The diverse field of material research has been steadily expanding with a great help from computational physics, especially in the investigation of the fundamental properties of materials. This has driven the computational physics to become one of the main branches of physics, allowing for density functional theory (DFT) to develop as one of the cornerstones of material research. Nowdays, DFT is the method of choice in a great variety of studies, from fundamental properties, to materials modelling and searching for new materials. In this thesis, DFT is employed for the study of a small part of this vast pool of applications. Specifically, the microscopic characteristics of Zn1-xCdxS alloys are studied by looking into the evolution of the local structure. In addition, the way to model the growth of graphene on Fe(110) surface is discussed. The structural stability of silicon nanocrystals with various shapes is analysed in detail, as well. DFT is further used in studying different properties of semiconductor nanocrystals. The size evolution of the character of the band gap in silicon nanocrystals is investigated in terms of changes in the character of the states around the band gap. The influence of various surface impurities on the band gap, as well as on the electronic and optical properties of silicon nanocrystals is further studied. In addition, the future use of silicon nanocrystals in photovoltaic devices is examined by studying the band alignment and the charge densities of silicon nanocrystals embedded in a silicon carbide matrix. Furthermore, the electronic and optical properties of different semiconductor nanocrystals is also investigated. In the case of the CdSe/CdS and CdS/ZnS core-shell nanocrystals the influence of the nanocrystal size and different structural models on their properties is analysed. For silicon nanocrystal capped with organic ligands, the changes in the optical properties and lifetimes is thoroughly examined with changes in the type of organic ligand.

Dans le domaine des nanosciences, la recherche sur les matériaux possédant des dimensions réduites a connu des progrès spectaculaires. Tandis que de nombreux travaux ont été fait initialement sur le graphène, l'attention s'est ensuite portée vers d'autres matériaux bidimensionnels, tels que le nitrure de bore hexagonal ou encore les dichalcogénures de métaux de transition. Néanmoins, il est toujours nécessaire de trouver des matériaux possédant des caractéristiques équivalentes ou supérieures à celles des composés déjà connus. Dans le cadre de cette thèse, nous avons utilisé le calcul ab initio et plus particulièrement la théorie de la fonctionnelle de la densité pour prédire et comprendre les propriétés de trois familles de matériaux bidimensionnels. Premièrement, en prenant la structure du phosphorène comme structure de référence et en remplaçant le phosphore par des atomes voisins dans le tableau périodique, nous avons pu obtenir des matériaux inconnus jusqu'ici. Ensuite, nous nous sommes intéressés à des matériaux à base d'halogénures tels que AcOBr ou BaFCl, parmi d'autres. Enfin, nous avons mis l'accent sur des composés bidimensionnels quaternaires, tels que ScP2AgSe6, P2AgSe6Bi, P2CuBiSe6 et CuInP2 S6. Pour chaque matériau, nous avons démontré qu'il était dynamiquement stable et étudié sa structure électronique, et pour certains l'effet d'un champ électrique sur le matériau, ce qui ouvre la porte à de futures études expérimentales dans le domaine / In the field of nanosciences, research on materials with reduced dimensions has seen spectacular progress. While many works were initially done on graphene, the attention then came to other two-dimensional materials, such as hexagonal boron nitride or transition metal dichalcogenides. Nevertheless, it is still necessary to find materials with characteristics equivalent to or superior to those of the already known compounds. In this thesis, we used ab initio calculations and more particularly density functional theory to predict and understand the properties of three families of two-dimensional materials. First, taking the phosphorene structure as the reference and replacing phosphorus with neighboring atoms in the periodic table, we have been able to obtain unknown materials so far. Then we looked at halide materials such as AcOBr or BaFCl, among others. Finally, we have focused on two-dimensional quaternary compounds, such as ScP2AgSe6, P2AgSe6Bi, P2CuBiSe6 and CuInP2S6. For each compound, we demonstrated that it was dynamically stable and studied its electronic structure, and for some the effect of an electric field on the material, which opens the door for future experimental studies in the field

