Submitted by Cleide Dantas (cleidedantas@ufpa.br) on 2014-04-30T12:33:42Z No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InvestigacaoCaracteristicasNCPS.pdf: 10527727 bytes, checksum: 7e320cfba4c6a329c0c2d91d6adbdff3 (MD5) / Approved for entry into archive by Ana Rosa Silva (arosa@ufpa.br) on 2014-06-11T13:18:53Z (GMT) No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InvestigacaoCaracteristicasNCPS.pdf: 10527727 bytes, checksum: 7e320cfba4c6a329c0c2d91d6adbdff3 (MD5) / Made available in DSpace on 2014-06-11T13:18:53Z (GMT). No. of bitstreams: 2 license_rdf: 23898 bytes, checksum: e363e809996cf46ada20da1accfcd9c7 (MD5) Dissertacao_InvestigacaoCaracteristicasNCPS.pdf: 10527727 bytes, checksum: 7e320cfba4c6a329c0c2d91d6adbdff3 (MD5) Previous issue date: 2006 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Neste trabalho, fizemos uma investigação sobre o estudo teórico das características I x V e C x V de Nanotubo Carbono de Parede Simples (NCPS) puro, com Nitrogênio substitucional carregado com cargas -1 (caracterizando um indicativo de dopagem tipo n) e +1 (caracterizando um indicativo de dopagem tipo p) e na presença de grupos doador (NO2)-aceitador (NH2), através da simulação computacional do estado fundamental de NCPS, bem como de sua estrutura eletrônica e propriedades ópticas, utilizando parametrizações semi-empíricas AM1 (Austin Mudel 1) e ZINDO/S-ClS (Zerner´s lntermediate Neglect of Differential Orbital/Spectroscopic - Cunfiguration lnteraction Single) derivadas da Teoria de Hartree-Fock baseada em técnicas de química quântica. Por meio deste modelo teórico analisamos as propriedades ópticas e eletrônicas, de maior interesse para esses materiais, a fim de se entender a melhor forma de interação desses materiais na fabricação de dispositivos eletrônicos, tais como TECs (Transistores de Efeito de Campo) ou em aplicações em optoeletrônica tais como DEL (Dispositivo Emissor de Luz). Observamos que NCPS com Nitrogênio substitucional apresentam defeitos conformacionais do tipo polarônico. Fizemos as curvas dos espectros UV-visível de Absorção para NCPS armchair e zigzag puro, com Nitrogênio substitucional carregado com cargas (-1 e +1) e na presença de grupos doador (NO2)-aceitador (NH2), quando perturbados por intensidades diferentes de campo elétrico. Verificamos que em NCPS zigzag ao aumentarmos a intensidade do campo elétrico, suas curvas sofrem grandes perturbações. Obtivemos as curvas p x E, I x V e C x V para esses NCPS, concluímos que NCPS armchair possui comportamento resistor, pois suas curvas são lineares e zigzag possui comportamento semelhante ao dos dispositivos eletrônicos importantes para o avanço tecnológico. Assim, nossos resultados estão de bom acordo com os resultados experimentais e teóricos de NCPS puro e com Nitrogênio encontrados na literatura. / In this work, we relate an investigation on the theoretical study of the I x V and C x V characteristics os SWCN pure, with substitutional Nitrogen charged with charge -1 (n-type material) and +1 (p-type material) and in the presence of donor (NO2)-aceptor (NH2) grups, through of the computational simulation of the SWCN ground states as well as your electronic structure and optics properties utilizing quantum chemical approaches: AM1 (Austin Model 1) and ZINDO/S-CIS (Zerner’s Intermediate Neglect of Differential Orbital/Spectroscopic – Configuration Interaction Simple) semi-empirical parametrization, Hartree-Fock based theory. By mean of this theoretical model, we analyse the electrons and optics properties, of more interest for that materials, the end understand the best shape of interation of this materials in the fabrication of electronic devices such as FETs (Field-Effect Transistors) or in optoelectronic applications such as LEDs (Light-Emitting Devices). We observate that SWCN with substitutional Nitrogen presents conformational defects of the polaron type. We made the curves of the UV-visivel Absorpion Spectra for armchair and zigzag SWCN pure, with substitutional Nitrogen charged with charge -1 (n-type material) and +1 (p-type material) and in the presence of donor (NO2)-aceptor (NH2) grups, when they are perturbed by different intensity of electric field. We examine in zigzag SWCN when it has na increase in the intensity of the electric field, yours curves suffer large perturbations. We get the curves p x E, I x V and C x V for this SWCN, we conclude that armchair armchair possess resistor behavior, therefore yours curves are linears and zigzag possess similar behavior at the importants electronic devices for the tecnologics advance. Our results are good agreement with the experimentals and theoretical results of the SWCN pure and with Nitrogen found in the literature.

