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This work presents a crystal chemistry study of seven compounds grouped into three classes: isoxazoles, pyrazoles and pyrazolines here called IPISOX, PRISOX, 4D, OCISOX, C90, B07 e 13B, in order to identify novel acetylcholinesterase inhibitors. The structures of the listed compounds were determined by X-ray diffraction method using monocrystalline samples of the aforementioned substances. The disagreement rates seen between the model and the model defined by the diffraction pattern were: 0.0708; 0.0399; 0.0513; 0.0562; 0.0726; 0.0519; 0.0457 to IPISOX, PRISOX, OCISOX, 4D, B07, 13B e C90, respectively. A appendix refers to several methods involved in the process of recrystallization was attached to work, since it received 13 of the 16 substances to study were improperly to be subjected to the technique of Xray diffraction. To obtain factors responsible for the stability of the lens system were carried Closed Layer Interactions Analysis (ICF). The average values of delocalized electron energies determined in kcal.mol-1 were: 19.00 (IPISOX) ; 23.00 (PRISOX) ; 12.00 (OCISOX and B07) ; 9.00 (4D) ; 6,00 (13B) and 5.00 (C90) . Such relocations are from electronic transitions of the type n * (donor receiver). Other electronic relocation of C-N *O-H and C-H *O-H were also observed for some compounds. However, the first mentioned are relevant to the stability of the electron lens packaging. / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Este trabalho apresenta um estudo cristaloquímico de sete compostos agrupados em três classes: isoxazóis, pirazóis e pirazolinas aqui denominados de IPISOX, PRISOX, 4D, OCISOX, C90, B07 e 13B, no intuito de identificar novos inibidores da Acetilcolinesterase. As estruturas dos compostos mencionados foram determinadas por método de difração de Raios X usando amostras monocristalinas das substâncias mencionadas anteriormente. Os índices de discordância verificado entre o modelo proposto e o modelo definido pelo padrão de difração foram: 0,0708; 0,0399; 0,0513; 0,0562; 0,0726; 0,0519; 0,0457 para IPISOX, PRISOX, OCISOX, 4D, B07, 13B e C90, respectivamente. Um apêndice referente aos diversos métodos envolvidos no processo de recristalização foi anexado ao trabalho, uma vez que 13 das 16 substâncias recebidas para estudo estavam em forma inadequada para serem submetidas à técnica de difração de raios X. Visando obter fatores responsáveis pela estabilidade do sistema cristalino foram realizadas Análises de Interações de Camada Fechada (ICF). Os valores médios das energias de deslocalização eletrônica determinados, em kcal.mol-1, foram: 19,00 kcal.mol-1 (IPISOX); 23,00 (PRISOX); 12,00 (OCISOX E B07); 9,00 (4D); 6,00 (13B) E 5,00 (C90). Tais deslocalizações são oriundas de transições eletrônicas do tipo n * (doador receptor). Outras deslocalizações eletrônicas do tipo C-N *O-H e C-H *O-H também foram observadas para alguns compostos. No entanto, as primeiras mencionadas são relevantes para a estabilidade eletrônica do empacotamento cristalino.

In 2010 high harmonic generation (HHG) in solids was first observed where high order harmonics of a strong laser field's frequency were observed. HHG in solids is now a rapidly developing field that allows for exciting applications like fully solid state attosecond XUV sources and new ultrafast resolution imaging techniques for quantum dynamics in solids. HHG in solids has been explained by two mechanisms: an interband mechanism, due to polarization associated with separate energy bands, and an intraband mechanism that results from nonlinearities and population changes associated with each individual band. While interband HHG has been seen in wide bandwidth semiconductors, intraband HHG has been observed in narrow bandwidth dielectrics. There has not yet been an explanation of the alternation of mechanisms with material differences. The main goal of this thesis is to attempt to provide a better understanding of the most important mechanisms and where they prevail. Although numerical modelling of HHG requires consideration of multiple energy bands, a two-band model consisting only of a valence band and a single conduction band can explain the most important mechanisms. This model requires a given material's band gap between its valence and conduction bands as well as dipole matrix elements between the bands. In this thesis we follow the Kronig-Penney model to develop a 1D delta-function potential model of solids to obtain these properties required of the two-band model. We implement this in a Wannier quasi-classical (WQC) model of interband HHG in semiconductors that explains the dominant dynamics leading to such through quasi-classical real space electron-hole pair trajectories. Although HHG in solids can be explained to be the result of a resonant process in which an electron-hole pair is generated in the first step, there are also virtual transition processes that lack consideration. These processes do not conserve energy and correspond to transitions to conduction bands resulting from field induced distortions of the ground state. We use methodology introduced by Keldysh for optical field ionization of atoms and solids along with the 1D delta-function potential model to quantify how both resonant and virtual transitions lead to HHG in solids for wide and low bandwidth solids.

