La collision entre l'ion hydroxyle (OH+) et l'atome d'hydrogène (H) joue un rôle majeur en physico-chimie de l'atmosphère et en astrophysique. Pour l'étude de ce système, nous avons générés la surface d'énergie potentielle tridimensionnelle (SEP-3D) globale doublet de la réaction H + OH+ --- H2O+ (X2B1)--- O + H2+. Les calculs électroniques ont été effectués au niveau MRCI avec la base aug-cc-pV5Z en incluant la correction des erreurs de superposition de base (BSSE). Cette SEP couvre la région moléculaire et les régions des longues portées pour les différents canaux : OH+ + H, O + H2+ et la réaction d'échange d'hydrogène. La qualité de la SEP a été validée après une comparaison des constantes spectroscopiques de H2O+ (X2B1) et des fragments diatomiques, des niveaux rovibroniques de H2O+ (X2B1), l'énergie de dissociation et de la barrière à linéarité pour H2O+ (X2B1) aux données expérimentales et théoriques existantes. Un bon accord est trouvé. Après avoir déterminé la SEP, nous avons utilisé les outils de la dynamique quantique indépendante du temps pour calculer les sections efficaces élastiques et inélastiques désexcitation de OH+ (v=0, j=1, 2, 3, 4, 5, 6 et 7) en collision avec l'atome d'hydrogène sur un large domaine d'énergie cinétique. Nous avons ainsi déterminé les taux désexcitation rotationnelle pour des températures allant de 10 à 200K. Nous avons également utilisé la surface quadruplet de Martinez et al. pour déduire ces taux désexcitation. Les résultats montrent que les sections efficaces inélastiques calculées sur la surface doublet sont en moyenne au moins deux à trois fois plus importantes que leurs correspondantes obtenues sur la surface quartet. Les potentiels à longue portée des deux surfaces étant identiques, ce résultat montre qu'un modèle basé sur la seule longue portée du potentiel ne pourrait pas rendre compte de la dynamique inélastique de ce système / The collision between the hydroxyl cation (OH+) and hydrogen atoms (H) plays a major role in physical chemistry of the atmosphere and astrophysics. To study this system, we generated the global three-dimensional potential energy surface (3D-PES) of the reaction H + OH+ ---- H2O+ (X2B1) ---- O + H2+. The electronic calculations were performed at the MRCI level with aug-cc-pV5Z basis including the basis set superposition error (BSSE) correction. This PES covers the molecular region and the long ranges close to the OH+ + H, O + H2+ and the hydrogen exchange channels. The quality of the PES is checked after comparison of the spectroscopic constants of H2O+ (X2B1) and of the diatomic fragments, the rovibronic levels, the dissociation energy, and the barrier to linearity of H2O+ (X2B1) to available experimental and theoretical data. A good agreement is found. Then, we used the tools of time-independent Quantum Dynamics to calculate the elastic and inelastic cross sections for the de-excitation of OH+ in collision with the hydrogen atom over a wide range of kinetic energy. We have thus determined the rotational de-excitation rate coefficients for temperatures ranging from 10 up to 200K. The results show that the inelastic cross sections on the doublet surface are on average at least two to three times larger than their cross section obtained on the previously computed cross sections using the quartet surface. Since, the long range parts of the doublet and the quartet PESs are identical, our work invalidates hence previous cross section determination. When only long range potentials are considered. Therefore, we recommend using fully the global 3D PES for scattering and reactive collision relevant for atmospheric and astrophysical studies