Molecular modeling, using both ab initio and semi-empirical methods has been undertaken for a series of dirhodium complexes in order to improve the understanding of the nature of the chemical bonding in this class of homogeneous catalysts. These complexes, with carboxylamidate and carboxylate ligands, are extremely functional metal catalysts used in the synthesis of pharmaceuticals and agrochemicals. The X-ray crystallography shows anomalies in the bond angles that have potential impact on understanding the catalysis. To resolve these issues, minimum energy structures of several examples (e.g. Rh2(NHCOCH3)4, Rh2(NHCOCH3)4NC, Rh2(CO2CH3)4, Rh2(CO2CH3)4NC, Rh2(CHO2)4, and Rh2(CHO2)4NC) were calculated using Hatree-Fock and Density Functional Theory/B3LYP with the LANL2DZ ECP (Rh), and cc-pVDZ (all other atoms) basis sets.

We study the application of Bose-Einstein condensates (BECs) to simulations of phenomena across a number of disciplines in physics, using theoretical and computational methods. ¶ Collapsing condensates as created by E. Donley et al. [Nature 415, 39 (2002)] exhibit potentially useful parallels to an inflationary universe. To enable the exploitation of this analogy, we check if current quantum field theories describe collapsing condensates quantitatively, by targeting the discrepancy between experimental and theoretical values for the time to collapse. To this end, we couple the lowest order quantum field correlation functions to the condensate wavefunction, and solve the resulting Hartree-Fock-Bogoliubov equations numerically. Complementarily, we perform stochastic truncated Wigner simulations of the collapse. Both methods also allow us to study finite temperature effects. ¶ We find with neither method that quantum corrections lead to a faster collapse than is predicted by Gross-Pitaevskii theory. We conclude that the discrepancy between the experimental and theoretical values of the collapse time cannot be explained by Gaussian quantum fluctuations or finite temperature effects. Further studies are thus required before the full analogue cosmology potential of collapsing condensates can be utilised. ¶ As the next project, we find experimental parameter regimes in which stable three-dimensional Skyrmions can exist in a condensate. We show that their stability in a harmonic trap depends critically on scattering lengths, atom numbers, trap rotation and trap anisotropy. In particular, for the Rb87 |F=1,m_f=-1>, |F=2,m_f=1> hyperfine states, stability is sensitive to the scattering lengths at the 2% level. We find stable Skyrmions with slightly more than 2*10^6 atoms, which can be stabilised against drifting out of the trap by laser pinning. ¶ As a stepping stone towards Skyrmions, we propose a method for the stabilisation of a stack of parallel vortex rings in a Bose-Einstein condensate. The method makes use of a ``hollow'' laser beam containing an optical vortex, which realises an optical tunnel for the condensate. Using realistic experimental parameters, we demonstrate numerically that our method can stabilise up to 9 vortex rings. ¶ Finally, we focus on analogue gravity, further exploiting the analogy between flowing condensates and general relativistic curved space time. We compare several realistic setups, investigating their suitability for the observation of analogue Hawking radiation. We link our proposal of stable ring flows to analogue gravity, by studying supersonic flows in the optical tunnel. We show that long-living immobile condensate solitons generated in the tunnel exhibit sonic horizons, and discuss whether these could be employed to study extreme cases in analogue gravity. ¶ Beyond these, our survey indicates that for conventional analogue Hawking radiation, simple outflow from a condensate reservoir, in effectively one dimension, has the best properties. We show with three dimensional simulations that stable sonic horizons exist under realistic conditions. However, we highlight that three-body losses impose limitations on the achievable analogue Hawking temperatures. These limitations vary between the atomic species and favour light atoms. ¶ Our results indicate that Bose-Einstein condensates will soon be useful for interdisciplinary studies by analogy, but also show that the experiments will be challenging.

La détermination de la masse nucléaire permet d'accéder à l'énergie de liaison donc au bilan de toutes les forces agissant dans le noyau. L'exploration de la structure nucléaire requiert la mesure des masses loin de la stabilité. Néanmoins la production des ions radioactifs est peu sélective et l'ion d'intérêt est souvent noyé dans un fond de contaminants isobariques. Ces dernières années, l'utilisation des pièges à ions linéaires et du refroidissement par gaz tampon a été fortement développée permettant la mesure de masse des noyaux exotiques avec une grande précision. Cette thèse porte sur le développement innovant d'un piège de Paul circulaire, "le cirque d'ions". Sa géométrie lui permet de confiner les ions sur un grand nombre de tours. Ainsi, ils peuvent être refroidis avec une pression de gaz tampon de l'ordre de 10-4 mbar. Par ailleurs, il est capable de trier en masse les ions piégés et refroidis avec un pouvoir de résolution suffisant pour séparer des isobares. Nous avons réalisé et testé le premier prototype de ce spectromètre à Orsay. Cette thèse étudie également les prédictions des masses par les différents modèles théoriques, en les comparant avec l'approche microscopique HFB-17. Actuellement, la masse des noyaux très exotiques peut seulement être prédite. L'étude de l'énergie de séparation de deux neutrons avec HFB-17 met en évidence des zones d'instabilité numérique. Afin de l'améliorer, nous avons apporté une correction aux énergies de déformation calculées par ce modèle, en utilisant comme référence les masses des chaînes isotopiques 143-146Xe et 223-229Rn que nous avons mesurées avec le spectromètre ISOLTRAP au CERN.