This study reports on the physical and optical characterization of scandium oxide thin films. Thin films of scandium oxide, 20-40 nm thick, were deposited on silicon wafers, quartz slides, and silicon photodiodes by reactively sputtering scandium in an oxygen environment. These samples were characterized using ellipsometry, high-resolution transmission electron microscopy, scanning transmission electron microscopy, and energy dispersive x-ray analysis. A 28.46 nm thick scandium oxide thin film was measured in the Extreme Ultraviolet (EUV) from 2.7 to 50 nm (459.3 to 24.8 eV) using synchrotron radiation at the Advanced Light Source Beamline 6.3.2 at the Lawrence Berkeley National Laboratory. In these measurements, a new method for data collection was used, in which the reflection and transmission data were collected simultaneously. Analysis of the EUV reflection and transmission data was performed using a front-side reflection, matrix-multiplication technique, which is novel among EUV analytical practice. During data analysis, a new weighting scheme was used, named "adaptive weighting". This analysis provides the first experimentally determined optical constants n and k for scandium oxide thin films from 4.5-30 nm. Also, the positions of the L2 and L3 electronic transitions of scandium oxide have been measured, at 3.069 and 3.101 nm (404.0 and 399.9 eV), respectively, while the measurements near the M transition suggest it to be at approximately 31.5 nm (39.4 eV). Comparing the electronic transition positions of scandium oxide to those of scandium show that the oxidation of scandium shifts the positions to lower energies. For L2 the shift is about 1.8 eV, for L3 the shift is about 1.4 eV, and for M the shift is about 1.9 eV. The binding energies of scandium oxide are greater than those of scandium, as is expected for an oxide compared to its parent metal. This trend in the shift of the transition positions is unexpected, and warrants further investigation.

The size and conformational complexity of proteins and other large systems represent major challenges for today's methods of quantum chemistry.This thesis is centered around the development of new computational tools to gain molecular-level insight into electronic transitions in such systems. To meet this challenge, we focus on the polarizable embedding (PE) model, which takes advantage of the fact that many electronic transitions are localized to a smaller part of the entire system.This motivates a partitioning of the large system into two regions that are treated at different levels of theory:The smaller part directly involved in the electronic process is described using accurate quantum-chemical methods, while the effects of the rest of the system, the environment, are incorporated into the Hamiltonian of the quantum region in an effective manner. This thesis presents extensions of the PE model with theaim of expanding its range of applicability to describe electronic transitions in large molecular systemsin the optical and X-ray regions. The developments cover both improvements with regardto the quantum region as well as the embedding potential representing the environment.Regarding the former, a damped linear response formulation has been implemented to allow for calculations of absorption spectra of large molecular systems acrossthe entire frequency range. A special feature of this development is its abilityto address core excitations that are otherwise not easily accessible.Another important development presented in this thesis is the coupling of the PE model to a multi-configuration self-consistent-field description of the quantum region and its further combination with response theory. In essence, this extends the PE model to the study of electronic transitions in large systems that are prone to static correlation --- a situation that is frequently encountered in biological systems. In addition to the direct environmental effects on the electronic structure of the quantum region, another important component of the description of electronic transitions in large molecular systems is an accurate account of the indirect effects of the environment, i.e., the geometrical distortions in the quantum region imposed by the environment. In thisthesis we have taken the first step toward the inclusion of geometry distortions in the PE frameworkby formulating and implementing molecular gradients for the quantum region. To identify critical points related to the environment description, we perform a theoretical analysis of the PE model starting from a full quantum-mechanicaltreatment of a composite system. Based on this, we present strategies for an accurate yet efficient construction of the embedding potentialcovering both the calculation of ground state and transition properties. The accurate representation of the environment makes it possible to reduce the size of the quantum region without compromising the overall accuracy of the final results. This further enables use of highly accurate quantum-chemical methods despite their unfavorable scaling with the size of the system. Finally, some examples of applications will be presented to demonstrate how the PE model may be applied as a tool to gain insight into and rationalize the factors influencing electronic transitions in large molecular systems of increasing complexity. / <p>The dissertation was awarded the best PhD thesis prize 2016 by the Danish Academy of Natural Sciences.</p><p></p><p>QC 20170209</p>

