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The focus of this thesis is on C-O bonds activation by transition metal atoms. Lignin is a potential alternative energy resource, but currently is an underused biomass species because of its highly branched structure. To aid in better understanding this species, the oxidative cleavage of the Cβ-O bond in an archetypal arylglycerol β-aryl ether (β–O–4 Linkage) model compound of lignin with late 3d, 4d, and 5d metals was investigated. Methoxyethane was utilized as a model molecule to study the activation of the C-O bond. Binding enthalpies (ΔHb), enthalpy formations (ΔH) and activation enthalpies (ΔH‡) have been studied at 298K to learn the energetic properties in the C-O bond cleavage in methoxyethane. Density functional theory (DFT) has become a common choice for the transition metal containing systems. It is important to select suitable functionals for the target reactions, especially for systems with degeneracies that lead to static correlation effects. A set of 26 density functionals including eight GGA, six meta-GGA, six hybrid-GGA, and six hybrid-meta-GGA were applied in order to investigate the performance of different types of density functionals for transition metal catalyzed C-O bond cleavage. A CR-CCSD(T)/aug-cc-pVTZ was used to calibrate the performance of different density functionals.

Quantum chemistry methodologies can be used to address a wide variety of chemical problems. Key to the success of quantum chemistry methodologies, however, is the selection of suitable methodologies for specific problems of interest, which often requires significant assessment. To gauge a number of methodologies, the utility of density functionals (BLYP, B97D, TPSS, M06L, PBE0, B3LYP, M06, and TPSSh) in predicting reaction energetics was examined for model studies of C-O bond activation of methoxyethane and methanol. These species provide excellent representative examples of lignin degradation via C-O bond cleavage. PBE0, which performed better than other considered DFT functionals, was used to investigate late 3d (Fe, Co, and Ni), 4d (Ru, Rh, and Pd), and 5d (Re, Os, and Ir) transition metal atom mediated Cβ -O bond activation of the β–O–4 linkage of lignin. Additionally, the impact of the choice of DFT functionals, basis sets, implicit solvation models, and layered quantum chemical methods (i.e., ONIOM, Our Own N-layered Integrated molecular Orbital and molecular Mechanics) was investigated for the prediction of pKa for a set of Ni-group metal hydrides (M = Ni, Pd, and Pt) in acetonitrile. These investigations have provided insight about the utility of a number of theoretical methods in the computation of thermodynamic properties of transition metal hydrides in solution. As single reference wavefunction methods commonly perform poorly in describing molecular systems that involve bond-breaking and forming or electronic near-degeneracies and are typically best described with computationally costly multireference wavefunction-based methods, it is imperative to a priori analyze the multireference character for molecular systems so that the proper methodology choice is applied. In this work, diagnostic criteria for assessing the multireference character of 4d transition metal-containing molecules was investigated. Four diagnostics were considered in this work, including the weight of the leading configuration of the CASSCF wavefunction, C02; T1, the Frobenius norm of the coupled cluster amplitude vector related to single excitations and D1, the matrix norm of the coupled cluster amplitude vector arising from coupled cluster calculations; and the percent total atomization energy, %TAE. This work demonstrated the need to have different diagnostic criteria for 4d molecules than for main group molecules.