L'unification entre structure et réaction a toujours été un grand défi de la physique nucléaire. L'extrème complexité rencontrée dans la description des systèmes quantiques finis a en effet mené la théorie nucléaire à dissocier ces deux approches. Une voie possible pour les réconcilier est le modèle en couches avec couplage aux états du continuum. Jusqu'alors, les applications numériques reposant sur ce modèle utilisaient un puit de potentiel local pour générer la base individuelle et une interaction résiduelle schématique de portéenulle pour les couplages au continuum. Nous avons développé le formalisme du modèle en couches avec couplage aux états du continuum avec une interaction nucléon-nucléon de portée finie. Nous avons ensuite généralisé le formalisme de manière à prendre en compte un nombre arbitraire de particules dans un état de diffusion. Le grand avantage de cette approche réside dans le fait que la même interaction est utilisée pour la construction de la base individuelle et pour le couplage aux états du continuum. Nous avons donc posé les bases nécessaires à un calcul ab initio, le but étant de dériver le champ moyen, les mélanges de configurations et le couplage aux états du continuum à partir de la seule interaction nucléon-nucléon dans le vide. Nous avons effectuée une première application réaliste en calculant les spectres de 17F et 17O, et les déphasages de difusion élastique 16O(p, p)16O.

Time-dependent density functional theory calculations have been carried out to determine the complex first-order hyperpolarizability in the two-photon resonance region of the molecule IDS-Cab. Calculations show that three strongly absorbing states, in the ultraviolet region, are separated to the extent that no significant interference of the imaginary parts of the tensor elements of the first-order hyper-polarizability occurs. Consequently, and in contrast to experimental findings [27], no reduced imaginary parts of the first-order hyperpolarizability in the two-photon resonant region can be seen.

pas de résumé

Computational chemists are concerned about two aspects when choosing between the myriad of theoretical methodologies: the accuracy (the "truth") and the computational cost (the tractability). Among the least expensive methods are the Hartree-Fock (HF), density functional theory (DFT), and second-order Moller-Plesset perturbation theory (MP2) methods. While each of these methods yield excellent results in many cases, the inadequate inclusion of certain types of electron correlation (either high-orders or nondynamical) can produce erroneous results. The compromise for the computation of noncovalent interactions often comes from empirically scaling DFT and/or MP2 methods to fit benchmark data sets. The DFT method with an empirically fit dispersion term (DFT-D) often yields semi-quantitative results. The spin-component scaled MP2 (SCS-MP2) method parameterizes the same- and opposite-spin correlation energies and often yields less than 20% error for prototype noncovalent systems compared to chemically accurate CCSD(T) results. There is no simple fix for cases with a large degree of nondynamical correlation (such as transition metal-salen complexes). While testing standard and new DFT functionals on the spin-state energy gaps of transition metal-salen complexes, no DFT method produced reliable results compared to very robust CASPT3 results. Therefore each metal-salen complex must be evaluated on a case-by-case basis to determine which methods are the most reliable. Utilizing a combination of DFT-D and SCS-MP2 methods, the reaction mechanism for the addition of cyanide to unsaturated imides catalyzed by the Al(Cl)-salen complex was performed. Various experimental observations are rationalized through this mechanism.

<p>This thesis is part of an effort to enable large-scale Hartree-Fock/Kohn-Sham (HF/KS) calculations. The objective is to model molecules and materials containing thousands of atoms at the quantum mechanical level. HF/KS calculations are usually performed with the Self-Consistent Field (SCF) method. This method involves two computationally intensive steps. These steps are the construction of the Fock/Kohn-Sham potential matrix from a given electron density and the subsequent update of the electron density usually represented by the so-called density matrix. In this thesis the focus lies on the representation of potentials and electron density and on the density matrix construction step in the SCF method. Traditionally a diagonalization has been used for the construction of the density matrix. This diagonalization method is, however, not appropriate for large systems since the time complexity for this operation is σ(n³). Three types of alternative methods are described in this thesis; energy minimization, Chebyshev expansion, and density matrix purification. The efficiency of these methods relies on fast matrix-matrix multiplication. Since the occurring matrices become sparse when the separation between atoms exceeds some value, the matrix-matrix multiplication can be performed with complexity σ(n).</p><p>A hierarchic sparse matrix data structure is proposed for the storage and manipulation of matrices. This data structure allows for easy development and implementation of algebraic matrix operations, particularly needed for the density matrix construction, but also for other parts of the SCF calculation. The thesis addresses also truncation of small elements to enforce sparsity, permutation and blocking of matrices, and furthermore calculation of the HOMO-LUMO gap and a few surrounding eigenpairs when density matrix purification is used instead of the traditional diagonalization method.</p>

<p>Time-dependent density functional theory calculations have been carried out to determine the complex first-order hyperpolarizability in the two-photon resonance region of the molecule IDS-Cab. Calculations show that three strongly absorbing states, in the ultraviolet region, are separated to the extent that no significant interference of the imaginary parts of the tensor elements of the first-order hyper-polarizability occurs. Consequently, and in contrast to experimental findings [27], no reduced imaginary parts of the first-order hyperpolarizability in the two-photon resonant region can be seen.</p>