Efeitos das correlações inter-átomos adsorvidos na densidade de estados do grafeno

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Análise da potencialidade a condução do BDT através da densidade eletrônica de estados via tight binding e desenvolvimento de software (B3J)

Neste trabalho nos propomos a fazer um estudo acerca da potencialidade de condução eletrônica no polímero BDT (1,3-benzoditiol 4H-ciclopenta[2,1-b:3,4b’]). O estudo usual de polímeros conjugados é feito de modo a obter sua densidade de estados com diversos tipos e níveis de dopagem. O método de Huckel é o mais utilizado e se baseia na separabilidade das ligações sigma e pi que é possível quando a molécula estudada é plana. Os polímeros conjugados são em sua maioria planos e estão inseridos nesta aproximação. O monômero do BDT apresenta sua geometria fora do plano por apresentar ligações com orbitais sp3. Para contornar esse problema foi desenvolvido o programa B3J, que considera todos os orbitais de valencia (s, px, py e pz). O programa B3J calcula a densidade de estados de sistemas poliméricos. O estudo das bandas do BDT foi feito com este software. Calculamos a densidade de estados do sistema neutro e com diversos níveis de dopagem, com distribuição aleatória e ordenada dos defeitos, dopagem do tipo n e do tipo p. O comportamento do quadrado do coeficiente da expansão da função de onda foi obtido para polímeros de até 20 monômeros. Estes cálculos foram obtidos com geometrias dos métodos AM1 e PM3. Obtivemos os espectros de absorção de oligômeros a fim de inferir seu comportamento para um polímero. Foram utilizados cálculos de otimização de geometria através dos métodos semi-empíricos AM1 e PM3 e ZINDO/S e o método DFT. Em outro objetivo desta monografia há o estudo do aproveitamento de tetrâmeros de BDT como dispositivos eletrônicos. Tais oligômeros foram otimizados em diversos valores de potencial elétrico, com a inserção em suas cadeias de moléculas doadoras e aceitadoras para induzir um aumento no momento de dipolo da mesma.

Capturando estados ligados no contínuo de átomos fantasmas no grafeno

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Batimentos quânticos dependentes do SPIN via STM

Pós-graduação em Ciência dos Materiais - FEIS

O grafeno versus gás de elétrons 2d: filtro fano relativístico de spins por meio de pontas de afm e stm

Pós-graduação em Ciência dos Materiais - FEIS

Sistemas Nanoestruturados: Heteroestruturas Quasi-Periódicas de Nitretos e Cálculos Ab initio em Polimorfos CaCO3

The physical properties and the excitations spectrum in oxides and semiconductors materials are presented in this work, whose the first part presents a study on the confinement of optical phonons in artificial systems based on III-V nitrides, grown in periodic and quasiperiodic forms. The second part of this work describes the Ab initio calculations which were carried out to obtain the optoeletronic properties of Calcium Oxide (CaO) and Calcium Carbonate (CaCO3) crystals. For periodic and quasi-periodic superlattices, we present some dynamical properties related to confined optical phonons (bulk and surface), obtained through simple theories, such as the dielectric continuous model, and using techniques such as the transfer-matrix method. The localization character of confined optical phonon modes, the magnitude of the bands in the spectrum and the power laws of these structures are presented as functions of the generation number of sequence. The ab initio calculations have been carried out using the CASTEP software (Cambridge Total Sequential Energy Package), and they were based on ultrasoft-like pseudopotentials and Density Functional Theory (DFT). Two di®erent geometry optimizations have been e®ectuated for CaO crystals and CaCO3 polymorphs, according to LDA (local density approximation) and GGA (generalized gradient approximation) approaches, determining several properties, e. g. lattice parameters, bond length, electrons density, energy band structures, electrons density of states, e®ective masses and optical properties, such as dielectric constant, absorption, re°ectivity, conductivity and refractive index. Those results were employed to investigate the confinement of excitons in spherical Si@CaCO3 and CaCO3@SiO2 quantum dots and in calcium carbonate nanoparticles, and were also employed in investigations of the photoluminescence spectra of CaCO3 crystal