Améliorer la représentation de la couche limite stable constitue un des grands challenges de la prévision numérique du temps et du climat. Sa représentation est clé pour la prévision du brouillard, du gel des surfaces, des inversions de température, du jet de basse couche et des épisodes de pollution. De plus, à l'échelle climatique, la hausse de la température moyenne globale de l'air en surface impacte davantage les régions polaires : améliorer la représentation de la couche limite stable est un enjeu important pour réduire les incertitudes autour des projections climatiques. Depuis une quinzaine d'années, les exercices d'intercomparaison de modèles GABLS ont montré que le mélange turbulent dans la couche limite stable est généralement surestimé par les modèles de prévision du temps. En effet, de nombreux modèles intensifient artificiellement l'activité de leur schéma de turbulence afin d'éviter une décroissance inévitable du mélange lorsque la stabilité dépasse un seuil critique en terme de nombre de Richardson gradient. Ce problème numérique et théorique n'est pas en accord avec de nombreuses observations et simulations à haute résolution qui montrent une activité turbulente séparée en deux régimes : un régime faiblement stable dans lequel l'atmosphère est turbulente de manière continue et intense, et un régime très stable dans lequel la turbulence est très intermittente, anisotrope et faible en intensité. Ces travaux de thèse s'articulent autour de deux parties dont l'objectif principal est d'améliorer la paramétrisation de la turbulence dans le modèle atmosphérique de recherche Méso-NH développé conjointement par Météo-France et le Laboratoire d'Aérologie, et dans le modèle opérationnel AROME. Cette étude utilise une méthodologie communément employée dans le développement de paramétrisations qui consiste à comparer des simulations à très haute résolution qui résolvent les structures turbulentes les plus énergétiques (LES) à des simulations uni-colonnes d'un modèle méso-échelle. Plusieurs simulations 3D couvrant différents régimes de stabilité de l'atmosphère sont réalisées avec Méso-NH. Les limites du modèle LES en stratification stable sont documentées. Une première partie répond à la problématique de la surestimation du mélange dans le régime faiblement stable. Une expression originale pour la longueur de mélange est formulée. La longueur de mélange est un paramètre clé pour les schémas de turbulence associés à une équation pronostique pour l'énergie cinétique turbulente. Cette longueur de mélange non-locale combine un terme de cisaillement vertical du vent horizontal à une formulation existante qui repose sur la flottabilité. Le nouveau schéma est évalué dans des simulations 1D par rapport aux LES d'une part ; et dans le modèle opérationnel AROME par rapport aux observations de l'ensemble du réseau opérationnel de Météo-France d'autre part. Une deuxième partie apporte des éléments d'évaluation d'un schéma combinant deux équations pronostiques pour les énergies cinétiques et potentielles turbulentes. En condition stable, le flux de chaleur négatif contribue à la production d'énergie potentielle turbulente. L'interaction entre les deux équations d'évolution permet, via une meilleure prise en compte de l'anisotropie et d'un terme à contre gradient dans le flux de chaleur, de limiter la destruction de l'énergie turbulente dans les modèles. Dans les cas simulés, cette nouvelle formulation ne montre pas un meilleur comportement par rapport à un schéma à une équation pour l'énergie cinétique turbulente car le mécanisme d'auto-préservation n'est pas dominant par rapport au terme de dissipation. Il conviendra d'améliorer la paramétrisation du terme de dissipation dans le régime très stable. / The modeling of the stable atmospheric boundary layer is one of the current challenge faced by weather and climate models. The stable boundary layer is a key for the prediction of fog, surface frost, temperature inversion, low-level jet and pollution peaks. Furthermore, polar regions, where stable boundary layer predominates, are one of the region with the largest temperature rise : the stable boundary layer modeling is crucial for the reduction of the spread of climate predictions. Since more than 15 years, the GABLS models intercomparison exercices have shown that turbulent mixing in the stable boundary layer is overestimated by numerical weather prediction models. Numerous models artificially strengthen the activity of their turbulence scheme to avoid a laminarization of the flow at a critical value of the gradient Richardson number. The existence of this threshold is only a theoretical and a numerical issues. Numerous observations and high-resolution numerical simulations do not support this concept and show two different regimes : the weakly stable boundary layer that is continuously and strongly turbulent; and the very stable boundary layer globally intermittent with a highly anisotropic and very weak turbulence. This thesis aims at improving the turbulence scheme within the atmospheric research model Méso-NH developped by Météo-France and the Laboratoire d'Aérologie, and the operational weather forecast model AROME. We use a traditional methodology based on the comparison of high-resolution simulations that dynamically resolve the most energetic turbulent eddies (Large-Eddy Simulations) to single-column simulations. Several LES covering the weakly and the very stable boundary layer were performed with Méso-NH. The limits of applicability of LES in stratified conditions are documented. The first part of the study deals with the overmixing in the weakly stable boundary layer. We propose a new diagnostic formulation for the mixing length which is a key parameter for turbulence schemes based on a prognostic equation for the turbulent kinetic energy. The new formulation adds a local vertical wind shear term to a non-local buoyancy-based mixing length currently used in Méso-NH and in the French operational model AROME. The new scheme is evaluated first in single-column simulations with Méso-NH and compared to LES, and then in the AROME model with respect to observations collected from the operational network of Météo-France. The second part presents a theoretical and numerical evaluation of a turbulence scheme based on two prognostic equations for the turbulent kinetic and potentiel energies. In stratified conditions, the heat flux contributes to the production of turbulent potential energy. The laminarization of the flow is then limited by a reduction of the destruction of the turbulent kinetic energy by a better representation of the anisotropy and a counter-gradient term in the heat flux. On the simulated cases, this new formulation behaves similarly than the scheme with one equation for the turbulent kinetic energy because the self-preservation mechanism is not dominant compared to the dissipation term. Further research should improve the turbulent kinetic energy dissipation closure in the very stable regime.