Ce travail consiste en une tentative de ré-examiner les propriétés électroniques du Fe, Cr et Au au sein de Ge, qui ont déjà été étudiées classiquement par DLTS (Deep Level Transient Spectroscopy). L'image générale qui en découle est que les métaux de transition dans Ge forment de manière prépondérante des centres accepteurs multiples, introduisant plusieurs niveaux profonds dans la bande de gap. A partir d'un modèle de liaison de valence simple, cette conclusion est en accord avec une survenue des impuretés sur des sites de substitution. Cependant, plusieurs questions demeurent ouvertes, comme le rôle de l'hydrogène en tant que contaminant dans l'élargissement des spectres DLTS. Notre contribution se base sur l'utilisation d'une approche plus performante nommée Laplace DLTS, en ce sens qu'elle autorise une meilleure résolution du signal. Nous présentons une analyse extensive par DLTS, MCTS et Laplace DLTS, afin d'étudier les propriétés électroniques des états accepteurs multiples, induits par les 4 métaux de transition sus-nommés. On distingue, parmis les paramètres étudiés, les barrières de capture des porteurs, les vraies sections efficaces de capture de sporteurs majoritaires (déterminées directement par la méthode de variation du pulse de remplissage), L'effet Pool-Frenkel (en lien avec la détermination de l'état de charge du niveau concerné). Ceci permet d'indiquer avec précision la position exacte des niveaux dans la bande interdite. Nous confirmons la plupart des résultats mis en évidence précédemment, tout en ajoutant quelques précisions sir le rôle de l'hydrogène dans la formation de nouveaux complexes. Une mise en parallèle avec le silicium. Dans le cas de Au, de nouveaux niveaux attribués aux complexes Au-Hn et Au-Sb sont observés. De manière générale, l'analyse des porteurs majoritaires et minoritaires par MCYS est toujours sujette à étude. En ce qui concerne le cas du Fe, la faible différence d'énergie entre ses deux niveaux soulève la possibilité d'un caractère de type U-négatif. L'ensemble de ses points devraient faire l'objet d'un travail approfondis dans un avenir proche. / The present work is an attempt to re-examine the electronic properties of Fe, Ni Cr and Au in Ge which have been already studied by conventional DLTS (Deep Level Transient Spectroscopy). A general picture, that emerged, is that transition metals in Ge predominantly form multiple-acceptor centres, introducing several deep levels in the band gap, which according to a simple valence bond model is in agreement with a preferential occurrence of the impurities on substitutional sites. However, some questions remained open such as the role of hydrogen as a natural contaminant in the broadening of the DLTS spectra. Our contribution is based on the use of a more powerfull approach called Laplace DLTS in the sense that it allows a better resolution of the signal. We present extensive DLTS, MCTS and Laplace DLTS results to investigate the electronic properties of the multi-acceptor states, induced by mentioned four transition metals. Among the studied parameters we may cite the barrier for carrier capture, the true majority carrier capture cross section directly measured by the variable pulse length method, the Poole-Frenkel effect related to the assignment of the charge states - all these parameters are important to locate the level positions in the band gap. We confirm in the present work most of the results obatained in the past, adding some insight into the role of hydrogen in the formation of new complexes and in this respect a parallel is made with silicon. In case of Au new levels attributed to conjectural Au-Hn and Au-Sb complexes are observed. In addition development of both majority and minority carriers in MCTS analysis still is under consideration. For the Fe case, the small difference in energy of its two levels raises the question as to the possibility of negative-U character. These mentioned points should be treated more thoroughly in a future work.

