et comprendre les leviers et les mécanismes qui participent à l’instauration d’un nouveau statut énergétique compatible avec le « développement durable ». Le développement durable n’étant pas un concept accepté de manière uniforme par tous les chercheurs, notre étude met en évidence la diversité des enjeux selon les échelles géographiques et repose sur des sources d’information variées, en essayant de distinguer les analyses théoriques et empiriques, et d’approcher la réalité de l’Europe par les réalités nationales et locales. Comme champ d’application de notre recherche nous avons choisi les îles de la Grèce, et nous avons cherché à voir comment les décideurs politiques de ce pays ont essayé de développer les énergies renouvelables en leur attribuant le statut de «formes énergétiques fondamentales » selon les lignes européennes. Nous avons cherché à élargir et valider nos conclusions par l’évaluation des « meilleures et des plus mauvaises pratiques » parmi diverses îles du monde. Nous avons revelé qu’il existe plusieurs dimensions du problème : - le jeu entre acteurs d'échelles différentes, aux enjeux souvent différents - le jeu et les interactions entre logiques sectorielles - le jeu des logiques spécifiques à certains milieux géographiques. Après des recommandations qui insistent sur l’importance de facteurs institutionnels et organisationnels dans le processus d’un développement durable, on parvient à conlure que, même si la multiplicité des échelles implique une grande complexité du développement durable, il y a toujours un espoir pour faire passer le message de Bruxelles à l’échelon local, sous la condition que certains paramètres soient pris en considération. / This research discusses the notion of sustainable development, and the way in which this concept is translated in the fields of renewable energies and “sustainable tourism” from the international to the local level. From this starting question, we wished to analyze the challenges of renewable energies regarding sustainability within tourist activity and understand the mechanisms which participate in the introduction of a new energy status compatible with “sustainable development”. The sustainable development not being an accepted concept in a uniform way by all the researchers, our study highlights the diversity of challenges met to various geographical scales. Our work is based on multiple information sources, while trying to distinguish theoretical and empirical analyses and to approach European reality through national and local realities. As field of application in our research, we have chosen the islands of Greece and we sought to see how political decision makers of this country have tried to develop renewable energies allocating them the status of “fundamental energy forms” in compliance with European guidelines. We sought to widen and validate our conclusions through the evaluation of “better and worst practices” among various islands of the world. We revealed that there are several dimensions of the problem: - interactions between actors of different scales, with often different challenges to meet - interactions between sectorial logics - interactions between specific logics applied to certain geographical environments. After our recommendations which insist on the importance of institutional and organisational factors in the process of sustainable development, we conclude that, even if the multiplicity of the scales implies a great complexity in the implementation of sustainable development practices, there is always a hope to transmit the message from Brussels to the local level, under the condition that certain parameters are taken into account.

Le raccordement des énergies renouvelables (ENR) aux réseaux de distribution peuvent nécessiter des travaux de renforcement coûteux et long à mettre en œuvre. Différentes solutions alternatives peuvent dans certains cas limiter l'ampleur des travaux à réaliser et donc leur montant et/ou leur durée. L’utilisation de telles solutions nécessite au préalable de réviser les méthodes de planification du réseau pour qu’elles puissent analyser leurs impacts technico-économiques. Cette thèse a pour objet d’apporter un cadre adapté à l’étude des leviers d’intégration des ENR à l’aide de nouvelles méthodes pour la planification pluriannuelle des réseaux de distribution. Comparée à l’état de l’art, l’approche adoptée présente l’avantage d’estimer les performances de ces leviers à moyen/long terme en considérant : 1) le comportement du gestionnaire de réseau de distribution, modélisé sous la forme d’une stratégie de planification multi-variables, 2) les interactions entre les réseaux de moyenne et basse tension, et 3) les incertitudes sur l’arrivée des ENR. Ces trois axes d’amélioration ont pu être abordés grâce à des méthodes de maîtrise du temps de calcul appliquées à l’estimation pluriannuelle de l’état électrique du réseau. Le potentiel de l’approche proposée est illustré via l’analyse technico-économique de plusieurs stratégies de planification incluant des leviers traditionnels et/ou des leviers d’effacement de production. Les travaux se concluent sur une première contribution sur l’optimisation des stratégies de planification compte tenu des incertitudes sur l’arrivée des ENR / The integration of Renewable Energy Sources (RES) into the distribution networks may require network reinforcements that can be expensive and take time. Different alternative solutions can limit the amount of work to be carried out and thus reduce their cost and/or duration. The use of such solutions requires modifying the network planning methods so as to analyze their techno-economic impacts. This research aims to provide a suitable framework for the study of RES-integration solutions using novel methods for the multi-year planning of distribution networks. Compared to the state of the art, the proposed approach provides the advantage of assessing the performance of these solutions in the medium/long run by considering: 1) the behavior of the distribution system operator, which is modeled as a multi-variable planning strategy, 2) the interactions between medium- and low-voltage networks, and 3) the uncertainties on the arrival of new RES. These three points could have been addressed by applying methods of reducing computation time to the multi-year estimation of the electrical network state. The potential of the proposed approach is illustrated through the techno-economic analysis of several planning strategies including traditional solutions and/or generation curtailment. The research concludes with a first contribution to the planning strategy optimization by taking into account the uncertainties on the arrival of new RES.