The discovery of superconductivity in iron-based pnictides in 2008 gave rise to a high advance in the research of high-temperature superconductors. But up to now there is no generally admitted theory of the non-BCS mechanism of these superconductors. The electron and hole doped Ba122 (BaFe2As2) compounds investigated in this thesis are supposed to be suitable model systems for studying the electronic behavior in order to shed light on the superconducting mechanisms. The 3d-transiton metal doped Ba122 compounds are investigated using the X-ray photoelectron spectroscopy (XPS), X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy (XES) and X-ray magnetic circular dichroism (XMCD), while the completely hole doped K122 is observed using XPS. The experimental measurements are complemented by theoretical calculations. A further new class of superconductors is represented by the electride 12CaO*7Al2O3: Here superconductivity can be realized by electrons accommodated in the crystallographic sub-nanometer-sized cavities, while the mother compound is a wide band gap insulator. Electronic structure investigations, represented by XPS, XAS and resonant X-ray photoelectron spectroscopy (ResPES), carried out in this work, should help to illuminate this unconventional superconductivity and resolve a debate of competing models for explaining the existence of superconductivity in this compound.

Lorsque la matière condensée est soumise à des rayonnements de haute énergie, des électrons secondaires de basse énergie (0-20 eV) sont produits en grande quantité. Ces électrons participent à part entière aux dommages induits dans la matière, incluant les processus d’érosion et de modifications chimiques. Les fragments produits au sein du milieu réagissent et de nouvelles espèces sont formées. Plusieurs domaines d’application sont concernés par ces processus, et plus particulièrement le design de dispositifs par lithographie ou par dépôts assistés par faisceaux focalisés et l’astrochimie. Les enjeux concernent l’identification des mécanismes induits par les électrons lents, le contrôle des fragments réactifs et espèces stables formés, ainsi que la détermination de grandeurs quantitatives permettant d’apprécier l’efficacité des processus impliqués. L’approche développée dans ce travail de thèse consiste à irradier des surfaces et interfaces directement avec des faisceaux d’électrons de basse énergie afin d’étudier les processus induits. Les réponses de films moléculaires supportés modèles (d’épaisseur variable) sont étudiées en fonction de l’énergie incidente des électrons et des doses délivrées. Dans les cas favorables, des méthodologies ont pu être proposées pour accéder à l’estimation de sections efficaces effectives. Pour ce faire, trois techniques expérimentales sont combinées. Les films déposés et les résidus formés sont analysés par spectroscopie de perte d'énergie d’électrons à haute résolution (HREELS) et désorption programmée en température (TPD). Les fragments neutres (et non pas ioniques comme le plus souvent) désorbant sous irradiation sont analysés en masse afin de mener une étude de désorption stimulée par impact d’électrons (ESD).Dans le contexte de la fonctionnalisation de surface, le greffage de centres carbonés hybridés sp2 sur un substrat de diamant poly-cristallin hydrogéné a été réalisé par irradiation électronique d’une couche mince de benzylamine. A 11 eV, le mécanisme dominant implique la dissociation en neutres du précurseur. La section efficace effective de greffage a pu être déterminée par HREELS suite à une unique irradiation, en tirant avantage du profil du faisceau d’irradiation. Dans le contexte de l’astrochimie, la réponse à l’irradiation par électrons lents de glaces d’ammoniac amorphes et cristallisées a été étudiée. La désorption de molécules d’ammoniac a été observée. Elle peut résulter de l’érosion directe du film et de mécanismes de désorption induite par excitation électronique (DIET). Différents processus de fragmentation/recombinaison ont été mis en évidence via la désorption des espèces neutres NHx (x = 1,2), H2 et N2. Une chimie particulièrement riche est induite par irradiation électronique à 13 eV. L’analyse temporelle des rendements ESD a permis la détermination de la section efficace de la désorption de NH3, et l’observation de la formation retardée de N2 et H2. L’analyse TPD des résidus a démontré la synthèse de diazène (N2H2) et d’hydrazine (N2H4) dans le film. Ces résultats peuvent aider à l’élucidation des écarts observés dans les abondances de NH3 et N2 dans les régions denses de l'espace. Enfin, les premiers travaux réalisés pour fonctionnaliser un substrat de façon résolue à l’échelle micrométrique sous irradiation d’électrons lents