This work concerns the interrelationship between thermodynamic, kinetic and structural aspects of crystal polymorphism. It is both experimental and theoretical, and limited with respect to compounds to substituted monocyclic aromatics. Two polymorphs of the compound m-aminobenzoic acid have been experimentally isolated and characterized by ATR-FTIR spectroscopy, X-ray powder diffraction and optical microscopy. In addition, two polymorphs of the compound m-hydroxybenzoic acid have been isolated and characterized by ATR-FTIR spectroscopy, high-temperature XRPD, confocal Raman, hot-stage and scanning electron microscopy. For all polymorphs, melting properties and specific heat capacity have been determined calorimetrically, and the solubility in several pure solvents measured at different temperatures with a gravimetric method. The solid-state activity (ideal solubility), and the free energy, enthalpy and entropy of fusion have been determined as functions of temperature for all solid phases through a thermodynamic analysis of multiple experimental data. It is shown that m-aminobenzoic acid is an enantiotropic system, with a stability transition point determined to be located at approximately 156°C, and that the difference in free energy at room temperature between the polymorphs is considerable. It is further shown that m-hydroxybenzoic acid is a monotropic system, with minor differences in free energy, enthalpy and entropy. 1393 primary nucleation experiments have been carried out for both compounds in different series of repeatability experiments, differing with respect to solvent, cooling rate, saturation temperature and solution preparation and pre-treatment. It is found that in the vast majority of experiments, either the stable or the metastable polymorph is obtained in the pure form, and only for a few evaluated experimental conditions does one polymorph crystallize in all experiments. The fact that the polymorphic outcome of a crystallization is the result of the interplay between relative thermodynamic stability and nucleation kinetics, and that it is vital to perform multiple experiments under identical conditions when studying nucleation of polymorphic compounds, is strongly emphasized by the results of this work. The main experimental variable which in this work has been found to affect which polymorph will preferentially crystallize is the solvent. For m-aminobenzoic acid, it is shown how a significantly metastable polymorph can be obtained by choosing a solvent in which nucleation of the stable form is sufficiently obstructed. For m-hydroxybenzoic acid, nucleation of the stable polymorph is promoted in solvents where the solubility is high. It is shown how this partly can be rationalized by analysing solubility data with respect to temperature dependence. By crystallizing solutions differing only with respect to pre-treatment and which polymorph was dissolved, it is found that the immediate thermal and structural history of a solution can have a significant effect on nucleation, affecting the predisposition for overall nucleation as well as which polymorph will preferentially crystallize. A set of polymorphic crystal structures has been compiled from the Cambridge Structural Database. It is found that statistically, about 50% crystallize in the crystallographic space group P21/c. Furthermore, it is found that crystal structures of polymorphs tend to differ significantly with respect to either hydrogen bond network or molecular conformation. Molecular mechanics based Monte Carlo simulated annealing has been used to sample different potential crystal structures corresponding to minima in potential energy with respect to structural degrees of freedom, restricted to one space group, for each of the polymorphic compounds. It is found that all simulations result in very large numbers of predicted structures. About 15% of the predicted structures have excess relative lattice energies of <=10% compared to the most stable predicted structure; a limit verified to reflect maximum lattice energy differences between experimentally observed polymorphs of similar compounds. The number of predicted structures is found to correlate to molecular weight and to the number of rotatable covalent bonds. A close study of two compounds has shown that predicted structures tend to belong to different groups defined by unique hydrogen bond networks, located in well-defined regions in energy/packing space according to the close-packing principle. It is hypothesized that kinetic effects in combination with this structural segregation might affect the number of potential structures that can be realized experimentally. The experimentally determined crystal structures of several compounds have been geometry-optimized (relaxed) to the nearest potential energy minimum using