121 f. / Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2013-04-12T15:31:22Z No. of bitstreams: 1 Dissertação final-Francisco Xavier Julião.pdf: 1887183 bytes, checksum: 43c99b717d99959d6c766aca8a3e7001 (MD5) / Approved for entry into archive by Ana Hilda Fonseca(anahilda@ufba.br) on 2013-05-13T17:47:56Z (GMT) No. of bitstreams: 1 Dissertação final-Francisco Xavier Julião.pdf: 1887183 bytes, checksum: 43c99b717d99959d6c766aca8a3e7001 (MD5) / Made available in DSpace on 2013-05-13T17:47:56Z (GMT). No. of bitstreams: 1 Dissertação final-Francisco Xavier Julião.pdf: 1887183 bytes, checksum: 43c99b717d99959d6c766aca8a3e7001 (MD5) Previous issue date: 2011 / CAPES / O presente trabalho investigou os efeitos das propriedades eletrônicas em catalisadores a base de Pd e Pt suportados em alumina modificada com o terra rara praseodímio, avaliando sua atividade e tolerância a compostos de enxofre na reação de hidrogenação de aromáticos. Os catalisadores foram preparados pelo método de impregnação difusional, caracterizados por FRX, DRX, DRS-UV-Vis, XPS e TPD de aminas e testados na reação de hidrogenação da tetralina, na presença de tiofeno, além da realização de um estudo termodinâmico da reação. Os testes catalíticos foram realizados em um sistema micro-catalítico pulsado. Os resultados mostraram que o catalisador Pd-Pt/Al2O3-Pr apresentou uma elevada tolerância ao tiofeno, devido a combinação dos seguintes efeitos: (i) a modificação do suporte com praseodímio, que favoreceu uma interação metalsuporte capaz de diminuir a força de ligação metal-adsorvato e favorecer as interação eletrônicas intermetálicas; (ii) o efeito sinérgico a adição de um segundo metal, paládio, em conjunto com a adição do modificador promovendo transferências eletrônicas do tipo Pt→Pd, Pt→Pr e Pd→Pr; (iii) a migração do paládio para superfície catalítica, considerando que o paládio apresenta uma maior resistência ao envenenamento por compostos sulfurados. Através do estudo da seletividade também foi verificado que as propriedades do paládio foram mais efetivas para os catalisadores bimetalicos, o qual favoreceu a formação do isômero trans-decalina. Também pode-se observar, através da relação trans/cis-decalina (estável), que o sistema bimetálico Pt-Pd sofreu pouca influência nas suas propriedades eletrônicas com a adição contínua do veneno. O sistema em estudo mostrou um efeito de conjunto, pois o catalisador Pd-Pt/Al2O3- Pr apresentou pouca sensibilidade ao envenenamento por enxofre e uma atividade moderada, para concentrações do veneno até 2500 ppm de tiofeno, mostrando-se um catalisador robusto para aplicação em processos de hidrotratamento . / Salvador

The major objective of this thesis is to systematically investigate the effect of hexagonal BN (h-BN) islands on electronic and vibrational properties of single wall carbon Nanotubes. All our investigation are based on first principle Density Functional Theory (DFT) calculations. Our study is motivated by interesting metal-semiconductor transition recently found in periodically patterned graphene with h-BN islands. After reproducing the electronic band structure for pristine single wall zigzag carbon nanotubes (which shows metallic or semiconducting properties depending on their chirality), we investigated their electronic band structure in the presence of h-BN islands. The band structure depends not only on the defect concentration, but also on the pattern of the defect atoms. Our results also suggest that, if we start with a metallic /semiconducting mixture of ZSWCNTs, upon h-BN addition, the sample converts to fully semiconducting. This is a promising result for applications of CNTs in molecular electronics. Fundamental understanding of vibrational properties of nano electronics component is equally important in their applications especially in thermal management and thermoelectric applications. Defect engineering is one of the potential approach for tuning nanoelectronic devices for optimal thermal management and thermoelectric devices. In this work, I present a systematic investigation on how the group velocity and frequency of different phonon modes depend on various h-BN defect concentrations and defect patterns in ZSWCNTs. The study was extended to investigate the effect of hexagonal-C defects on the electronic and vibrational properties of zigzag single wall Boron Nitride nanotubes (ZSWBNNTs).