Magnetic ordering of dopants in diamond holds the prospect of exploiting diamond’s unique properties in the emerging field of spintronics. Several transition metal defects have been reported to order ferromagnetically in various semiconductors, however, low Curie temperatures and lack of other fundamental material properties have hindered practical implementation in room temperature spintronic applications. In this Thesis, we consider the energetic stability of 3d transition metal doped-diamond and its magnetic ordering properties at various lattice sites and charge states using ab initio Density Functional Theory methods. We find the majority of 3d transition metal impurities in diamond at any charge state to be energetically most stable at the divacancy site compared to substitutional or interstitial lattice sites, with the interstitial site being highly unstable (by ~8 - 10 eV compared to the divacancy site). At each lattice site and charge state, we find the formation energies of transition metals in the middle of the 3d series (Cr, Mn, Fe, Co, Ni) to be considerably lower compared to those early or late in the series. The energetic stability of transition metal impurities across the 3d series is shown to be strongly dependent on the position of the Fermi level in the diamond band gap, with the formation energies at any lattice site being lower in p-type or ntype diamond compared to intrinsic diamond. Further, we show that incorporation of isolated transition metal impurities into diamond introduces spin polarised impurity bands into the diamond band gap, while maintaining its semiconducting nature, with band gaps in both the spin-up and spin-down channels. These impurity bands are shown to originate mainly from s, p-d hybridization between carbon sp 3 orbitals with the 3d orbitals of the transition metal. In addition, the 4p orbitals contribute significantly to hybridization for transition metal atoms at the substitutional site, but not at the divacancy site. In both cases, the spin polarisation and magnetic stabilization energies are critically dependent on the lattice site and charge state of the transition metal impurity. By allowing magnetic interactions between transition metal atoms, we find that ferromagnetic ordering is likely to be achieved in divacancy Cr+2, Mn+2, Mn+1 and Co0 as well as in substitutional Fe+2 and Fe+1, indicating that transition metal-doped diamond is likely to form a diluted magnetic semiconductor which may successfully be considered for room temperature spintronic applications. In addition, these charge states correspond to p-type diamond, except for divacancy Co0, suggesting that co-doping with shallow acceptors such as B ( will result in an increase of charge concentration, which is likely to enhance mediation of ferromagnetic spin coupling. The highest magnetic stabilization energy occurs in substitutional Fe+1 (33.3 meV), which, also exhibits half metallic ferromagnetic ordering at the Fermi level, with an induced magnetic moment of 1.0 μB per ion, thus suggesting that 100 % spin polarisation may be achieved in Fe-doped diamond. / Physics / D. Litt. et Phil. (Physics)

A busca por grandes estruturas lineares em conjuntos de funções com propriedades pa-tológicas é um tópico que fora desenvolvido nos últimos vinte anos. Esse trabalho detalhaalguns desses resultados sobre lineabilidade e espaçabilidade de forma clara e diluida parafacilitar a introdução desses conceitos para um pesquisador não familiarizado.Veremos que os seguintes conjuntos são lineáveis: funçõesCnão analíticas, funçõescom apenas uma quantidade finita de pontos de continuidade, funções cujas derivadas sãoilimitadas num intervalo fechado, funções sobrejetoras em todo lugar que se anulam quasesempre. Também mostraremos a espaçabilidade dos seguintes conjuntos: funções de variaçãolimitada com um conjunto denso de descontinuidades em salto e funções Lebesgue integráveisem [0,1] não essencialmente limitadas em nenhum intervalo. Finalmente, veremos algunsresultados sobre a lineabilidade no conjunto dos funcionais lineares que atingem a norma. / Finding large linear structures in sets of functions with pathological properties is a topicthat has been developed in the last twenty years. This work details some of these resultsabout lineability and spaceability in a clear and diluted way to make the introduction ofthese concepts easier for an unfamiliar researcher.We show that the following sets are lineable:Cnon-analytic functions, functions witha finite number of points of continuity, functions whose derivative is unbounded on a closedinterval and everywhere surjective functions that are almost everywhere zero. We also showthe spaceability of the following sets: functions of bounded variation which have a denseset of jump discontinuities and Lebesgue integrable functions in [0,1] which are nowhereessentially bounded. At last, we show some results about lineability in the set of linearfunctionals that attain their norm.