Propriedades estruturais e optoeletrônicas dos compostos SrSnO3, SrxBa1-xSnO3 e BaSnO3

In this work we present a study for the structural, electronic and optical properties, at ambient conditions of SrSnO3, SrxBa1

Coupling of magnetic, strain and electric polarization fields in the structure of multiferroic material

The comprehensive study on the coupling of magnetism, electrical polarization and the crystalline lattice with the off-stoichiometric effects in self-doped multiferroic hexagonal h-LuMnxO3±δ (0.92≤x≤1.12) ceramic oxides was carried out for the PhD work. There is a complex coupling of the three ferroic degrees. The cancelation of the magnetic moments of ions in the antiferromagnetic order, electric polarization with specific vortex/antivortex topology and lattice properties have pushed researchers to find out ways to disclose the underlying physics and chemistry of magneto-electric and magneto-elastic couplings of h-RMnO3 multiferroic materials. In this research work, self-doping of Lu-sites or Mn-sites of h-LuMnxO3±δ ceramics prepared via solid state route was done to pave a way for deeper understanding of the antiferromagnetic transition, the weak ferromagnetism often reported in the same crystalline lattices and the ferroelectric properties coupled to the imposed lattice changes. Accordingly to the aim of the PhD thesis, the objectives set for the sintering study in the first chapter on experimental results were two. First, study of sintering off-stoichiometric samples within conditions reported in the bibliography and also extracted from the phase diagrams of the LuMnxO3±δ, with a multiple firings ending with a last high temperature step at 1300ºC for 24 hours. Second, explore longer annealing times of up to 240 hours at the fixed temperature of 1300 ºC in a search for improving the properties of the solid solution under study. All series of LuMnxO3±δ ceramics for each annealing time were characterized to tentatively build a framework enabling comparison of measured properties with results of others available in literature. XRD and Rietveld refinement of data give the evolution the lattice parameters as a function to x. Shrinkage of the lattice parameters with increasing x values was observed, the stability limit of the solid solution being determined by analysis of lattice parameters. The evolution of grain size and presence of secondary phases have been investigated by means of TEM, SEM, EDS and EBSD techniques. The dependencies of grain growth and regression of secondary phases on composition x and time were further characterized. Magnetic susceptibility of samples and magnetic irreversibility were extensively examined in the present work. The dependency of magnetic susceptibility, Neel ordering transition and important magnetic parameters are determined and compared to observation in other multiferroics in the following chapter of the thesis. As a tool of high sensitivity to detect minor traces of the secondary phase hausmannite, magnetic measurements are suggested for cross-checking of phase diagrams. Difficulty of previous studies on interpreting the magnetic anomaly below 43 K in h-RMnO3 oxides was discussed and assigned to the Mn3O4 phase, with supported of the electron microscopy. Magneto-electric coupling where AFM ordering is coupled to dielectric polarization is investigated as a function of x and of sintering condition via frequency and temperature dependent complex dielectric constant measurements in the final chapter of the thesis. Within the limits of solid solubility, the crystalline lattice of off-stoichiometric ceramics was shown to preserve the magneto-electric coupling at TN. It represents the first research work on magneto-electric coupling modified by vacancy doping to author’s knowledge. Studied lattices would reveal distortions at the atomic scale imposed by local changes of x dependent on sintering conditions which were widely inspected by using TEM/STEM methods, complemented with EDS and EELS spectroscopy all together to provide comprehensive information on cross coupling of distortions, inhomogeneity and electronic structure assembled and discussed in a specific chapter. Internal interfaces inside crystalline grains were examined. Qualitative explanations of the measured magnetic and ferroelectric properties were established in relation to observed nanoscale features of h-LuMnxO3±δ ceramics. Ferroelectric domains and topological defects are displayed both in TEM and AFM/PFM images, the later technique being used to look at size, distribution and switching of ferroelectric domains influenced by vacancy doping at the micron scale bridging to complementary TEM studies on the atomic structure of ferroelectric domains. In support to experimental study, DFT simulations using Wien2K code have been carried out in order to interpret the results of EELS spectra of O K-edge and to obtain information on the cation hybridization to oxygen ions. The L3,2 edges of Mn is used to access the oxidation state of the Mn ions inside crystalline grains. In addition, rehybridization driven ferroelectricity is also evaluated by comparing the partial density of states of the orbitals of all ions of the samples, also the polarization was calculated and correlated to the off-stoichiometric effect.

