This thesis combines solid-state nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), chemical synthesis, isotopic enrichment and density-functional theory (DFT) calculations to provide insight into a number of microporous materials. The first class of materials studied is metal-organic frameworks (MOFs), where the presence of paramagnetic ions has a range of effects on the ¹³C NMR spectra, depending on the nature of the ligand-metal interactions. For the Cu²⁺-based MOFs, HKUST-1 and STAM-1, the assignment of the NMR spectra is non-intuitive, and unambiguous assignment requires specific ¹³C labelling of the organic linker species. It is shown that ¹³C NMR spectra of these two MOFs could act as a sensitive probe of the nature of “guest” molecules bound to the Cu²⁺. The second class of materials is aluminophosphates (AlPOs). It is shown that, using a series of relatively simple linear relationships with the crystal structure, the NMR parameters calculated by DFT (with calculation times of several hours) can be predicted, often with experimentally-useful accuracy, in a matter of seconds using the DIStortion analysis COde (DISCO), which is introduced here. The ambient hydration of the AlPO, JDF-2, to AlPO-53(A) is shown to occur slowly, with incomplete hydration after ~3 months. The resulting AlPO-53(A) is disordered and some possible models for this disorder are investigated by DFT. The final class of materials is gallophosphates (GaPOs), particularly GaPO-34 and related materials. The two as-prepared forms of GaPO-34 are characterised by solid-state NMR, and their calcination investigated by TGA and in-situ powder XRD. An unusual dehydrofluorinated intermediate phase is isolated and characterised for the first time by solid-state NMR. The fully calcined material is shown to be stable under anhydrous conditions, but hydrates rapidly in air. The hydrated material is stable under ambient conditions, but collapses upon heating. Partial dehydration without collapse is achieved by gentle heating or room-temperature evacuation. The impurity phases, GaPO₄ berlinite and GaPO-X are investigated by solid-state NMR and, while the structure of GaPO-X remains unknown, much structural information is obtained.

Theoretical studies using the Kohn-Sham density functional formalism have been carried out to identify and investigate the stability of a variety of atomic clusters for their use in cluster assembled materials. The stable behavior found in a cluster system provides a way to classify inorganic clusters. The clusters in this study can be categorized in one of the following, jellium, all-metal aromatic, Zintl analogue or as a covalent metal-carbide. By understanding the electronic structure and ultimately the stable nature of a cluster first, it is proposed one can construct assemblies based on the stable cluster. The methodology presented is a viable way to design future nanomaterials with a variety of architectures and precise control over properties based on stable cluster motifs.

Le travail de thèse "Modification of the electronic structure of catalytic active metal centres upon adsorption of molecules : a XAS and XES study" porte sur l'étude de la structure électronique des métaux de transition utilisés dans les catalyseurs par les techniques spectroscopiques d'absorption et d'émission de rayons durs (rayonnement synchrotron). Il s'agit, en particulier, d'utiliser les avancées dans les techniques spectroscopiques des rayons X pour l'étude des matériaux nanostructurés en conditions in situ. Le premier chapitre de la thèse, "X-Ray Spectroscopy: an Overview", présente brièvement les techniques spectroscopiques disponibles sur la ligne de lumière ID26 de l'Installation Européenne de Rayonnement Synchrotron (en anglais European Synchrotron Radiation Facility (ESRF), Grenoble), où toutes les mesures présentées dans ce travail ont été effectuées. Dans le deuxième chapitre, "Study of the Electronic structure of the Ti-sites in TS-1 using X-ray spectroscopy", est décrite la caractérisation électronique des centres de Ti en TS-1, qui est un important catalyseur, employé dans de nombreuses usines à travers le monde. Nous montrons que la combinaison des techniques spectroscopiques d'absorption et d'émission des rayons avec des calculs de mécanique quantique permet d'obtenir des informations importantes sur la structure électronique des centres de Ti dans des conditions in situ. Le troisième chapitre, “Identification of the Ti-Ligands in a Silica Supported Ziegler-Natta Catalyst by X-Ray Emission Spectroscopy", présente l'étude d'un catalyseur (une variante du catalyseur Ziegler-Natta), qui affiche un degré élevé/important de désordre chimique. L'utilisation de la théorie fonctionnelle de la densité des états (DFT) pour l'interprétation des données expérimentales a permis de développer des modèles possibles pour l'environnement d'un ligand Ti. Le