Cuno Kibele was the most prolific and most influential architect to live and work in Muncie, Indiana, in the first decades of the twentieth century. From 1905 to 1927, Kibele designed Muncie's grandest public buildings as well as schools, churches, factories, and commercial buildings. Kibele is most often identified with these buildings. The purpose of this thesis is to study a portion of Kibele's work that has been generally overlooked, his residential designs.Kibele was a reputable residential designer in Muncie. He was a sought-after architect for the city's rising middle class who lived in the suburbs just outside of town. Kibele's residential designs were unlike his other types of commissions in their simplicity and restraint of form and style. Kibele did not include stylistic details in his residential designs to the extent that he did in his other commissions. The few stylistic elaborations that Kibele did include in his residential designs were common-place Craftsman and Prairie style details.Kibele's residences were not high style or innovative in design, however they incorporated the latest social thinking and technological advances. In the early decades of the twentieth century, middle class residential design in America underwent a dramatic transformation. The Victorian home, with its rambling, asymmetrical plan, dense cluttered interior, and ornate detailing was pushed aside in favor of a new, modem aesthetic that favored simple clean lines, reduction of ornamentation, and an open interior arrangement. Kibele's residential commissions demonstrate the modem design principles that resulted from this transformation: the inclusion of modem technological advances; a kitchen redesigned for efficiency; simpler outline and reduction of ornamentation; a simple, open floor plan; and provisions for healthy living. / Department of Architecture

This thesis aims at validating a theoretical protocol to develop global potential energy surfaces for use in the spectroscopy and dynamics of transition metal nitrosyl complexes. To get an insight into the homogeneous catalysis of NO with Cu and the chemical reaction dynamics, an accurate prediction of the nature of the interaction, as well as of the global potential energy surfaces (PES) is necessary in the gas phase. Experimental data are difficult to obtain, hence the importance of carrying out calculations of the lowest electronic states as accurate as possible to address the structure , spectroscopy and dynamics of this system. All ab initio calulations we report here were performed at the multi-reference configuration interaction (MRCI) and at the coupled cluster level of theory. We aslo investigate the importance of relativistic effects in the systems. For CuNO system, it is shown that a complete active space involving 18 valence electrons, 11 molecular orbitals and the prior determination of 12 roots in the MCSCF calculation is needed for overall qualitatively correct results from the MRCI calculations. The present calculations yield a bound singlet A' ground state for CuNO and comparared with previous results. We have obtained new, complete potential energy functions of the ground electronic states of CuO and CuN systems. Comparison of the term values for the lowest electronic states of CuO and CuN with those previously reported in the literature shows a quite good agreement. We derived a novel analytical representation of the adiabatic potential energy surface in the ground electronic state of the CuNO system as a sum of two-body and three-body terms. This compact and flexible representation enables us to make a physically correct interpolation of the ab initio data points at the MRCI level of theory. We use a modified Levenberg-Marquardt algorithm for fitting the potential, which has 19 adjustable parameters and which now enables us to do scattering dynamics of the CuNO system. We perform full dimensional quantum dynamical studies with this new potential. Convergence of the time dependent wavepacket calculation has been achieved. We find that the scattering in CuNO is highly inelastic. Intermediate, excited meta stable reaction products CuNO∗ live for about 0.5 to 1 ps and maybe more.