En biologie, lorsqu'une quantité importante de phospholipides est insérée dans un milieu aqueux, ceux-Ci s'assemblent alors par paires pour former une bicouche, plus communément appelée vésicule. En 1973, Helfrich a proposé un modèle simple pour décrire la forme prise par une vésicule. Imposant la surface de la bicouche et le volume de fluide qu'elle contient, leur forme minimise une énergie élastique faisant intervenir des quantités géométriques comme la courbure, ainsi qu'une courbure spontanée mesurant l'asymétrie entre les deux couches. Les globules rouges sont des exemples de vésicules sur lesquels sont fixés un réseau de protéines jouant le rôle de squelette au sein de la membrane. Un des principaux travaux de la thèse fut d'introduire et étudier une condition de boule uniforme, notamment pour modéliser l'effet du squelette. Dans un premier temps, on cherche à minimiser l'énergie de Helfrich sans contrainte puis sous contrainte d'aire. Le cas d'une courbure spontanée nulle est connu sous le nom d'énergie de Willmore. Comme la sphère est un minimiseur global de l'énergie de Willmore, c'est un bon candidat pour être un minimiseur de l'énergie de Helfrich parmi les surfaces d'aire fixée. Notre première contribution dans cette thèse a été d'étudier son optimalité. On montre qu'en dehors d'un certain intervalle de paramètres, la sphère n'est plus un minimum global, ni même un minimum local. Par contre, elle est toujours un point critique. Ensuite, dans le cas de membranes à courbure spontanée négative, on se demande si la minimisation de l'énergie de Helfrich sous contrainte d'aire peut être effectuée en minimisant individuellement chaque terme. Cela nous conduit à minimiser la courbure moyenne totale sous contrainte d'aire et à déterminer si la sphère est la solution de ce problème. On montre que c'est le cas dans la classe des surfaces axisymétriques axiconvexes mais que ce n'est pas vrai en général.Enfin, lorsqu'une contrainte d'aire et de volume sont considérées simultanément, le minimiseur ne peut pas être une sphère qui n'est alors plus admissible. En utilisant le point de vue de l'optimisation de formes, la troisième et plus importante contribution de cette thèse est d'introduire une classe plus raisonnable de surfaces, pour laquelle l'existence d'un minimiseur suffisamment régulier est assurée pour des fonctionnelles et des contraintes générales faisant intervenir les propriétés d'ordre un et deux des surfaces. En s'inspirant de ce que fit Chenais en 1975 quand elle a considéré la propriété de cône uniforme, on considère les surfaces satisfaisant une condition de boule uniforme. On étudie d'abord des fonctionnelles purement géométriques puis nous autorisons la dépendance à travers la solution de problèmes aux limites elliptiques d'ordre deux posés sur le domaine intérieur à la surface / In biology, when a large amount of phospholipids is inserted in aqueous media, they immediatly gather in pairs to form bilayers also called vesicles. In 1973, Helfrich suggested a simple model to characterize the shapes of vesicles. Imposing the area of the bilayer and the volume of fluid it contains, their shape is minimizing a free-Bending energy involving geometric quantities like curvature, and also a spontanuous curvature measuring the asymmetry between the two layers. Red blood cells are typical examples of vesicles on which is fixed a network of proteins playing the role of a skeleton inside the membrane. One of the main work of this thesis is to introduce and study a uniform ball condition, in particular to model the effects of the skeleton. First, we minimize the Helfrich energy without constraint then with an area constraint. The case of zero spontaneous curvature is known as the Willmore energy. Since the sphere is the global minimizer of the Willmore energy, it is a good candidate to be a minimizer of the Helfrich energy among surfaces of prescribed area. Our first main contribution in this thesis was to study its optimality. We show that apart from a specific interval of parameters, the sphere is no more a global minimizer, neither a local minimizer. However, it is always a critical point. Then, in the specific case of membranes with negative spontaneous curvature, one can wonder whether the minimization of the Helfrich energy with an area constraint can be done by minimizing individually each term. This leads us to minimize total mean curvature with prescribed area and to determine if the sphere is a solution to this problem. We show that it is the case in the class of axisymmetric axiconvex surfaces but that it does not hold true in the general case. Finally, considering both area and volume constraints, the minimizer cannot be the sphere, which is no more admissible. Using the shape optimization point of view, the third main and most important contribution of this thesis is to introduce a more reasonable class of surfaces, in which the existence of an enough regular minimizer is ensured for general functionals and constraints involving the first- and second-Order geometric properties of surfaces. Inspired by what Chenais did in 1975 when she considered the uniform cone property, we consider surfaces satisfying a uniform ball condition. We first study purely geometric functionals then we allow a dependence through the solution of some second-Order elliptic boundary value problems posed on the inner domain enclosed by the shape

Xu, Xiao-ping. / "March 1999." / Thesis (Ph.D.)--Chinese University of Hong Kong, 1999. / Includes bibliographical references (p. 152-166). / Electronic reproduction. Hong Kong : Chinese University of Hong Kong, [2012] System requirements: Adobe Acrobat Reader. Available via World Wide Web. / Mode of access: World Wide Web. / Abstracts in English and Chinese.