quatrième chapitre, "Observing the dd-Excitations in CPO-27-Ni using Resonant Inelastic X-ray Scattering", conclut la partie principale de la thèse. Il présente un exemple d'utilisation de la diffusion inélastique des rayons X (RIXS) en chimie pour la détermination des excitations du champ cristallin des ions Ni dans l'oxyde de nickel et d'une cage organique autour d'un Ni métallique (CPO-27-Ni). Le chapitre explique brièvement les différentes approches théoriques qui peuvent être utilisées pour l'interprétation des caractéristiques spectrales. De plus, l'adsorption de molécules sonde, comme le CO sur les centres de Ni en CPO-27-Ni, est discutée sur la base des données expérimentales RIXS. Le dernier chapitre synthétise les résultats obtenus et indique des perspectives futures. Enfin, dans les annexes sont reportés les dispositifs expérimentaux développés dans le cadre du travail de thèse pour des mesures résolues en temps, ainsi que le curriculum vitae et les publications du candidat. / The purpose of this research project was to apply advanced X-ray based spectroscopic techniques for investigating the electronic structure of transition metals within catalysts and molecular sieves under in-situ conditions. Thus, the first chapter of the thesis, "X-Ray Spectroscopy: an Overview " briefly presents the spectroscopic techniques available at ID26, beamline of the European Synchrotron Radiation Facility (Grenoble) where all the measurements reported in this work have been obtained. In the second chapter, "Study of the Electronic structure of the Ti-sites in TS-1 using hard X-ray spectroscopy", it is reported the electronic characterization of the Ti centres in titanium silicalite-1 (TS-1), that is a relevant catalyst employed in industrial plants worldwide. The chapter shows that the combination of X-ray absorption and X-ray emission spectroscopy with quantum mechanical calculations is effective to obtain important insights on the electronic structure of the Ti-centres under in-situ conditions. The third chapter entitled “Identification of the Ti-Ligands in Silica Supported Ziegler-Natta Catalyst by X- Ray Emission Spectroscopy" presents the study of a variant of the Ziegler-Natta catalyst. The chapter discusses the interpretation of the valence emission lines within the theoretical framework provided by the density functional theory (DFT) and proposes possible models for the Ti-ligand-environment. The fourth chapter, entitled "Observing the dd-Excitations in CPO-27-Ni using Resonant Inelastic X-ray Scattering", concludes the main part of the thesis. It presents the application of resonant inelastic X-ray scattering (RIXS) for obtaining the crystal field excitations of the Ni ions within nickel oxide and within a Ni- metal-organic-framework (CPO-27-Ni). The chapter briefly describes the different theoretical approaches that can be used for the interpretation of the spectral features and discusses the adsorption of probe molecules like H2O, CO and H2S on the Ni centres of CPO-27-Ni. The last chapter (Chapter five) drawn a series of conclusions concerning the performed investigations and indicates possible future research directions. In Appendix A entitled "Pump and Probe Time Resolved Experiments at ID26" it is reported the description of the experimental setup co-developed and co-realized by the candidate for time resolved experiments. The appendix also accounts for the scientific outcome of the performed pump and probe measurements. The curriculum vitae and the publications list of the candidate are respectively reported in Appendix B and C.

Zeolites have been widely used in many different fields including catalysis, adsorption and separation, ion exchange, or gas storage. Conventional zeolites have three- dimensional (3D) structures with microporous channel system; typical pore sizes are well below 1 nanometer, therefore, diffusion limitation plays important role in many process and bulkier reactants (or products) cannot enter (or leave) the zeolite channel system. Two-dimensional (2D) zeolites prepared in last years can lift all diffusion limitation and they thus offer a very attractive alternative to conventional 3D zeolites. 2D zeolites attracted considerable attention on the experimental side; however, understanding of 2D zeolites based on computational investigation or on a combination of experimental and computational investigation is limited. A motivation for the computational work presented here is to improve our understanding of properties of 2D zeolites based on computational investigation. The originality of the research presented herein is in the strategy: we carried out systematic investigation of properties of corresponding 2D and 3D zeolites and we focus on the identification of similarities and differences. The most important zeolite properties, i.e., presence of Brønsted and Lewis acid sites, are investigated. A number of...