xxi, 134 p. : ill. (some col.) / Hydrogenated nanocrystalline silicon (nc-Si:H) is a semiconducting material that is very useful as a thin film photovoltaic. A mixture of amorphous and crystalline silicon components, nc-Si:H shows good carrier mobilities, enhanced infrared response, and high resilience to light-induced degradation of its electronic properties, a thermally reversible degenerative phenomenon known as the Staebler-Wronski Effect (SWE). However, production of nc-Si:H is difficult in part because the structural and electronic properties of this material are not well understood. For example, its electronic properties have even been observed by some authors to improve upon prolonged light exposure, in direct opposition to the SWE observed in purely amorphous thin film silicon. We used several junction capacitance based measurements together with characterization methods such as Raman spectroscopy and secondary ion mass spectroscopy to better understand the structure/function relationships present in nc-Si:H. Drive level capacitance profiling (DLCP) was used to determine densities, spatial distributions, and energies of deep-gap defects. Transient photocapacitance (TPC) and transient photocurrent (TPI) were used to characterize optical transitions and the degree of minority carrier collection. Materials had crystallite volume fractions between 20% and 80% and were deposited using RF and modified VHF glow discharge (PECVD) processes at United Solar Ovonic, LLC. Measurements were made as a function of metastable state: annealed states were produced by exposing the material to temperatures above 370K for 0.5h and the lightsoaked state was produced by exposure to 200mW/cm 2 610nm long-pass filtered light from an ELH halogen source for 100h. We identified two deep defects in nc-Si:H. A primary defect appearing throughout the material at an electronic transition energy of roughly 0.7eV below the conduction band, and a second defect 0.4eV below the conduction band which was localized near the p/i junction interface. Results suggested that the deeper defect is related to the presence of oxygen and is located in grain boundary regions. The energy depth of this defect appears also to be somewhat dependent on metastable state. This phenomenon, and the universal decrease in minority carrier collection upon lightsoaking are accounted for in a model of electronic behavior we have developed over the course of this study. / Committee in charge: Dr. Miriam Deutsch, Chairperson; Dr. J. David Cohen, Advisor; Dr. Roger Haydock, Member; Dr. Heiner Linke, Member Dr. Mark Lonergan Outside Member

MAIA JÚNIOR, Francisco Franciné. Cristais anidros das bases do ADN são semicondutores de Gap largo. 2011. 243 f. Tese (Doutorado em Física) - Programa de Pós-Graduação em Física, Departamento de Física, Centro de Ciências, Universidade Federal do Ceará, Fortaleza, 2011. / Submitted by francisco lima (admir@ufc.br) on 2014-03-18T13:34:36Z No. of bitstreams: 1 2011_Tese_ffmaiajunior.pdf: 27698119 bytes, checksum: f4553d0bed3b17a38cc9b90fb8e55c88 (MD5) / Approved for entry into archive by Edvander Pires(edvanderpires@gmail.com) on 2014-05-19T19:27:28Z (GMT) No. of bitstreams: 1 2011_Tese_ffmaiajunior.pdf: 27698119 bytes, checksum: f4553d0bed3b17a38cc9b90fb8e55c88 (MD5) / Made available in DSpace on 2014-05-19T19:27:28Z (GMT). No. of bitstreams: 1 2011_Tese_ffmaiajunior.pdf: 27698119 bytes, checksum: f4553d0bed3b17a38cc9b90fb8e55c88 (MD5) Previous issue date: 2011 / Guanine (G), adenine (A), cytosine (C), and thymine (T) nucleotide bases are the essential building blocks of DNA (deoxyribonucleic acid), which contains the genetic information used to build living cells. DNA strands are also promising candidates to fabricate molecular nanodevices, since they are stable polymers easy to replicate. Despite the early suggestion of the possibility of using DNA as a nanoscale conductor almost ten years after the elucidation of its helical structure, charge carrier transport through DNA-based structures is still a matter of debate. Here, we present the structural, electronic and optical properties of anhydrous crystals of DNA nucleobases found after DFT (Density Functional Theory) calculations, as well as experimental measurements of optical absorption for powders of these crystals. Experimental measurements of the UV absorption spectra for the anhydrous crystals were carried out on these pellets using a Varian Cary 5000 UV-visible NIR spectrophotometer. The absorption spectrum of the samples was recorded in the wavelength range between 200 and 800 nm (50000-12500 cm-1). The computational simulations of the present work were performed using the CASTEP code, which is based in the DFT approach. The Local Density