ten different combinations of common potential energy functions (force fields) and techniques for assigning nucleus-centred point charges used in the electrostatic description of the energy. Changes in structural coordinates upon relaxation have been quantified, crystal lattice energies calculated and compared with experimentally determined enthalpies of sublimation, and the energy difference before and after relaxation computed and analysed. It is found that certain combinations of force fields and charge assignment techniques work reasonably well for modelling crystal structures of small aromatics, provided that proper attention is paid to electrostatic description and to how the force field was parameterized. A comparison of energy differences for randomly packed as well as experimentally determined crystal structures before and after relaxation suggests that the potential energy function for the solid state of a small organic molecule is highly undulating with many deep, narrow and steep minima. / QC 20110527

Les travaux réalisés au cours de cette thèse se décomposent en deux thèmes principaux, eux-même subdivisés enplusieurs projets. D'une part, des travaux ont été menés concernant l'analyse et le développement de fonctionnelles « doubles hybrides ». Une analyse des fonctionnelles « doubles hybrides » à séparation linéaire le long de la connexionadiabatique a été proposée. Une nouvelle fonctionnelle « double hybride » à séparation de portée basée sur uneséparation alternative de l'énergie d'échange et de corrélation, RSDHf, a été développée. D'autre part, des travaux quant au développement de surfaces d'énergie potentielle (SEP) analytiques ont été menés. Un nouveau potentiel analytique a été proposé pour la description de la SEP des systèmes triatomiques. La combinaison de ce potentiel avec un potentiel électrostatique a été utilisé pour le développement de SEP analytiques pour de petits systèmes en interaction faible : H2O···HF, HF2-, Ne···ClF. / Works done during this thesis split into two main themes, themselves subdivided in several projects. On the one hand, works have been led concerning the analysis and the development of double-hybrid functionals. An analysis of linearly-separated double-hybrid functionals along the adiabatic connection has been proposed. A new range-separated double-hybrid functional based on an alternative separation of the exchange-correlation energy, RSDHf, has been developed. On the other hand, works related to the development of analytic potential energy surfaces (PES) has been led. A new analytic potential has been proposed for the description of the PES of triatomic systems. The combinaition of this potential with an electrostatic potential has been used for the development of analytic PES for small systems in weak interaction : H2O···HF, HF2-, Ne···ClF.

Em geral, as formulações disponíveis na literatura para a análise de cascas laminadas reforçadas com fibras substituem o meio original heterogêneo por um homogêneo equivalente, que dificulta a identificação das tensões fibra-matriz, ou requerem que a malha de elementos finitos seja disposta de modo que os nós dos elementos finitos de fibra coincidam com os nós dos elementos finitos de casca, que é uma exigência bastante restritiva e que aumenta o número de graus de liberdade do sistema de equações resultante. Neste sentido, o objetivo geral desta tese consiste em desenvolver uma formulação para a inclusão de fibras longas e curtas aleatórias nas diversas lâminas de cascas laminadas anisotrópicas com não linearidade geométrica utilizando o método dos elementos finitos sem aumentar o número de graus de liberdade do sistema de equações resultante e sem a necessidade de coincidência de nós na discretização das fibras e da matriz. Nesta formulação, o elemento finito triangular de casca laminada utilizado para discretizar a matriz possui dez nós e sete graus de liberdade por nó, sendo três translações, três componentes do vetor generalizado e a taxa de variação linear da deformação ao longo da espessura. As fibras curvas, curtas aleatórias ou longas, são introduzidas, em qualquer camada do laminado, por meio de relações cinemáticas que garantem sua aderência à matriz sem a introdução de novos graus de liberdade no sistema de equações resultante. Para discretizá-las são utilizados elementos finitos unidimensionais de ordem qualquer com três graus de liberdade por nó e que consideram consistentemente a não linearidade geométrica. Todas as grandezas envolvidas são escritas em relação à configuração inicial do corpo, caracterizando a descrição Lagrangeana total ou material do movimento. Para modelar o comportamento do material adota-se a Lei Constitutiva de Saint-Venant-Kirchhoff que relaciona de forma linear o tensor de tensões de Piolla-Kirchhoff de segunda espécie e o tensor