Nesta dissertação, estudamos cadeias unidimensionais antiferromagnéticas de spins 1/2 modeladas pelo Hamiltoniano de Heisenberg na presença de inomogeneidades causadas principalmente pela introdução de ligações substitucionais (defeitos nas ligações) e por efeitos de borda. Interessados então em determinar a energia do estado fundamental de sistemas com quaisquer distribuições das ligações, utilizamos o formalismo da Teoria do Funcional da Densidade (DFT) desenvolvido para o modelo de Heisenberg. O formalismo da DFT permite a estimativa da energia do estado fundamental de sistemas não-homogêneos conhecendo-se o sistema homogêneo. Construímos funcionais na aproximação da ligação local (LBA), proposta recentemente em analogia à já conhecida LSA (aproximação local para o spin). A obtenção dos funcionais se baseou no estudo do modelo de uma cadeia de spins em que as ligações são alternadas, isto é, a interação de troca se alterna em valor de sítio para sítio. Isso originou um funcional não-local na interação de troca da cadeia. Apesar disso, continuamos utilizando a nomenclatura LBA. Todos os resultados fornecidos pelos funcionais são comparados a dados provenientes de diagonalização numérica exata. / In this dissertation, we use the Heisenberg model to describe inhomogeneous antiferromagnetic spin 1/2 chains. The translational invariance is broken mainly due to the non-uniform distribution of bond interactions (defects) and the presence of boundaries. Interested in obtaining the ground-state energy of systems with any distribution of exchange couplings (Jij), we use the density-functional theory (DFT) formalism, developed for the Heisenberg model. The DFT formalism allows an estimate of the ground-state energy of inhomogeneous systems based on the homogeneous systems. We build functionals for the ground-state energy using a local bond approximation (LBA), recently proposed in analogy to the already known LSA (local spin approximation). To obtain the functionals we studied a model that describes an alternating chain, in which the exchange coupling alternates from site-to-site. This resulted in non-local functionals on the spin-spin exchange interaction. Nevertheless, we still call them LBA functionals. All the results from the functionals are compared with exact numerical data.

O efeito Hall quântico surge em gases de elétrons bidimensionais (2DEG) na presença de altos campos magnéticos B. O campo magnético quantiza o movimento planar dos elétrons em órbitas ciclotrônicas caracterizadas pelos níveis de Landau. Neste regime a resistividade transversal (ou Hall) ρxy em função de B exibe platôs em submúltiplos inteiros de e2/h, i.e., ρxy = ν-1 e2/h, sendo ν o fator de preenchimento dos níveis de Landau. Por sua vez, a resistividade longitudinal ρxx apresenta picos nas transições entre platôs de ρxy. Em primeira instância, ρxx é uma medida indireta da densidade de estados no nível de Fermi g(εF), e os picos dos mesmos indicam cruzamentos do nível de Fermi εF com niveis de Landau. Assim, o diagrama de densidade de elétrons n2D e B dos picos de ρxx ~ g(εF) fornece um mapa topológico da estrutura eletrônica do sistema. Em sistemas de duas subbandas, ρxx(n2D, B) exibe estruturas em forma de anel devido a cruzamentos de níveis de Landau de subbandas distintas [experimentos do grupo do Prof. Jiang (UCLA)]. Estes cruzamentos podem ainda levar a instabilidades ferromagnéticas. Investigamos estas instabilidades usando a teoria do funcional da densidade (DFT) para o cálculo da estrutura eletrônica, e o modelo de Ando (formalismo de Kubo) para o cálculo de ρxx e ρxy. Para temperaturas mais altas (340 mK) obtemos as estruturas em forma de anel em ρxx. Para temperaturas mais baixas (70 mK), observamos uma quebra dos anéis devido a transições de fase ferromagnéticas. Variando-se o ângulo θ de B com relação ao 2DEG observa-se o encolhimento do anel. Nossos resultados mostram que o ângulo de colapso total do anel depende de uma competição entre o termo de troca da interação de