Dans cette thèse, nous avons optimisé avec succès tous les paramètres pour calculer l'état fondamental du systéme neutre [N,O, Cu]. L'étude de réactions impliquant NO et des métaux de transition est particulièrement intéressante pour le développement de catalyses efficaces pour la réduction de NO, en vue de sonder la possibilité d'une catalyse homogène impliquant les fragments Cu et NO; une prévision précise de la nature de l'interaction entre ces deux fragments est nécessaire en phase gaz. Il a été montré que les calculs MCSCF incluant 12 racines sont nécessaires pour avoir une convergence propre mais donnent des états inversés, l'asymptote. Pour décrire proprement l'état fondamental, nous utilisons les calculs MRCI sur 6 états par espèce de symétrie simultanément. Aussi nous montrons par calculs MRCI, que l'espace actif peut contenir tous les électrons 3d de Cu pour décrire précisément le système. Ici nous utilisons un CAS (22, 13) qui est proche de l'espace de valence complète du système. Nous avons développé une SEP analytique globale qui peut être utilisée pour modéliser les données ab initio obtenues. L'état lié est un état 1 A’ avec une énergie de rCu = 2.382 pm, rNO = 1.134 pm et tCu = 133.495. Nous avons également effectué des calculs précis sur l'état électronique fondamental et sur les états électroniques excités des diatomiques CuO et CuN et obtenu l'énergie de dissociation qui a ensuite été utilisée comme paramètre d'ajustement dans la représentation analytique. Les fondamentaux vibrationnels calculés se comparent bien avec les données expérimentales disponibles. Le potentiel analytique a été utilisé avec succès avec les meilleurs paramètres ajustés pour effectuer des calculs de dynamique quantique sur le complexe, dont les résultats indiquent une diffusion réactive avec un transfert de l'énergie translatoire vers l'énergie vibrationnelle dans le domaine de temps de la femtoseconde. Des résultats plus avancés non-inclus dans ce résumé impliquent des calculs CCSD(T), incluant des corrections relativistes, et une fusion originale entre les données MRCI et CCSD(T) et modélisées avec la SEP analytique, dont les résultats donnent un puit de potentiel plus profond et réduisent la distance de liaison rCu (distance Cu-NO). Nous avons aussi effectué des études de dynamique quantique avec un facteur d'impact variant (J > 0) et une diffusion des énergies de collision, toutes deux dans une approche soit isotrope, soit directionnelle du paquet d'onde initial. / This thesis aims at validating a theoretical protocol to develop global potential energy surfaces for use in the spectroscopy and dynamics of transition metal nitrosyl complexes. To get an insight into the homogeneous catalysis of NO with Cu and the chemical reaction dynamics, an accurate prediction of the nature of the interaction, as well as of the global potential energy surfaces (PES) is necessary in the gas phase. Experimental data are difficult to obtain, hence the importance of carrying out calculations of the lowest electronic states as accurate as possible to address the structure , spectroscopy and dynamics of this system. All ab initio calulations we report here were performed at the multi-reference configuration interaction (MRCI) and at the coupled cluster level of theory. We aslo investigate the importance of relativistic effects in the systems. For CuNO system, it is shown that a complete active space involving 18 valence electrons, 11 molecular orbitals and the prior determination of 12 roots in the MCSCF calculation is needed for overall qualitatively correct results from the MRCI calculations. The present calculations yield a bound singlet A' ground state for CuNO and comparared with previous results. We have obtained new, complete potential energy functions of the ground electronic states of CuO and CuN systems. Comparison of the term values for the lowest electronic states of CuO and CuN with those previously reported in the literature shows a quite good agreement. We derived a novel analytical representation of the adiabatic potential energy surface in the ground electronic state of the CuNO system as a sum of two-body and three-body terms. This compact and flexible representation enables us to make a physically correct interpolation of the ab initio data points at the MRCI level of theory. We use a modified Levenberg-Marquardt algorithm for fitting the potential, which has 19 adjustable parameters and which now enables us to do scattering dynamics of the CuNO system. We perform full dimensional quantum dynamical studies with this new potential. Convergence of the time dependent wavepacket calculation has been achieved. We find that the scattering in CuNO is highly inelastic. Intermediate, excited meta stable reaction products CuNO∗ live for about 0.5 to 1 ps and maybe more.

O filtro cuno faz parte do circuito de tratamento de água do reator IEA-R1 que , quando saturado, é substituído, se tornando um rejeito radioativo que deve ser gerenciado. Neste trabalho foi realizada a caracterização primária do filtro cuno do reator nuclear IEA-R1 do IPEN utilizando-se espectrometria gama associada ao método de Monte Carlo. A espectrometria gama foi realizada utilizando-se um detector de germânio hiperpuro (HPGe). O cristal de germânio representa o volume ativo de detecção do detector HPGe, que possui uma região denominada camada morta ou camada inativa. Na literatura tem sido reportada uma diferença entre os valores experimentais e teóricos na obtenção da curva de eficiência desses detectores. Neste trabalho foi utilizado o código MCNP-4C para a obtenção da calibração em eficiência do detector para a geometria do filtro cuno, onde foram estudadas as influências da camada morta e do efeito de soma em cascata no detector HPGe. As correções