The fully quantum mechanical 'direct-potential-fit' (DPF) method has become increasingly widely used in the reduction of diatomic spectra. The central problem of this method is the representation of the potential energy and Born-Oppenheimer breakdown (BOB) correction functions. There are a number of problems associated with the existing method and potential forms. This thesis delineates these problems and finds solutions to some of them. In particular, it is shown that use of a different expansion variable and a new treatment of some of the expansions resolves most of the problems. These techniques have been successfully tested on the ground electronic states of the coinage metal hydrides and the Rb2 molecule. To address the problem of representing 'barrier' potential curves, a flexible new functional form, the 'double-exponential long-range' (DELR) potential function, is introduced and applied to the B barrier state of Li2. In addition, the Lambda-doubling level splitting which occurs for singlet Pi electronic states has been taken into account by extending the effective Schrodinger equation. The computer program DSPotFit developed in our laboratory for performing DPF analyses has been extended to incorporate the ability to fit the analytical potential energy functions to tunneling predissociation line widths for quasibound levels. Finally, an attempt is made to investigate whether there exists a hump in the ground state rotationless potential curve of beryllium hydride.

The fully quantum mechanical 'direct-potential-fit' (DPF) method has become increasingly widely used in the reduction of diatomic spectra. The central problem of this method is the representation of the potential energy and Born-Oppenheimer breakdown (BOB) correction functions. There are a number of problems associated with the existing method and potential forms. This thesis delineates these problems and finds solutions to some of them. In particular, it is shown that use of a different expansion variable and a new treatment of some of the expansions resolves most of the problems. These techniques have been successfully tested on the ground electronic states of the coinage metal hydrides and the Rb2 molecule. To address the problem of representing 'barrier' potential curves, a flexible new functional form, the 'double-exponential long-range' (DELR) potential function, is introduced and applied to the B barrier state of Li2. In addition, the Lambda-doubling level splitting which occurs for singlet Pi electronic states has been taken into account by extending the effective Schrodinger equation. The computer program DSPotFit developed in our laboratory for performing DPF analyses has been extended to incorporate the ability to fit the analytical potential energy functions to tunneling predissociation line widths for quasibound levels. Finally, an attempt is made to investigate whether there exists a hump in the ground state rotationless potential curve of beryllium hydride.

Chemically and physically patterned surfaces can be used as templates to guide nano- and micro- scale particle assembly, but the design is often limited by an inability to sufficiently characterize how pattern features influence local particle-surface interactions on the order of thermal energy, kT. The research outlined in this dissertation describes comprehensive optical microscopy (i.e. evanescent wave, video) measurements and analyses of many-body and multi-dimensional interactions, dynamics and structure in inhomogeneous colloidal fluid systems. In particular, I demonstrate how non-intrusive observation of an ensemble of particles diffusing past each other and over a physically patterned surface topography can be used to obtain sensitive images of energy landscape features. I also link diffusing colloidal probe dynamics to energy landscape features, which is important for understanding the temporal imaging process and self-assembly kinetics. A complementary effort in this dissertation investigated the use of external AC electric fields to reversibly tune colloidal interactions to produce metastable ordered configurations. In addition, the electrical impedance spectra associated with colloidal assemblies formed between interfacial microelectrode gaps was measured and consistently modelled using representative equivalent circuits. Significant results from this dissertation include the synergistic use of the very same colloids as both imaging probes and building blocks in feedback controlled selfassembly on patterns. Cycling the AC field frequencies was found to be an effective way to anneal equilibrium colloidal configurations. Quantitative predictions of dominant transport mechanisms as a function of AC electric field amplitude and frequency were able to consistently explain the steady-state colloidal microstructures formed within electrode gaps observed using video microscopy. A functional electrical switch using gold nanoparticles was realized by reversibly forming and breaking colloidal wires between electrode gaps. Extension of the concepts developed in this dissertation suggest a general strategy to engineer the assembly of colloidal particles into ordered materials and controllable devices that provide the basis for numerous emerging technologies (e.g. photonic crystals, nanowires, reconfigurable antennas, biomimetic materials).