The main focus of the current dissertation thesis is research of gold catalyzed reactions. I was using mass spectrometry as the primary research technique. I complemented the results with infrared multiphoton dissociation spectroscopy, nuclear magnetic resonance spectroscopy and quantum chemical calculations. I have investigated the interaction of the gold(I) cation with unsaturated hydrocarbons in the first part of my thesis. Secondly, I have studied gold(I) or silver(I) affinity to gold acetylides. In the last part, I have investigated the reaction mechanism of a gold mediated addition of methanol to alkynes. I found out that the gold(I) cation interacts stronger with gold acetylides than with nonactivated triple CC bonds. I showed that the complexes containing two gold atoms represent the key intermediates in the mechanism of addition of methanol to alkynes and that the ligand on the gold catalyst plays a fundamental role in the determination of the mechanism. Powered by TCPDF (www.tcpdf.org)

La théorie de la fonctionnelle de la densité dépendante du temps (TDDFT) est aujourd'hui une méthode de référence pour le calcul des énergies d'excitation électroniques. Cependant, dans les approximations usuelles, elle n'est pas capable de décrire correctement les excitations de Rydberg, à transfert de charge ou présentant un caractère multiple. La séparation de portée de l'interaction électronique permet de combiner rigoureusement les méthodes fonctionnelles pour décrire la courte portée de l'interaction et les méthodes fonctions d'onde ou fonctions de Green pour la longue portée. Dans cette thèse, les effets de cette séparation de portée sur les énergies d'un système en interaction partielle sont d'abord étudiés le long de la connection adiabatique dans le cas indépendant du temps afin d'aider le développement des méthodes à séparation de portée pour les énergies d'excitation. La séparation de portée est ensuite appliquée dans le cadre de la TDDFT aux noyaux d'échange et de corrélation, où dans le cas d'une approximation monodéterminentale, la longue portée du noyau de corrélation est absente. Afin de prendre en compte l'effet des doubles excitations, un noyau de corrélation de longue portée dépendant de la fréquence est développé en s'inspirant du noyau Bethe-Salpeter. Ce noyau est alors ajouté de façon perturbative au noyau TDDFT à séparation de portée afin de prendre en compte les effets des excitations doubles. / Linear-response time-dependent density-functional theory (TDDFT) is nowadays a method of choice to compute molecular excitation energies. However, within the usual adiabatic semi-local approximations, it is not able to describe properly Rydberg, charge-transfer or multiple excitations. Range separation of the electronic interaction allows one to mix rigorously density-functional methods at short range and wave function or Green’s function methods at long range. When applied to the exchange functional, it already corrects most of these deficiencies but multiple excitations remain absent as they need a frequency-dependent kernel. In this thesis, the effects of range separation are first assessed on the excitation energies of a partially-interacting system in an analytic and numerical study in order to provide guidelines for future developments of range-separated methods for excitation energy calculations. It is then applied on the exchange and correlation TDDFT kernels in a single-determinant approximation in which the long-range part of the correlation kernel vanishes. A long-range frequency-dependent second-order correlation kernel is then derived from the Bethe-Salpeter equation and added perturbatively to the range-separated TDDFT kernel in order to take into account the effects of double excitations.