de deformações de Green-Lagrange. O equilíbrio é encontrado a partir do Princípio da Mínima Energia Potencial Total e o sistema não linear de equações resultante é resolvido utilizando-se o procedimento iterativo de Newton-Raphson. As ações externas podem ser introduzidas ao sistema de forma total ou incremental e a contribuição das fibras para a energia do sistema é adicionada na matriz global do problema. Os exemplos numéricos testados validam e demonstram as potencialidades da formulação proposta. / In general, the Finite Element (FE) formulations available in the literature for the analysis of fibre reinforced laminated shells replace the original heterogeneous medium by an equivalent homogeneous one, which makes difficult the identification of fiber-matrix stress distribution, or require that the finite element mesh is arranged in a way that the fibre finite element nodes coincide with the shell finite element ones, which is a very restrictive requirement and increases the number of degrees of freedom of the resulting system of equations. In this sense, the objective of this thesis is to develop a formulation for the inclusion of long and random short fibres in any layer of FE laminated anisotropic shells developing large displacement and rotations without increasing the number of degrees of freedom and the necessity of matching nodes in the discretization of the fibre and the matrix. In this formulation, the triangular laminated shell finite element used to discretize the matrix has ten nodes and seven degrees of freedom per node, that are, three translations, three components of a generalized vector and the linear rate of strain variation along the thickness. The curved fibres, long or random short, are introduced in any layer of the laminate shell by means of kinematic relation to ensure its adherence to the matrix without introducing new degrees of freedom in the resulting system of equations. To discretize them, any order one-dimensional finite elements with three degrees of freedom per node are used. These fibres elements are consistently considered by Geometric nonlinearity. All involved variables are written with respect to the initial configuration of the body, characterizing the Total Lagrangian description. To model the behavior of the material we use the Saint-VenantKirchhoff Constitutive Law that relates linearly the second Piolla-Kirchhoff stress tensor and Green-Lagrange strain tensor. The equilibrium is achieved from the Principle of Minimum Potential Energy and the non-linear system of equations is solved by the Newton-Raphson iterative procedure. External loads may be introduced to the system by one or various steps and the contribution of fibres to the energy of the system is added to the global matrix of the problem. The numerical examples validate and demonstrate the potential of the proposed formulation.

Les travaux réalisés au cours de cette thèse portent sur la dynamique quantique de diffusion d'atomes d'hydrogène sur une surface de palladium (111). L'étude du système 3D a permis de détailler le spectre infrarouge de H/Pd(111) en mettant en évidence l'existence sur différents sites d'adsorption d'états localisés fortement couplés (résonance de Fermi). Ce phénomène gouverne la diffusion des atomes d'hydrogène sur une échelle de temps ultra-rapide (fs).L'étude du système 6D (H2/Pd(111)) a montré que les transitions observées sont, en fait, des bandes de transition entre plusieurs états d'adsorption quasi-dégénérés. L'accord entre les valeurs calculées et mesurées est, par contre, significativement moins bon qu'entre celles calculées pour le système 3D et les données mesurées. Est-ce que l'hydrogène adsorbé sur le palladium existe sous la forme d'une molécule diatomique faiblement lié? Cette thèse a fourni certains éléments de réponse à cette question, qui reste cependant encore ouverte. / The work carried out during this thesis focuses on the quantum dynamics of the diffusion of hydrogen atoms on a surface of palladium (111). The study of the 3D system allowed us to detail the infrared spectrum of H/Pd (111), showing the existence of different adsorption sites on which localized states exist that are strongly coupled (Fermi resonance). This phenomenon governs the diffusion of hydrogen atoms in an ultra-fast time scale (fs).The study of the (6D) H2/Pd(111) system has shown that the transitions observed are in fact transition bands between several quasi-degenerate adsorption states. The agreement between the calculated and measured values is significantly less good than that between the data calculated for the 3D system and the measured data. Does adsorbed hydrogen on palladium exist in the form of a weakly bound H2 molecule? This thesis has provided some answers to this question, which remains open, hovewer, to some extent.