Approximation (LDA) exchange-correlation potential developed by Ceperley and Alder and parametrized by Perdew and Zunger was adopted as well. With respect to our choice of functional, a note of caution must be made: in anhydrous DNA bases crystals, van der Waals interactions along the molecular stacking axis and hydrogen bonding between molecules in the same stacking plane are relevant to explain their structural features, and it is well known that pure DFT methods are unable to give a good description of dispersive forces. Besides, the LDA approximation is not the best option to provide an accurate account of hydrogen bonds. However, some DFT studies of layered crystals such as graphite as well as guanine hydrated crystals have shown that the LDA gives reasonable values for atomic distances, notwithstanding the limitations of this functional. This and the relatively low cost of LDA computations have motivated us to its adoption instead of more sophisticated (and computationally expensive) means. Guanine and cytosine (adenine and thymine) anhydrous crystals are predicted from the DFT simulations to be direct (indirect) band gap semiconductors, with values 2.68 eV and 3.30 eV (2.83 eV and 3.32 eV), respectively, while the experimentally estimated band gaps we have measured are 3.7 eV and 3.8 eV (3.5 eV and 4.0 eV), in the same order. Our LDA figures for the energy gaps are smaller than experimental values, as expected, and the gaps estimated from the optical absorption measurements presented in this work are in general smaller than experimental data available in the literature (except for guanine). The LDA ordering of increasing band gaps is G < A < C < T, while the ordering of gaps obtained experimentally is not settled: our work finds (from optical absorption measurements) A < G < C < T in contrast with the X-ray measurements, that indicate the energy gap sequence G < C < A < T. For electrons and holes moving along selected hydrogen bonds (parallel to the molecular plane of a given nucleobase), effective masses are in general large, exception made to thymine. When the same electrons move along the pi-stacking axis, however, effective masses stay between 4.0 and 6.3 free electron masses (m0), which suggests that stackings of nucleobases behave like wide gap semiconductors for electrons. The perpendicular transport of holes is also favored for nucleobase stackings without thymine. Finally, the complex dielectric function was calculated for each anydrous DNA base crystal, and a very pronounced anisotropy was observed for polarized incident light in the cases of guanine, adenine, and thymine, but not for cytosine. / As bases nucleotídicas guanina (G), adenina (A), citosina (C) e timina (T) são bases nucleotídicasos blocos essenciais da molécula do ácido desoxiribonucleico (ADN), que contém a as informações genéticas usadas pelas células vivas. Filamentos de ADN são também candidatos promissores para fabricação nanodispositivos moleculares, visto que polímeros estáveis e de fácil replicação. Apesar desta sugestão inicial da possibilidade de usar o ADN como condutor em nanoescala apenas dez anos após a elucidação da estrutura helicoidal do ADN, o transporte de portadores de cargas através de estruturas baseadas no ADN ainda são matéria de debate. Aqui, são apresentadas as propriedades estruturais, eletrônicas e ópticas dos cristais anidros das bases do ADN obtidas após cálculos baseados na teoria do funcional da densidade (DFT, do inglês Density Functional Theory), assim como medidas de absorção ótica para o pó desses cristais. Os experimentos do espectro absorção UV para os cristais foram realizadas sobre pastilhas usando o espectrometro Varian Cary 5000 UV-visible NIR, considerando o intervalo de 200 and 800 nm (50000-12500 cm-1). Os cálculos teóricos da presente tese foram desenvolvidos usando o pacote CASTEP, baseado na teoria DFT. Na descrição do potencial de troca e correlação, foi utilizada aproximação local da densidade (LDA, do inglês Local Density Approximation) desenvolvida por Cerpeley e Alder e parametrizado por Perdew e Zunger (CA-PZ). Sobre a escolha do funcional, uma observação deve ser feita: nos cristais anidros das bases do ADN, interações de van der Waals ao longo do eixo de empilhamento molecular e as ligações de hidrogênio entre as moléculas do mesmo plano são relevantes na explicação das suas características, e é bem conhecido que os métodos de DFT puro são incapazes de uma boa descrição das forças dispersivas. Além disso, a aproximação LDA não é a melhor opção para cálculos precisos das ligações de hidrogênio. Entretanto, alguns trabalhos DFT de cristais formados por camadas tais como grafite e o cristal hidratado da guanina mostraram que o funcional