sont également présentés. La faisabilité de la procédure utilisant un microscope électronique à basse énergie (LEEM) a été démontré sur une monocouche de terphenylthiol (TPT). Des motifs de 5 μm de travaux de sortie différents ont été imprimés en travaillant à des énergies de 10-50 eV. Ensuite la réponse de films modèles de résines lithographiques (PMMA, polyméthacrylate de méthyle) à des irradiations électroniques a été étudiée, afin d’identifier les énergies favorables en vue d’une modification de surface résolue spatialement. / High-energy irradiation of condensed matter leads to the production of copious amounts of low-energy (0-20 eV) secondary electrons. These electrons are known to trigger various dissociative processes leading to observed damages including erosion and chemical modifications. The resulting reactive species within the condensed media can also lead to the synthesis of new molecules. This has implications in several applications most especially in the design of lithographic methods, focused beam-assisted deposition, as well as in astrochemistry. In all these applications, it is important to identify the processes induced by low-energy electrons, study the reactive fragments and stable molecules produced to determine possibilities of controlling them, and generate quantitative data to gauge the efficiencies of these processes. The approach developed for this PhD work consists of directly irradiating surfaces and interfaces using low-energy electrons and studying the processes that arise. The responses of different model molecular films (of varying thickness) were studied as a function of incident electron energy and dose. In favorable cases, methodologies proposed herein can be used to estimate effective cross sections of observed processes. Three complementary surface-sensitive techniques were utilized for this purpose. To characterize the deposited films and formed residues, the High Resolution Electron-Energy Loss Spectroscopy (HREELS) and Temperature Programmed Desorption (TPD) were used. Neutral fragments (as opposed to their often-detected ionic counterparts) desorbing under electron irradiation were monitored using a mass spectrometer in a technique called Electron Stimulated Desorption (ESD).Within the context of surface functionalization, the grafting of sp2-hybridized carbon centers on a polycrystalline hydrogenated diamond substrate was realized through electron irradiation of a thin layer of benzylamine precursor deposited on its surface. At 11 eV, the dominant mechanism is proposed to be neutral dissociation of the precursor molecules. The effective cross section of the grafting process was estimated in only a single measurement from the HREELS map of the sample surface, taking advantage of the electron beam profile. Within the context of astrochemistry, on the other hand, the responses of crystalline and amorphous NH3 ices were studied under electron impact. The desorption of intact NH3 was observed which resulted in the direct erosion of the film proceeding through a mechanism consistent with desorption induced by electronic transitions (DIET). Different fragmentation and recombination processes were also observed as evidenced by detected neutral species like NHx (x=1,2), N2, and H2. Aside from desorption, a wealth of chemical processes was also observed at 13 eV. Temporal ESD at this energy allowed for the estimation of the effective cross section of NH3 desorption and observing the delayed desorption of N2 and H2. TPD analysis of the residues also provided evidence of N2H2 and N2H4 synthesis in the film. These results can help explain the observed discrepancies in abundances of NH3 and N2 in dense regions in space. Lastly, this PhD work will present prospects for these electron-induced processes to be constrained spatially in microscopic dimensions for lithographic applications. The feasibility of the procedure utilizing Low-Energy Electron Microscope (LEEM) was demonstrated on a terphenylthiol self-assembled monolayer (TPT SAM) specimen. Spots of 5 μm in diameter with different work functions were imprinted on the surface using energies from 10-50 eV. Electron-induced reactions in thin-film resists (PMMA, poly(methyl methacrylate)) were also studied at low-energy identifying opportunities for energy- and spatially-resolved surface modification.

In this work the electronic and magnetic structure of the crystals Sr2FeMoO6, Fe0.5Cu0.5Cr2S4, LuFe2O4 and the molecules FeStar, Mo72Fe30, W72Fe30 are investigated by means of X-ray spectroscopic techniques. These advanced materials exhibit very interesting properties like magnetoresistance or multiferroic behaviour. In case of the molecules they also could be used as spin model systems. A long standing issue concerning the investigation of these materials are contradicting results found for the magnetic and electronic state of the iron (Fe) ions present in these compounds. Therefore this work focuses on the Fe state of these materials in order to elucidate reasons for these problems. Thereby the experimental results are compared to multiplet simulations.