The atmospheric boundary layer (ABL) is the lowest layer of the atmosphere where surface effects are felt on time scales of about an hour. While its properties are determined by the surface characteristics, season and synoptic conditions, they in turn determine convective cloud properties and are required for the representation of cloud processes in atmospheric models. Further, interaction of the ABL with the surface layer of the ocean is a key component of ocean-atmosphere coupling. ABL characteristics over ocean surrounding the sub-continent become very important for understanding the monsoon processes during the monsoon season because the roots of many monsoon systems, that give rain to India, are over there. In this thesis data used are from three major field experiments namely the Bay of Bengal Monsoon Experiment (BOBMEX, 1999), Arabian Sea Monsoon Experiment (ARMEX, in two phases, ARMEX-I during 2002 and ARMEX-II in 2003), and Continental Tropical Convergence Zone (CTCZ) experiment (Pilot in 2009) which were carried out under the Indian Climate Research Programme (ICRP). While there have been few studies on ABL characteristics for individual cruises, a comprehensive study considering all available radiosonde data from the above cruises has been missing. This study fills this gap and focuses on the vertical structure of ABL using more than 400 high resolution Vaisala GPS radiosonde data collected over Bay of Bengal and Arabian Sea. The study attempts at first to look at the ABL characteristics of individual cruises and then compare and contrast them over the Bay of Bengal and Arabian Sea. ABL height Hm, estimated by using virtual potential temperature (θv) profile, shows diurnal variation during weak phase of convection while maximum in early morning during active phase of convection. Different variables i.e. moist static energy (h), specific humidity (q), convective available potential energy (CAPE), virtual potential temperature (θv) and equivalent potential temperature (θe) also differ during weak and active convection periods. Conserved variables mixing line approach gives the height up to which ground thermals penetrate in the vertical. This height, denoted by MH that represents the actual ABL height, is 2-3 times larger than Hm when shallow convective clouds are present. In general both Hm and MH are 20-30% larger over Arabian Sea compares to that over Bay of Bengal. Comparison of surface convective available potential energy (CAPE) and equivalent potential temperature (θe) between normal and deficit monsoon years shows that convective instability was as large in deficit years. This means that dynamic and not thermodynamics, controlled the occurrence of convection.

Une approche donnant de meilleurs résultats pour les potentiels interatomiques en apprentissage-machine à la volée est proposée en comparant trois approches pour la recherche de processus activés par la technique d'activation-relaxation. Tout d'abord, nous discutons de l'intérêt et des enjeux de l'utilisation des potentiels en apprentissage-machine et justifions l'utilisation de l'apprentissage à la volée pour la recherche de processus activés. Cela nous mène à présenter la forme générale des potentiels en apprentissage-machine, quelques modèles via leurs descripteurs de configuration atomique, paramètres et hyperparamètres ainsi que la méthode de l'apprentissage à la volée. Ensuite, nous présentons les méthodes d'exploration utilisées et les détails d'intégration du potentiel à la volée. Enfin, nous menons une étude comparative des trois approches pour un système de Si et de SiGe avec diffusion de lacune. La méthodologie proposée de potentiel de haute précision permet d'étendre la gamme de problèmes pouvant être étudiés par la technique d'activation-relaxation. / An approach giving better results for on-the-fly machine learning interatomic potential proposed by comparing three approaches for exploration of activated processes by the activationrelaxation technique. We first discuss the interest and challenges of on-the-fly machine learning potential and justify the use of on-the-fly learning for the search for activated processes. This leads us to present the general form of machine learning potentials and some models via their atomic configuration descriptors, parameters and hyperparameters as well as the on-the-fly learning method. Then, the exploration methods used are defined and the details of the integration of the potential are presented. Finally, a study is conducted comparing the three approaches for a Si and SiGe system with vacancy diffusion. The proposed methodology of high-precision potential allows to extend the range of possible problems to be studied by the activation-relaxation technique.