Coulomb (princípio de Pauli) e cruzamentos evitados devido ao ângulo θ finito. As transições de fase exibem ainda o fenômeno de histerese. Na região de instabilidade ferromagnética obtemos diferentes soluções variando B de forma crescente ou decrescente. Estas soluções possuem energias total diferentes, de forma que representam estados fundamental e excitado de muitos corpos. Esta observação, juntamente com resultados anteriores do grupo [Freire & Egues (2007)], representam as primeiras realizações teóricas da previsão da possibilidade de estados excitados como mínimos locais do funcional de energia do estado fundamental [Perdew & Levy (1985)]. O modelo aqui proposto fornece excelente acordo com os experimentos considerados. Adicionalmente, a observação sistemática e experimentalmente verificada dos estados excitados valida as previsões de Perdew & Levy. Aplicamos ainda estas mesmas ideias no cálculo da estrutura eletrônica e condutância de fios quânticos na presença de campos magnéticos, mostrando que cruzamentos de modos transversais também exibem instabilidades ferromagnéticas observadas em experimentos recentes [Dissertação de Mestrado de Filipe Sammarco, IFSC/USP], fortalecendo a validade do modelo apresentado nesta tese. / The quantum Hall effect arises in two dimensional electron gases (2DEG) under high magnetic fields B. The magnetic field quantizes the planar motion of the electrons into cyclotron orbits given by the Landau levels. In this regime the transversal (Hall) resistivity ρxy shows plateaus as a function of B at integer sub-multiples of e2/h, i.e., ρxy = ν-1 e2/h, where n is the filling factor of the Landau levels. The longitudinal resistivity ρxx shows peaks at the transition between the plateaus of ρxy. In principle, ρxx is an indirect measure of the density of states at the Fermi level g(εF), so that the peaks indicate when the Fermi level εF crosses a Landau level. Therefore, a density-B-field diagram n2D-B of the ρxx ~ g(εF) peaks shows a topological map of the electronic structure of the system. In two-subband systems, ρxx( n2D, B) shows ringlike structures due to crossings of spin-split Landau levels from distinct subbands [experiments from the group of Prof. Jiang (UCLA)] that could lead to ferromagnetic instabilities. We study these instabilities using the density functional theory (DFT) to calculate the electronic structure, and Ando\'s model (Kubo formalism) for ρxx and ρxy. At higher temperatures (340 mK) we also obtain the ringlike structures in ρxx. At lower temperatures (70 mK) we see broken rings due to quantum Hall ferromagnetic phase transitions. Tilting B by theta with respect to the 2DEG normal we find that the ring structure shrinks. Our results show that the angle of full collapse depends on a competition between the exchange term from the Coulomb interaction (Pauli principle) and the anticrossing of Landau levels due to the finite angle theta. Additionally, at the instabilities we observe hysteresis. Sweeping the B field up or down near these regions we obtain two different solutions with distinct total energies, corresponding to the ground state and an excited state of the many-body system. This result, together with previous results of our group [Freire & Egues (2007)], are the first realizations of the theoretical prediction of the possibility of excited states as local minima of the ground state energy functional [Perdew & Levy (1985)]. The model proposed here shows an excellent agreement with the experiments. Additionally, the systematic and experimentally verified observation of excited states corroborates the predictions of Perdew & Levy. Similar ideas as presented here when applied to the electronic structure and conductance of quantum wires with an in-plane magnetic field show ferromagnetic instabilities at crossings of the wire transverse modes [Master Thesis of Filipe Sammarco, IFSC/USP], also with excellent experimental agreement. This strengthen the range of validity of the model proposed in this Thesis.