Confinement effect on semiconductor nanowires properties. Alexis Nduwimana 100 pages Directed by Dr. Mei-Yin Chou We study the effect of confinement on various properties of semiconductor nanowires. First, we study the size and direction dependence of the band gap of germanium nanowires. We use the density functional theory in the local density approximation. Results shows that the band gap decreases with the diameter The susceptibility of these nanowires is also computed. Second, we look at the confinement effect on the piezoelectric coefficients of ZnO and AlN nanowires. The Berry phase method is used. It is found that depending on passivation, thepiezoelectric effect can decrease or increase. Finally, we study the size and direction dependence of the melting temperature of silicon nanowires. We use the molecular dynamics with the Stillinger Weber potential. Results indicate that the melting temperature increases with the nanowire diameter and that it is direction dependent.

Cette thèse porte sur les fondations de la théorie des préférences et de l'utilité utilisée dans les domaines du choix social et de la théorie de la décision. Le premier chapitre est l'introduction. Le second chapitre est composé d'une revue de la littérature et des résultats existants, d'une discussion des motivations pour envisager un nouveau cadre théorique permettant de combiner différentes approches de l'agrégation des préférences individuelles, et d'une proposition d'un modèle hybride appelé modèle de préférence-approbation. Le troisième chapitre pose la question du sens que l'on peut donner au consensus dans un tel cadre théorique. Pour y répondre, ce travail fournit une approche basée sur la notion de distance, c'est-à-dire d'une métrique définie sur le domaine des préférence-approbations, et examine différentes façons de mesurer l'homogénéité au sein d'un ensemble d'opinions individuelles. Dans cette nouvelle modélisation des opinions, les individus s'expriment à la fois à travers un classement défini sur l'ensemble des alternatives et par un niveau de seuil, permettant de distinguer dans ce classement les alternatives "approuvées" de celles qui sont "désapprouvées". Le quatrième chapitre comporte une analyse de la manipulabilité des règles d'agrégation définies sur un profil de votes composés de classements et d'évaluations binaires. En introduisant une nouvelle notion de non-manipulabilité, cette étude offre un résultat de possibilité, ainsi que certaines caractérisations d'impossibilités. La conclusion permet de discuter plusieurs questions de recherche future sur la manière de définir de nouveaux systèmes d'élections et mécanismes de votes, ainsi que leurs impacts potentiels sur la société.

Fuel cells have the potential to change the energy paradigm by allowing more efficient use of energy. In particular, Polymer Electrolyte Membrane Fuel Cells (PEMFC) are interesting because they are low temperature devices. However, there are still numerous challenges limiting their widespread use including operating temperature, types of permissible fuels and optimal use of expensive catalysts. The first two problems are related mainly to the ionomer electrolyte, which largely determines the operating temperature and fuel type. While new ionomer membranes have been proposed to address some of these issues, there is still a lack of fundamental knowledge to guide ionomer design for PEMFC. This work is a computational study of the effect of temperature and water content on sulfonated poly(ether ether ketone) and the effect of acidity on sulfonated polystyrene to better understand how ionomer material properties differ. In particular we found that increased water content preferentially solvates the sulfonate groups and improves water and hydronium transport. However, we found that increasing an ionomer’s acid strength causes similar effects to increasing the water content. Finally, we used Density Functional Theory (DFT) to study platinum nano-clusters as used in PEMFCs. We developed a model using the atom’s coordination number to quickly compute the energy of a cluster and therefore predict which platinum atoms are most loosely held. Our model correctly predicted the energy of various clusters compared to DFT. Also, we studied the interaction between the various moieties of the electrolyte including the catalyst particle and developed a force field. The coordination model can be used in a molecular dynamics simulation of the three phase region of a PEMFC to generate unbiased initial clusters. The force field developed can be used to describe the interaction between this generated cluster and the electrolyte.