LDA fornece valores razoáveis para as distâncias atômicas, contrariando as limitações desse funcional. Isso e o baixo custo computacional foram as motivações que levaram a sua escolha em vez da adoção de funcionais mais sofisticados (e computacionalmente mais pesados). Os cristais de guanina e citosina (adenina e timina) são previstos terem gaps diretos (indiretos), com os valores experimentais estimados a partir da absorção de 3,7 eV e 3,8 eV (3,8 eV e 4,0 eV), na mesma ordem. Os resultados LDA mostraram gaps de energia menores do que os valores experimentais, como esperado, e os gaps experimentais estimados a partir da absorção ótica são, em geral, menores do que os valores experimentais disponíveis na literatura (exceto, para a guanina). A ordem crescente nos valores calculados dos gaps de energia para os cristais é dada por G < A < C < T, enquanto os valores experimentais obtidos nesta tese (a partir da absorção óptica) seguem a ordem A < G < C < T em contraste com as medidas de raios-x, que indicam a sequência G < C < A < T. Para os elétrons e buracos se movendo das ligações de hidrogênio (paralelas ao plano molecular da base), as massas efetivas são geralmente elevadas, exceto para a timina. Quando os mesmos elétrons se movimentam ao do eixo de empilhamento molecular, entretanto, as massas efetivas ficam entre 4,0 e 6,3m0, sugerindo estes cristais se comportam como semicondutores de gap largo ao longo das direções de empilhamento molecular. O transporte de buracos também é favorecido ao longo da direção de empilhamento, exceto para a timina. Finalmente, a função dielétrica complexa foi calculada para cada cristal anidro das bases do ADN, sendo observada uma forte anisotropia para a incidência de luz polarizada nos casos da guanina, adenina e timina, mas não para a citosina.

Made available in DSpace on 2018-06-27T18:55:56Z (GMT). No. of bitstreams: 3 Paulo Inacio Obregon do Carmo.pdf: 2602281 bytes, checksum: 7b94441337f178869475a9dda7ce86a5 (MD5) Paulo Inacio Obregon do Carmo.pdf.txt: 111751 bytes, checksum: 0fc962a4e4b8838558177bcf7859a818 (MD5) Paulo Inacio Obregon do Carmo.pdf.jpg: 3913 bytes, checksum: 6352e7404ddd8978e5632801dda2b544 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Carbon Nanotubes (CNTs) they are object of intense theoretical and experimental researches, tends in view the extreme sensibility of their electronic properties, deformations and to defects in the hexagonal net to alterations in the structural parameters. The structural and electronic properties of CNTs have been considered the base for the development of coverings nanoestruturados destined to the research space, sensor and fotovoltaics devices, among others. A better knowledge of the properties of these materials is necessary so that we can project more efficient and durable devices, besides assisting to crescent it disputes of the market of technological innovation. In this work analyses of the elastic and electronic properties of single-walled nanotubes carbon (SWCNT) and multi-walled with two (DWCNT) and three (TWCNT) shells deformed by axial traction were accomplished. The structural and energy properties of CNTs studied were obtained through calculations of first beginnings, with base in the Theory of the Functional of the Density, that one find implemented in the program SIESTA (Spanish Initiative goes Electronic Simulations with Thousand of Atoms). Considering CNTs discreet shells and making use of the mechanics solids continuous, we obtained that the elasticity modulus varies of 0,65TPa - for the nanotubo (4,4), to 0,95 TPa - for NTC (10,10). It was verified that the mechanical resistance increases with the diameter of CNT, except for CNT (15,15) that presents smaller mechanical resistance than CNT (10,10). We determined with base in the variation of the elastic energy and of the connection length the modulus of young. We observed that the nanotubos with different layers have behaviors differentiated front to the tensions, so much in points of rupture of the chemical structure, when to the electronic properties. Nanotubes of carbon of the type armchair are metallic, however starting from certain deformations, they become semiconductors and their energy gap varies in agreement with the intensity of the applied tension. / Nanotubos de carbono (NTCs) são objeto de intensas pesquisas teóricas e experimentais, tendo em vista a extrema sensibilidade das suas propriedades eletrônicas a alterações nos parâmetros estruturais, deformações e a defeitos na rede hexagonal. As propriedades estruturais e eletrônicas dos NTCs têm sido consideradas a base para o desenvolvimento de revestimentos nanoestruturados destinados à pesquisa espacial, sensores, dispositivos fotovoltaicos, entre