Simulações de propriedades de estrutura eletrônica possuem fundamental importância para a física do estado sólido e química quântica. A teoria do funcional da densidade (DFT) é atualmente o método de estrutura eletrônica mais empregado, desde escalas atômicas e nanoscópicas até aglomerados biomoleculares. A acurácia da DFT depende essencialmente de aproximações para os efeitos de troca e correlação, para as quais existem vínculos a serem satisfeitos como forma de controlar sua construção. Esse é um tópico de grande importância, pois a construção de melhores funcionais é necessária para uma descrição cada vez mais precisa dos efeitos de muitos corpos na DFT. No presente trabalho, investigamos o comportamento da energia de troca e correlação e o desenvolvimento de funcionais aproximados sob a ótica de um vínculo universal de sistemas de interação Coulombiana, o limite inferior de Lieb-Oxford. Primeiramente apresentamos evidências de que em diversas classes de sistemas a energia de troca e correlação é distante do limite de Lieb-Oxford. A redução do limite foi implementada nos funcionais Perdew-Burke-Erzenhof (PBE), porém a forma com que o vínculo é implementado apenas aumentou a energia de troca. Propusemos em seguida que o limite de Lieb-Oxford não fosse utilizado apenas para determinar o valor de um parâmetro, como em PBE, mas que fosse ponto-de-partida de uma nova forma família de funcionais, do tipo hiper-GGA. Exploramos uma construção não-empírica, com implementação pós-autoconsistente. A particular forma proposta se beneficiou da redução do limite Lieb-Oxford, obtendo resultados satisfatórios para as energias de correlação. / Electronic-structure calculations play a fundamental role in solid-state physics and quantum chemistry. Density-functional theory (DFT) is today the most-widely used electronic-structure method, from atomic and nanoscopic scales to biomolecular aggregates. The accuracy of DFT depends essentially on approximations to the exchange and correlation energy, which are controlled by exact constraints. This is a very important issue, since the improvement of functionals is the key to a better description of many-body effects. In the present work, we investigate the exchange-correlation energy and approximate functionals from the viewpoint of an universal constraint on interacting Coulomb systems: the Lieb-Oxford lower bound. Initially we present evidence that for several classes of systems (atoms, ions, molecules and solids), the actual exchange-correlation energies are far from the Lieb-Oxford lower bound. A tighter form of this bound was conjectured; implemented in the Perdew-Burke-Erzenhof (PBE) functionals, and tested for atoms, molecules and solids. Finally, we propose to use the Lieb-Oxford bound not just to fix the value of a parameter as in PBE, but as a starting point for a new family of hyper-GGA functionals. For these, we explored a non-empirical construction, investigating its performance for atoms and small molecules post-selfconsistently. The particular HGGA proposed benefited from the tightening of the Lieb-Oxford bound and exhibited satisfactory correlation energies.

O uso de nanomateriais em aplicações como catálise e medicina, despertou nos últimos anos o interesse no estudo das propriedades de nanoclusters. O estudo das propriedades termodinâmicas desses sistemas é essencial, pois mudanças estruturais originadas de mudanças de fase podem alterar propriedades como atividade catalítica, momento magnético e propriedades óticas. A dinâmica molecular vêm sendo utilizada para o estudo computacional das propriedades termodinâmicas de diversos nanomateriais, enquanto o uso de métodos de Monte Carlo (MC), nesse contexto, tem se restringido ao estudo de nanoclusters de Lennard-Jones (LJ). Para avaliar a viabilidade do uso de métodos de MC no estudo de propriedades de sistemas reais, uma implementação do método Parallel Tempering Monte Carlo (PTMC) utilizando algoritmos do estado da arte para realização de trocas, determinação de temperaturas e ajuste de deslocamentos foi construída. Através de testes, é mostrado que alguns dos algoritmos implementados podem não ser adequados ao estudo do problema em questão. A implementação foi validada com o estudo das propriedades termodinâmicas de nanoclusters de LJ com 38, 55 e 147 átomos, que possuem resultados conhecidos na literatura. Além disso, resultados para propriedades do nanocluster LJ98 são apresentados, e devido à características estruturais desse sistema, é observada uma transição sólido-sólido entre as estruturas tetraédricas e icosaédricas em temperatura abaixo da de fusão. A hipótese do uso do algoritmo PTMC para o estudo de propriedades de materiais reais, foi testada nas nanoligas (PtCo)55 e (PtNi)55, descritas pelo potencial de Gupta. Através da comparação das estruturas de mais baixa energia com resultados de teoria do funcional da densidade (DFT, do inglês), é mostrado que o uso do potencial de Gupta pode ser justificado, dados os baixos desvios no comprimento de ligação (menores que 2.4%) e a semelhança de outras características estruturais. Os resultados obtidos indicam que o método PTMC é capaz de identificar