Estudo de modelos epidemiológicos determinísticos básicos que incluem transmissão vertical

No estudo da propagação de uma doença infecciosa, diz-se que sua transmissão ocorre horizontalmente, quando um indivíduo suscetível tem um contato direto ou indireto com um indivíduo infeccioso. Algumas doenças, entretanto, também podem ser transmitidas verticalmente, entendendo-se que, neste caso, a doença é transmitida a um indivíduo, ao ser gerado por uma mãe infecciosa. Fazendo uso de modelos epidemiológicos determinísticos básicos, envolvendo sistemas de equações diferenciais ordinárias, nosso principal objetivo, neste trabalho, consiste em investigar qual o papel da transmissão vertical na propagação de doenças causadas por microparasitas. Diversas formas de inclusão de transmissão vertical são apresentadas e, em cada modelo estudado, investigamos a existência e a estabilidade local dos estados de equilíbrio da população hospedeira, identificamos os parâmetros e limiares que caracterizam a dinâmica do sistema, e completamos as informações decorrentes dos resultados analíticos com a apresentação de soluções numéricas do mesmo. Por fim, comparamos os efeitos da transmissão horizontal com aqueles decorrentes da transmissão vertical.

Propriedades física de molécilas orgânicas e compostos do tipo perovskita CdSiO3 e CaPbO3

In the first part of this work our concern was to investigate the thermal effects in organic crystals using the theory of the polarons. To analyse such effect, we used the Fröhlich s Hamiltonian, that describes the dynamics of the polarons, using a treatment based on the quantum mechanics, to elucidate the electron-phonon interaction. Many are the forms to analyzing the polaronic phenomenon. However, the measure of the dielectric function can supply important information about the small polarons hopping process. Besides, the dielectric function measures the answer to an applied external electric field, and it is an important tool for the understanding of the many-body effects in the normal state of a polaronic system. We calculate the dielectric function and its dependence on temperature using the Hartree-Fock decoupling method. The dieletric function s dependence on the temperature is depicted by through a 3D graph. We also analyzed the so called Arrhenius resistivity, as a functionof the temperature, which is an important tool to characterize the conductivity of an organic molecule. In the second part we analyzed two perovskita type crystalline oxides, namely the cadmium silicate triclinic (CdSiO3) and the calcium plumbate orthorhombic (CaPbO3), respectively. These materials are normally denominated ABO3 and they have been especially investigated for displaying ferroelectric, piezoelectric, dielectrics, semiconductors and superconductors properties. We found our results through ab initio method within the functional density theory (DFT) in the GGA-PBE and LDA-CAPZ approximations. After the geometry optimization for the two structure using the in two approximations, we found the structure parameters and compared them with the experimental data. We still determined further the angles of connection for the two analyzed cases. Soon after the convergence of the energy, we determined their band structures, fundamental information to characterize the nature of the material, as well as their dielectrics functions, optical absorption, partial density of states and effective masses of electrons and holes

Estudo teórico das propriedades eletrônicas e termodinâmicas de nanofitas quasiperiódicas BCN

Nanoscale materials composed of boron, nitrogen, and carbon have unique properties and may be useful in new technologies. In this thesis, we investigate some properties of BCN nanoribbons constructed according to the Fibonacci quasiperiodic sequence. We analyze properties such as structural stability, electronic density of states, electronic specific heat, band structure, and energy band gap. We have performed first-principles calculations based on density functional theory implemented in the SIESTA code. The results showed that nanoribbons present a fixed value of the formation energy. The electronic density of states was used to calculate the specific heat. We found an oscillatory behavior of the electronic specific heat, in the low temperature regime. We analyze the electronic band structure to determine the energy band gap. The energy band gap oscillates as a function of the Fibonacci generation index n. Our work suggest that appropriate choice of the building block materials of the quasiperiodic sequence, may lead to a tuneable band gap of the quasiperiodic nanoribbons.