This report aims to make a comparison between the Swedish and Spanish electricity market, the design of new improvements that could achieve a better operation for both markets as well as the price forecasting for both spot markets. These enhancements are oriented to decrease electricity prices, energy use and the system CO2 emissions. Also, the main organizations of the market and their roles has been characterized, clarifying the functions of the Market Operator and the System Operator. In addition, the different markets, the trading products and the price formation have been explained and the picture of the market structure has been achieved with enough depth. Moreover, some of the most used methods in Time Series Analysis has been enumerated to understand which techniques are needed for forecast the electricity prices and the methodology used (Box-Jenkins Method) has been explained in detail. Later, all these methods have been implemented in an own code developed in Python 3.6 (TSAFTools .py) with the help of different statistics libraries mentioned during the method chapter. On the other hand, the description of the market situation has been carried out for both countries. Power installed capacity, electricity generation, average prices, main renewable technologies and policies to increase the renewable energy share has been analysed and corresponding described. Then, to estimate the market’s future spot electricity prices, ARIMA models have been selected to analyse the evolution of the day-ahead price using the TSAFTools.py. The final models show a proper performance in the two markets, especially in the Nordpool, achieving an RMSE: 37.68 and MAPE: 7.75 for the year in 2017 in Nordpool and a RMSE: 270.08 and MAPE: 20.24 in OMIE for 2017. Nordpool spot prices from 2015 to 2016 has been analysed too but obtaining a result not as good as the year 2017 with an RMSE: 49.01 and MAPE: 21.42. After this analysis, the strengths and weaknesses of both markets are presented and the main problems of the Spanish electricity system (power overcapacity, fuel dependency, non-cost-efficient renewable energies policies, lack of interconnexion capacity etc.) and the Swedish electricity system (dependency for nuclear power, uncertainty for solar electricity Generation) are presented. Finally, due to the quick development of the energy sector in the last years and the concern of the European Committee to reach a new design for the electricity market, different kinds of recommendations for the future have been considered.

Les sursauts gamma se divisent entre sursauts courts, issus de la coalescence de deux objets compacts, et sursauts longs, issus de l'effondrement d'une étoile très massive de type Wolf-Rayet. Ce phénomène cataclysmique produit un jet ultra-relativiste. La dissipation de l'énergie au sein de ce jet est à l'origine d'une bouffée de photons gamma (keV-GeV) d'une durée moyenne de 10 s que l'on nomme émission prompte. Elle est suivie d'une phase d'émission rémanente détectable en X, en optique et en radio qui est visible de quelques secondes après le sursauts à quelques jours voir semaines et provient de la dissipation de l'énergie du jet dans le milieu environnant. Il s'agit des événements transitoires les plus lumineux que nous connaissons ce qui permet de les détecter jusqu'à des valeurs de décalage cosmologique (redshift) de l'ordre de 8-9. Cela permet l'exploration du diagramme de Hubble à grand redshift qui reste encore mal connu. Mais pour cela, il est nécessaire de standardiser ces sources astrophysiques afin de calibrer leur luminosité. Diverses relations, liant la luminosité des sursauts gamma à un paramètre indépendant de la cosmologie, ont été mises en évidence permettant de transformer les sursauts en " chandelles standards ". Au cours de cette thèse, nous avons étudié ces relations afin d'apporter un éclairage nouveau sur la façon dont elles sont affectées par divers effets de sélection instrumentaux. Les relations spectrales lient la luminosité isotropique ou l'énergie isotropique à l'énergie du maximum spectral de l'émission prompte. Nous avons montré que la combinaison de deux effets de sélection (détection