The geometrically nonlinear constant moment triangle based on the von Karman theory of thin plates is first described. This finite element, which is believed to be the simplest possible element to pass the totality of the von Karman patch test, is employed throughout the present work. It possesses the special characteristic of providing a tangent stiffness matrix which is accurate and without approximation. The stability of equilibrium of discrete conservative systems is discussed. The criteria which identify the critical points (limit and bifurcation), and the method of determination of the stability coefficients are presented in a simple matrix formulation which is suitable for computation. An alternative formulation which makes direct use of higher order directional derivatives of the total potential energy is also presented. Continuation along the stable equilibrium solution path is achieved by using a recently developed Newton method specially modified so that stable points are points of attraction. In conjunction with this solution technique, a branch switching method is introduced which directly computes any intersecting branches. Bifurcational buckling often exhibits huge structural changes and it is believed that the computation of the required switch procedure is performed here, and for the first time, in a satisfactory manner. Hence, both limit and bifurcation points can be treated without difficulty and with continuation into the post buckling regime. In this way, the ability to compute the stable equilibrium path throughout the load-deformation history is accomplished. Two numerical examples which exhibit bifurcational buckling are treated in detail and provide numerical evidence as to the ability of the employed techniques to handle even the most complex problems. Although only relatively coarse finite element meshes are used it is evident that the technique provides a powerful tool for any kind of thin elastic plate and shell problem. The thesis concludes with a proposal for an algorithm to automate the computation of the unknown parameter in the branch switching method.

Noncovalent interactions in complex chemical systems are examined by considering model systems which capture the essential physics of the interactions and applying correlated electronic structure techniques to these systems. Noncovalent interactions are critical to understanding a host of energetic and structural properties in complex chemical systems, from base pair stacking in DNA to protein folding in organic solids. Complex chemical and biophysical systems, such as enzymes and proteins, are too large to be studied using computational techniques rigorous enough to capture the subtleties of noncovalent interactions. Thus, the larger chemical system must be truncated to a smaller model system to which rigorous methods can be applied in order to capture the essential physics of the interaction. Computational methodologies which can account for high levels of electron correlation, such as second-order perturbation theory and coupled-cluster theory, must be used. These computational techniques will be used to study several types (pi stacking, S/pi, and C-H/pi) of noncovalent interactions in two chemical contexts: biophysical systems and organic solids.

De récentes études expérimentales de la dynamique de colloïdes illuminés par une figure d'interférence optique aléatoire (tavelures ou speckle) ont montré l'existence de phénomènes de sous-diffusion, de piégeage, ou de ségrégation dans le cas de mélanges, sous l'effet de cet environnement désordonné. L'objet de ce travail de doctorat est d'approfondir la compréhension de ces phénomènes par une étude théorique. Dans ce but, une version de la théorie de couplage de modes (MCT), initialement développée pour les fluides confinés dans des solides poreux désordonnés, a été appliquée au cas d'un fluide plongé dans un potentiel aléatoire gaussien de covariance gaussienne. La résolution numérique des équations asymptotiques de cette théorie a permis la construction de diagrammes d'état, lesquels reproduisent, par exemple, le comportement réentrant non trivial de la diffusivité observé dans les expériences, dont une interprétation physique simple est proposée.Les résultats suggèrent en outre une forte dépendance de la dynamique du système par rapport à la longueur de corrélation du désordre. Une étude détaillée de la relaxation du fluide a été effectuée, dans le but d'apporter une compréhension de la dynamique à toutes les échelles de temps. En parallèle, il a été montré que de nombreuses approximations classiques utilisées dans le calcul des propriétés structurales des fluides conduisent à des résultats non physiques dans le cas présent.Finalement, un programme de simulation Monte Carlo a été développé, et les premiers résultats sont comparés à la théorie et aux expériences. / Recent experimental studies of the dynamics of colloids beamed by a random light pattern (speckle) showed the existence of subdiffusion, trapping, or mixture separation phenomena, under the action of that disordered environment.To this end, a version of the Mode Coupling Theory (MCT), initially developed for fluids in confinement in sol id porous matrices has been applied to the case of a fluid plunged in a random Gaussian potential with a Gaussian correlation function.The aim of this PhD work is to further improve the understanding of these phenomena by the addition of a theoretical study.The numerical resolution of the asymptotic equations of this theory leads to the construction o phase diagrams, which reproduce for example the non trivial reentrent behaviour of the diffusivity, observed in related experiments, for which a physical interpretation is proposed. Furthermore, results suggest a strong depend ence of the dynamics on the disorder correlation length. A detailed study of the relaxation of the fluid has been made, in order to bring an understandin( of the dynamics at ali timescales. Simultaneously, it has been showed that a number of common approximations used in the calculation of the structural properties of fluids lead in the present case to non-physical results. Finally, a Monte-Carlo simulation program has been developed, and the first results are compared to theory and experiments.

