Cette thèse est consacrée à l'étude de la méthode PAW (projector augmented-wave) et d'une de ses modifications, baptisée méthode PAW variationnelle (VPAW), pour le calcul de l'état fondamental d'Hamiltoniens en géométrie périodique. Ces méthodes visent à améliorer la vitesse de convergence des méthodes d'ondes planes (ou méthodes de Fourier) en appliquant une transformation inversible au problème aux valeurs propres initial agissant au voisinage de chaque site atomique. Cette transformation permet de capter une partie des difficultés dues aux singularités coulombiennes. La méthode VPAW est analysée pour un opérateur de Schr\"odinger unidimensionnel avec des potentiels de Dirac. Les fonctions propres de ce modèle comprennent des sauts de dérivées similaires aux cusps électroniques. Le saut de dérivée des fonctions propres du problème aux valeurs propres issu de la méthode VPAW est réduit de façon importante. Cela entraîne une accélération de convergence en ondes planes du calcul des valeurs propres corroborée par une étude numérique. Une étude de la méthode VPAW est conduite pour des Hamiltoniens 3D périodiques avec des singularités coulombiennes, parvenant à des conclusions similaires. Pour la méthode PAW, la transformation inversible comporte des sommes infinies qui sont tronquées en pratique. Ceci introduit une erreur, qui est rarement quantifiée en pratique. Elle est analysée dans le cas de l'opérateur de Schrödinger unidimensionnel avec des potentiels de Dirac. Des bornes sur la plus basse valeur propre en fonction des paramètres PAW sont prouvées conformes aux tests numériques. / This thesis is devoted to the study of the PAW method (projector augmented-wave) and of a variant called the variational PAW method (VPAW). These methods aim to accelerate the convergence of plane-wave methods in electronic structure calculations. They rely on an invertible transformation applied to the eigenvalue problem, which acts in a neighborhood of each atomic site. The transformation captures some difficulties caused by the Coulomb singularities. The VPAW method is applied to a periodic one-dimensional Schr\"odinger operator with Dirac potentials and analyzed in this setting. Eigenfunctions of this model have derivative jumps similar to the electronic cusps. The derivative jumps of eigenfunctions of the VPAW eigenvalue problem are significantly reduced. Hence, a smaller plane-wave cut-off is required for a given accuracy level. The study of the VPAW method is also carried out for 3D periodic Hamiltonians with Coulomb singularities yielding similar results. In the PAW method, the invertible transformation has infinite sums that are truncated in practice. The induced error is analyzed in the case of the periodic one-dimensional Schrödinger operator with Dirac potentials. Error bounds on the lowest eigenvalue are proved depending on the PAW parameters.

Quantum mechanics became a foundation for incessant development of versatile computational methods for analysis of chemical and physical properties of molecules and crystals. A huge progress has been made in the fifield of density functional theory, since nowadays this theory offers the best compromise between precision of results and efficiency fiof computation. The chemical bonding analysis can be easily performed with real space methods based on chemical concepts introduced via partitioning of real space into chemically meaningful domains, since the orbital based approach is not well applicable due to the delocalized nature of plane waves. However the practical usage of those methods often requires a signifificant amount of computational resources. Some methods require the evaluation of so called domain overlap matrices, that is a formidable task for complex and low-symmetry systems. In the present research the author enables the investigation of complex solid compounds with real space chemical bonding indicators by introducing the derivation of the expression for the evaluation of the domain overlap matrix elements from the projected-augmented wave method. The corresponding program module was developed, which is capable to perform the real space chemical bonding analysis with a number of methods, like electron localizability indicators, electron localization function, localization/delocalization indices and domain averaged Fermi hole orbitals. The efficiency and the accuracy of the developed implementation is demonstrated by the comparison with the domain overlap matrix elements evaluation from the full-potential linearized augmented plane wave method on a set of simple compounds with three atoms per primitive cell at most. A set of complex periodic structures is analyzed and the capability of the present implementation to unravel intricate chemical bonding patterns is demonstrated.

Quantum mechanics became a foundation for incessant development of versatile computational methods for analysis of chemical and physical properties of molecules and crystals. A huge progress has been made in the fifield of density functional theory, since nowadays this theory offers the best compromise between precision of results and efficiency fiof computation. The chemical bonding analysis can be easily performed with real space methods based on chemical concepts introduced via partitioning of real space into chemically meaningful domains, since the orbital based approach is not well applicable due to the delocalized nature of plane waves. However the practical usage of those methods often requires a signifificant amount of computational resources. Some methods require the evaluation of so called domain overlap matrices, that is a formidable task for complex and low-symmetry systems. In the present research the author enables the investigation of complex solid compounds with real space chemical bonding indicators by introducing the derivation of the expression for the evaluation of the domain overlap matrix elements from the projected-augmented wave method. The corresponding program module was developed, which is capable to perform the real space chemical bonding analysis with a number of methods, like electron localizability indicators, electron localization function, localization/delocalization indices and domain averaged Fermi hole orbitals. The efficiency and the accuracy of the developed implementation is demonstrated by the comparison with the domain overlap matrix elements evaluation from the full-potential linearized augmented plane wave method on a set of simple compounds with three atoms per primitive cell at most. A set of complex periodic structures is analyzed and the capability of the present implementation to unravel intricate chemical bonding patterns is demonstrated.