puis mesure du redshift) permettait d'expliquer les contradictions entre les études reposant sur les sursauts avec redshift et celles incluant les sursauts sans redshift. Cela a conduit à la mise en évidence d'un lien entre l'émission prompte en gamma et l'émission rémanente en optique. Nous nous sommes également intéressé à l'une des relations temporelles, celle reliant Liso au délai spectral. Ce paramètre correspond à la différence entre le temps d'arrivée des photons de hautes et de basses énergies. Après avoir développé notre propre méthode de calcul de cette quantité, nous avons obtenu des résultats intéressants sur les distributions de ce paramètre et son lien avec l'évolution spectrale au sein des sursauts gamma. Nous avons également mis en évidence l'existence d'effets de sélection impactant cette relation et compromettant son usage pour la cosmologie. Plus généralement, cette thèse a permis de mettre en évidence la complexité de la standardisation des sursauts gamma qui ne peut être faites de manière aussi simple que celle utilisée jusqu'à présent. Nous avons montré qu'une étude détaillée des effets de sélection qui affectent ces relations de standardisation est un préalable indispensable avant toute utilisation de ces dernières à des fins cosmologiques. / GRBs are divided between short bursts, resulting from the coalescence of two compact objects, and long bursts, resulting from the collapse of a very massive star (Wolf-Rayet type). This cataclysmic phenomenon produces an ultra-relativistic jet. Energy dissipation in this jet produces flashes of gamma photons (keV-GeV) with an average duration of 10 seconds which is called prompt emission. It is followed by a detectable afterglow phase in X, optical and radio band which is visible from a few seconds after the bursts to several days or weeks and results from the dissipation of the energy contained in the jet into the surrounding medium. They are the most luminous transient events that we know, which can be detected up to redshifts of about 8-9. Being so bright, GRBs may allow the exploration of the Hubble diagram at high redshift, which is still poorly understood. To do this, it is however necessary to standardize these astrophysical sources and calibrate their brightness. Various relationships linking the intrinsic luminosity of GRBs with a parameter independent from cosmology have been highlighted allowing GRBs standardization. To achieve this goal, it is necessary to assess whether the observed correlations represent an intrinsic property of GRBs. In this thesis, we study selection effects to understand their impact on several relations which have been used to standardize GRBs. Spectral relationships connect the isotropic brightness or isotropic energy, and the peak energy of the prompt emission. We show that a combination of two selection effects, respectively associated with the GRB detection and the measure of their redshift, explains the contradiction between studies based on GRBs with a redshift and studies based on larger samples of GRBs without a redshift. Our study led us to discover a link between the prompt gamma emission and the optical afterglow that is a first step to understand the link between these two phases of the gamma-ray burst emission. Among the second category of relations, we focused on the relation between the luminosity and the spectral lag of the prompt emission. This parameter corresponds to the difference between the times of arrival of GRB photons at high and low energies. We developed our own method for the measure of the spectral lag, which led us to discuss the distribution of this parameter and its relationship to the spectral evolution within GRBs. We also confirmed the existence of selection effect affecting this relationship and compromising its use for cosmology. This thesis highlights the strong impact of observational selection effects on the relations which have been proposed for GRB standardization. We conclude that the study of selection effects is essential to understand if the relations proposed for the standardization of GRBs are intrinsic or due to selection effects, and if they can be used for cosmological purposes.