as mudanças de fase das nanoligas estudadas. Essas mudanças são ilustradas e analisadas com o uso de um algoritmo para a comparação da similaridade de estruturas, com o qual foi possível analisar a fusão dos nanoclusters Co55, Ni55, Pt30Co25 e Pt40Ni15 (obtida em temperaturas entre 900 e 1100 K); além da fusão, a 727 K, e transição sólido-sólido, a 300 K, para a Pt55. Com as estruturas mais frequentes, encontradas através da análise de similaridade, e com a realização de cálculos DFT, foi possível observar um deslocamento do centro da banda d em direção ao HOMO (Highest Occupied Molecular Orbital) causado pelo aumento da temperatura. Esse deslocamento, segundo o modelo da banda d válido para superfícies, pode indicar uma maior reatividade dos nanoclusters nesses casos. / The use of nanomaterials in applications such as catalysis and medicine, aroused in the last years interest in studying properties of nanoclusters. The study of thermodynamic properties of these systems is essential, since structural changes originated from phase changes can alter properties such as catalytic activity, magnetic moment and optical properties. Molecular dynamics have been used for the computational study of thermodynamic properties of various nanomaterials, while the use of Monte Carlo methods (MC), in this context, has been restricted to the study of Lennard-Jones (LJ) nanoclusters. To evaluate the feasibility of using MC methods to study properties of real systems, an implementation of the Parallel Tempering Monte Carlo (PTMC) method using state of the art algorithms to perform exchanges, determine the temperature set and adjust the maximum displacement, was built. Through testing, it is shown that some of the implemented algorithms may not be suitable for the study of the problem in question. The implementation was validated by studying the thermodynamic properties of LJ nanoclusters with 38, 55 and 147 atoms, which have results known in the literature. In addition, results for the properties of the LJ98 nanocluster are reported, and due to the structural features of this system, a solid-solid transition between the tetrahedral and icosahedral structures in a temperature below melting is observed. The possibility of using the PTMC algorithm in the study of properties of real materials, is tested in the (PtCo)55 and (PtNi)55 nanoalloys, described by the Gupta potential. By comparing the lowest energy structures with density functional theory (DFT) results, it is shown that the use of the Gupta potential can be justified, given the small deviation in the bond lenght (less than 2.4%) and the similarity of other structural features. The results indicate that the PTMC method is able to identify the phase changes in the studied nanoalloys. These changes are illustrated and analyzed with the use of an algorithm for comparing the structure similarity, which made possible the analysis of the melting of the Co55, Ni55, Pt30Co25 e Pt40Ni15 nanoclusters (obtained at temperatures between 900 e 1100 K); and the melting at 727 K, and solid-solid transition at 300 K, for Pt55. With the most frequent structures, obtained by the similarity analysis, and through DFT calculations, it was possible to observe a shift in the d band center to the HOMO (Highest Occupied Molecular Orbital) caused by the temperature increase. This shift, following the d band model valid for surfaces, may indicate a higher reactivity of the nanocluster in these cases.

When doing computations on the negatively (positively) charged NV-center in diamond, the common procedure is to add (subtract) an electron from the system. However, when using periodic boundary conditions, this addition/subtraction of an electron from the supercell would result in a divergent electrostatic energy. So an artificial background jellium charge of opposite charge that compensate the electronic charge to make the supercell neutral is needed. This introduces further problems that needs corrections. And this method is especially problematic for slab supercells, as the compensating background charge leads to a dipole, which diverges as the vacuum between the slab images increases. An alternative, recently proposed way of charging the NV-center is to introduce electron donors/acceptors in the form of nitrogen/boron atoms (at substitutional sites in the diamond lattice). In this way, we keep the supercell/slab neutral, and avoid correction schemes. In this work we verify that the addition of a substitutional nitrogen atom indeed has the same effect on the NV-center as the more traditional method of adding an extra electron to the system. Further, we investigate the effects of 1. Adding two substitutional nitrogen atoms to the system (3 nitrogen atoms in total, neutral supercell), 2. Adding a substitutional nitrogen atom and an electron to the system (2 nitrogen atom in total, negatively charged supercell), 3. Adding two electrons to the system (1 nitrogen atom, doubly negatively charged supercell). Additionally, we investigate the addition of acceptor dopants (boron) in order to analyze the effect on the electronic structure of the NV-center and diamond.

No description available.