Random path sampling applied to vector models of magnetism

The recently reported Monte Carlo Random Path Sampling method (RPS) is here improved and its application is expanded to the study of the 2D and 3D Ising and discrete Heisenberg models. The methodology was implemented to allow use in both CPU-based high-performance computing infrastructures (C/MPI) and GPU-based (CUDA) parallel computation, with significant computational performance gains. Convergence is discussed, both in terms of free energy and magnetization dependence on field/temperature. From the calculated magnetization-energy joint density of states, fast calculations of field and temperature dependent thermodynamic properties are performed, including the effects of anisotropy on coercivity, and the magnetocaloric effect. The emergence of first-order magneto-volume transitions in the compressible Ising model is interpreted using the Landau theory of phase transitions. Using metallic Gadolinium as a real-world example, the possibility of using RPS as a tool for computational magnetic materials design is discussed. Experimental magnetic and structural properties of a Gadolinium single crystal are compared to RPS-based calculations using microscopic parameters obtained from Density Functional Theory.

Distribuição espacial do pico e ultraplâncton na plataforma continental e talude entre Cabo Frio (RJ) e Ubatuba (SP) e sua relação com a hidrodinâmica local: inverno de 2010

O picoplâncton (0,2 - 2,0 m) e ultraplâncton (> 2,0 - 5,0 m) despertam interesse por utilizarem ativamente a matéria orgânica dissolvida, estabelecendo a alça microbiana. Responsáveis por 50-80% da produção primária em águas oligotróficas, essas frações apresentam elevadas eficiência luminosa e razão superfície/volume que as permitem alcançar alto desenvolvimento mesmo sob baixas luminosidade e disponibilidade de nutrientes. Buscando relacionar a distribuição espacial e composição da comunidade pico e ultraplanctônica aos controles bottom-up na plataforma continental e talude ao largo dos Estados do Rio de Janeiro e São Paulo (22S a 26S), foram coletadas amostras de água em 39 estações oceanográficas e utilizadas as imagens dos sensores MODIS Terra e Aqua, bem como dados de hidrografia, para a descrição dos fenômenos oceanográficos de mesoescala. A abundância total de ambas as frações de tamanho, assim como a dominância do picoplâncton, reduziu em função do distanciamento da costa. Os organismos autotróficos foram em média (102 cél.mL-1 a 104 cél.mL-1 ) majoritariamente uma ordem de grandeza inferiores aos heterotróficos (103 cél.mL-1 a 105 cél.mL-1). A Água Central do Atlântico Sul (ACAS) e as plumas das baías de Guanabara e Sepetiba (RJ) permaneceram na plataforma interna favorecendo o aumento na concentração dos macronutrientes e refletindo na mudança da estrutura da comunidade através do aumento da contribuição de autótrofos no centro da plataforma, principalmente do ultraplâncton à superfície (cerca de 21%) e na profundidade do máximo de clorofila (44%). O transporte de águas costeiras carreadas por uma corrente de origem sul gerou o vórtice de plataforma identificado nas imagens de satélite para a região da plataforma interna de Ubatuba (SP), onde concentrações mais elevadas de amônio (0,28 M) e fosfato (9,64 M) a partir dos 50 m sustentaram maior densidade do ultra autótrofo (2,89 x 103 cél.mL-1) que superou a densidade de heterótrofos (2,50 x 103 cél.mL-1) no máximo de clorofila. Os resultados destacaram um forte gradiente nerítico-oceânico na distribuição dos organismos. Sugerem ainda a predominância do metabolismo heterotrófico na maior parte das águas oligotróficas da plataforma e talude entre o Rio de Janeiro e São Paulo, bem como a presença de caráter autotrófico naquelas regiões influenciadas por feições de mesoescala, como plumas estuarinas e vórtices de plataforma.

Turismo, território e desenvolvimento local: práticas de participação e governança no Baixo Guadiana

Tese de doutoramento, Turismo, Faculdade de Economia, Universidade do Algarve, 2013