In a energy scenario moving fast towards the deployment of renewable energy technologies and the need of reducing CO2 emissions, hybrid energy systems for rural electrification are a feasible alternative solution to the utilization of conventional Diesel generators. The project focuses on the design and optimization of an off-grid hybrid energy system for a village of around 250 inhabitants in Gujarat, India. The energy system is part of a bigger project, “G.I.V.E. Center of Excellence”, which has an innovative concept on a more sustainable rural lifestyle. The system, which has to depend mainly on locally available resources, intends to serve three main services: electrical demand, water purification and thermal energy for cooking. Two system configurations were designed and optimized to supply the estimated demand. The main outcome is a techno-economic analysis of the different system performances, which leads to a conclusion: dealing with the services individually has lower costs of implementation, less than half if compared to the implementation of a conventional Diesel generator. Furthermore, CO2 emissions are drastically reduced. A sensitivity analysis was performed to address the different uncertainties such as the cost of the fuel. The result shows that if enough biomass resource would be available, a system based only on renewable energy technologies is economically profitable. / G.I.V.E. Scandinavia

A perda de energia de íons na matéria é um tópico de grande interesse não apenas por suas aplicações diretas em técnicas de análises de materiais bem como nos estudos teóricos das interações íon-átomo. No entanto, o poder de freamento de sólidos para íons pesados é ainda pouco compreendido especialmente para baixas velocidades devido principalmente a complicada dependência nos números atômicos do meio freador e do íon incidente. Neste trabalho são apresentados os dados experimentais para o freamento de Cu em Au na região de velocidades de 2 - 4% da velocidade da luz. Os dados experimentais foram obtidos com uso da técnica de espalhamento elástico, onde um feixe primário de 16O e 28Si, com energias entre 35 - 52 MeV e 49 - 79 MeV respectivamente, foram tilizados para produzir íons de Cu em recuo a partir de um alvo fino ( 160 g/cm2). O feixe primário espalhado é detectado a 60o por um detector de Si, produzindo átomos de Cu do alvo recuando em um ângulo denido pela cinemática da colisão elástica. Os íons em recuo medidos em coincidência temporal com o feixe primário espalhado compõe o feixe secundário de interesse. A perda de energia, em uma folha de Au com espessura em torno de 530 g/cm2, foi obtida medindo-se a energia do feixe secundário com um detector de Si, com e sem a folha de Au interceptando os íons em recuo. Os dados experimentais foram comparados com teorias e modelos semi-empíricos aplicáveis a esse caso. Bom acordo entre a previsão da Aproximação de Convolução Unitária e nossos dados experimentais é observado. / The energy loss of ions in materials is an important issue not only because of its direct applications in analytic techniques of materials but also for studying the basics of ion-atom interactions. Nevertheless, the Stopping Power of heavy ions in solids is still poorly understood which is especially true at low velocities mainly due to the complicated dependence on the atomic numbers of the stopper medium and of the stopping ion. In this work we present new experimental data for Copper ions slowing down in Gold foil in the velocity range of 2 to 4% of the velocity of light. Experimental data were obtained using the elastic scattering technique, where primary beams of 16O and 28Si, with energies from 35 to 52 MeV and 49 to 79 MeV respectively, were used to scatter Cu íons from a thin target ( 160 g/cm2). The scattered primary beam is detected at 60 with a Si detector, producing recoiling atoms of the target in an angle given by the elastic scattering kinematics. The recoiling ions in temporal coincidence with the scattered primary beam will compose the secondary beam. The energy loss, in a gold foil with thickness about 530 g/cm2, was obtained by measuring the energy of the secondary beam with a Si detector, with and without the Au foil intercepting the recoiling ions. Experimental results were compared with theories and semi-empirical models applied to this case. Good agreement between Unitary Convolution Approximation (UCA) prediction and our data is observed.

Ca2+ is an important messenger that affects almost all cellular processes. Ca2+ signaling involves events that happen at various time-scales such as Ca2+ diffusion, trans-membrane Ca2+ transport and Ca2+-mediated protein-protein interactions. In this work, we utilized multi-scale computational methods to quantitatively characterize Ca2+ diffusion efficiency, Ca2+ binding thermodynamics and molecular bases of Ca2+-dependent protein-protein interaction. Specifically, we studied 1) the electrokinetic transport of Ca2+ in confined sub-µm geometry with complicated surfacial properties. We characterized the effective diffusion constant of Ca2+ in a cell-like environment, which helps to understand the spacial distribution of cytoplasmic Ca2+. 2) the association kinetics and activation mechanism of the protein phosphatase calcineurin (CaN) by its activator calmodulin (CaM) in the presence of Ca2+. We found that the association between CaM and CaN peptide is diffusion-limited and the rate could be tuned by charge density/distribution of CaN peptite. Moreover, we proposed an updated CaM/CaN interaction model in which a secondary interaction between CaN’s distal helix motif and CaM was highlighted. 3) the roles of Mg2+ and K+ in the active transport of Ca2+ by sarco/endoplasmic reticulum Ca2+-ATPase (SERCA) pump. We found that Mg2+ most likely act as inhibitor while K+ as agonist in SERCA’s transport process of Ca2+. Results reported in this work shed insights into various aspects of Ca2+ signaling from molecular to cellular level.