This work proposes a methodology to evaluate the performance of operating wind farms via the use of Supervisory Control and Data Acquisition System (SCADA) and modeled data. The potential annual energy is calculated per individual turbine considering underperforming/loss events to have their power output in accordance with a representative derived operational power curve. Losses/underperformance events are calculated and categorized into several groups aiming at identifying and quantify their causes. The methodology requires both anemometry data from SCADA system as well as modeled data. The discrepancy of the data representing the valid points of the power curve is taken into consideration as well when assessing the performance, i.e. wind speed vs power output of events that are not loss/underperformance. Production loss and relative standard deviation of power output of what is defined as “valid sample” in this work (per each turbine) are the main results obtained in this work. Finally, a number of optimization measures are suggested in order to enhance the performance, which can lead to a boost in the financial output of a wind farm. Aiming at judging the reliability of the proposed methodology, a case study is conducted and evaluated. The investigated case study shows that the methodology is capable of determining potential energy and associated losses/underperformance events. Several questions were raised during the assessment and are discussed in this report, recommendation for optimization measures are presented at the end of the study. Also, a discussion on the limitations and uncertainties associated to the presented methodology and the case study.

Abstract This thesis presents computational studies of both the static and dynamic parameters of the nuclear magnetic resonance (NMR) spectroscopy of gaseous xenon. First, state-of-the-art static magnetic resonance parameters are computed in small xenon clusters by using methods of quantum chemistry, and second, time-dependent relaxation phenomena are investigated via molecular dynamics simulations at different experimental conditions. Based on the underlying quantum and classical mechanics concepts, computational methods represent a procedure complementary to experiments for investigating the properties of atoms, molecules, clusters and solids. Static NMR spectral parameters, chemical shift, shielding anisotropy and asymmetry parameter, nuclear quadrupole coupling, and spin-rotation coupling, are calculated using different electronic structure methods ranging from the uncorrelated Hartree-Fock method to correlated second-order Møller-Plesset many-body perturbation, complete/restricted active space multiconfiguration self-consistent field, and to coupled-cluster approaches. The bond length dependence of these properties is investigated in the xenon dimer (Xe2). A well-characterized property in experimental NMR, the second virial coefficient of nuclear shielding, is theoretically calculated by a variety of methods and convincingly verified against experimental findings. Here, it is mandatory to include effects from special relativity as well as electron correlation. As a side result, a purely theoretical potential energy curve for Xe2, comparable to best experimental ones, is calculated. A pairwise additive scheme is established to approximate the NMR properties in differently coordinated sites of xenon clusters Xen (n = 2 - 12). Especially the pairwise additive chemical shift values are found to be in close agreement with quantum-chemical results and only a small scaling factor close to unity is needed for the correct behavior. Finally, a dynamical magnetic resonance property, the experimental nuclear spin-lattice relaxation rate R1 of monoatomic Xe gas due to the chemical shift anisotropy (CSA) mechanism is validated from first principles. This approach is based on molecular dynamics simulations over a large range of temperatures and densities, combined with the pairwise additive approximation for the shielding tensor. Therein, the shielding time correlation function is seen to reflect the characteristic time scales related to both interatomic collisions and cluster formation. For the first time, the physics of gaseous xenon is detailed in full in the context of CSA relaxation.