dos valores de camada morta foram realizadas variando-se a espessura e o raio do cristal de germânio. O detector possui 75,83 cm3 de volume ativo de detecção, segundo informações fornecidas pelo fabricante. Entretanto os resultados encontrados mostraram que o valor de volume ativo real é menor do que o especificado, onde a camada morta representa 16% do volume total do cristal. A análise do filtro cuno por meio da espectrometria gama, permitiu a identificação de picos de energia. Por meio desses picos foram identificados três radionuclídeos no filtro: 108mAg, 110mAg e 60Co. A partir da calibração em eficiência obtida pelo método de Monte Carlo, o valor de atividade estimado para esses radionuclídeos está na ordem de MBq. / The Cuno filter is part of the water processing circuit of the IEA-R1 reactor and, when saturated, it is replaced and becomes a radioactive waste, which must be managed. In this work, the primary characterization of the Cuno filter of the IEA-R1 nuclear reactor at IPEN was carried out using gamma spectrometry associated with the Monte Carlo method. The gamma spectrometry was performed using a hyperpure germanium detector (HPGe). The germanium crystal represents the detection active volume of the HPGe detector, which has a region called dead layer or inactive layer. It has been reported in the literature a difference between the theoretical and experimental values when obtaining the efficiency curve of these detectors. In this study we used the MCNP-4C code to obtain the detector calibration efficiency for the geometry of the Cuno filter, and the influence of the dead layer and the effect of sum in cascade at the HPGe detector were studied. The correction of the dead layer values were made by varying the thickness and the radius of the germanium crystal. The detector has 75.83 cm3 of active volume of detection, according to information provided by the manufacturer. Nevertheless, the results showed that the actual value of active volume is less than the one specified, where the dead layer represents 16% of the total volume of the crystal. A Cuno filter analysis by gamma spectrometry has enabled identifying energy peaks. Using these peaks, three radionuclides were identified in the filter: 108mAg, 110mAg and 60Co. From the calibration efficiency obtained by the Monte Carlo method, the value of activity estimated for these radionuclides is in the order of MBq.

O filtro cuno faz parte do circuito de tratamento de água do reator IEA-R1 que , quando saturado, é substituído, se tornando um rejeito radioativo que deve ser gerenciado. Neste trabalho foi realizada a caracterização primária do filtro cuno do reator nuclear IEA-R1 do IPEN utilizando-se espectrometria gama associada ao método de Monte Carlo. A espectrometria gama foi realizada utilizando-se um detector de germânio hiperpuro (HPGe). O cristal de germânio representa o volume ativo de detecção do detector HPGe, que possui uma região denominada camada morta ou camada inativa. Na literatura tem sido reportada uma diferença entre os valores experimentais e teóricos na obtenção da curva de eficiência desses detectores. Neste trabalho foi utilizado o código MCNP-4C para a obtenção da calibração em eficiência do detector para a geometria do filtro cuno, onde foram estudadas as influências da camada morta e do efeito de soma em cascata no detector HPGe. As correções dos valores de camada morta foram realizadas variando-se a espessura e o raio do cristal de germânio. O detector possui 75,83 cm3 de volume ativo de detecção, segundo informações fornecidas pelo fabricante. Entretanto os resultados encontrados mostraram que o valor de volume ativo real é menor do que o especificado, onde a camada morta representa 16% do volume total do cristal. A análise do filtro cuno por meio da espectrometria gama, permitiu a identificação de picos de energia. Por meio desses picos foram identificados três radionuclídeos no filtro: 108mAg, 110mAg e 60Co. A partir da calibração em eficiência obtida pelo método de Monte Carlo, o valor de atividade estimado para esses radionuclídeos está na ordem de MBq. / The Cuno filter is part of the water processing circuit of the IEA-R1 reactor and, when saturated, it is replaced and becomes a radioactive waste, which must be managed. In this work, the primary characterization of the Cuno filter of the IEA-R1 nuclear reactor at IPEN was carried out using gamma spectrometry associated with the Monte Carlo method. The gamma spectrometry was performed using a hyperpure germanium detector (HPGe). The germanium crystal represents the detection active volume of the HPGe detector, which has a region called dead layer or inactive layer. It has been reported in the literature a difference between the theoretical and experimental values when obtaining the efficiency curve of these detectors. In this study we used the MCNP-4C code to obtain the detector calibration efficiency for the geometry of the Cuno filter, and the influence of the dead layer and the effect of sum in cascade at the HPGe detector were studied. The correction of the dead layer values were made by varying the thickness and the radius of the germanium crystal. The detector has 75.83 cm3 of active volume of detection, according to information provided by the manufacturer. Nevertheless, the results showed that the actual value of active volume is less than the one specified, where the dead layer represents 16% of the total volume of the crystal. A Cuno filter analysis by gamma spectrometry has enabled identifying energy peaks. Using these peaks, three radionuclides were identified in the filter: 108mAg, 110mAg and 60Co. From the calibration efficiency obtained by the Monte Carlo method, the value of activity estimated for these radionuclides is in the order of MBq.