outros. Um melhor conhecimento das propriedades destes materiais é necessário para que se possa projetar dispositivos mais eficientes e duráveis, além de atender a crescente demanda do mercado de inovação tecnológica. Neste trabalho foram realizadas análises das propriedades elásticas e eletrônicas de nanotubos de carbono de uma (SWCNT), duas (DWCNT) e três (TWCNT) camadas deformados por tração axial. As propriedades estruturais e energéticas dos NTCs estudados foram obtidas através de cálculos de primeiros princípios, com base na Teoria do Funcional da Densidade, que se encontra implementada no programa SIESTA (Spanish Initiative for Electronic Simulations with Thousand of Atoms). Considerando os NTCs cascas discretas e fazendo uso da mecânica dos sólidos contínuos, obtivemos que o módulo de elasticidade varia de 0,65TPa - para o nanotubo (4,4), a 0,95 TPa para o NTC (10,10). Constatou-se que a resistência mecânica aumenta com o diâmetro do NTC, com exceção do NTC (15,15) que apresenta resistência mecânica menor que o NTC (10,10). Determinamos com base na variação da energia elástica e do comprimento de ligação o módulo de Young. Observamos que os nanotubos com diferentes camadas têm comportamentos diferenciados frente às tensões, tanto em pontos de ruptura da estrutura química, quanto às propriedades eletrônicas. Nanotubos de carbono do tipo armchair são metálicos, porém a partir de determinadas deformações, tornam-se semicondutores e seus gaps de energia variam de acordo com a intensidade da tensão aplicada.

As diimidas naftálicas simétricas têm sido vastamente estudadas devido suas propriedades químicas, ópticas, e eletrônicas. A possibilidade de modular suas propriedades com a substituição de grupos diversos na formação da imida, viabiliza aplicações em dispositivos eletrônicos, conversão de energia e produção de redes de coordenação metalo-orgânicas. Neste trabalho sintetizou-se uma série de 5 diimidas naftálicas (NDIs) simétricas com substituintes aromáticos. Foram analisadas as características espectroscópicas e eletrônicas com obtenção dos valores de band-gap óptico através de ensaios de voltametria cíclica e cálculos teóricos (DFT), mostrando a influência dos substituintes nas propriedades eletrônicas. Estas moléculas apresentam indícios de agregação em determinados solventes tornando possível a produção de filmes finos. As NDIs produzidas foram intercaladas em uma matriz inorgânica lamelar, o pentóxido de vanádio amorfo, e melhorando consideravelmente, via de regra, a capacidade específica de carga quando analisados em sistemas trocadores de íon lítio, aplicados geralmente em cátodos de bateria, com valores da ordem de 190 mA.h.g-1 (sob 100 uA, variação de E +1,2V à -1,2V). É provavelmente um dos primeiros trabalhos a utilizar NDIs em sistemas mistos de matrizes inorgânicas aplicados em trocadores de íons. Algumas apresentam potencial para dispositivos de conversão de luz em eletricidade. / Symmetric naphthalic diimides have been extensively studied due to their chemical, optical, and electronic properties. The possibility of modulating their properties by substitution with several groups in the formation of imides allows diverse applications in electronic devices, energy conversion, production of metallo-organic frameworks (MOFs). In this thesis, a series of 5 symmetrical aromatic-substituted naphthalic diimides (NDIs) were sinthesized. We have studied their optical and electronic characteristics obtaining optical band-gap with cyclic voltammetry tests and theoretical calculations (DFT), showing the influence of substituent in the electronic properties. Some of these imides may aggregate in certain solvents allowing this way the production thin films. The NDIs were intercalated in the inorganic intercalation matrix of amorphous vanadium pentoxide, and showed generally considerable improvement in the specific charge capacity when used in lithium ion exchange systems, that are usually applied in battery cathodes, reaching values of the order of 190 mA.h.g-1 (under 100 uA, E variation of + 1.2V to -1.2V). This is probably one of the first works using NDIs in mixed systems to applied inorganic matrices as ion exchangers. Some of them may be used for light conversion to electricity devices.

This diploma thesis is focused on calculation of both structure and electronic properties of the graphene after the adsorption of atomic and molecular oxygen and urea using the Density Functional Theory (DFT). The influence of van der Waals interactions on the structure and adsorption energy is studied, as well as influence of the thermal corrections, the charge density spatial distribution and the electronic doping of graphene after the adsorption of the adsorbant on the graphene.