Índice de aromaticidade baseado na deslocalização, degenerescência e densidade (D3BIA) para acenos e moléculas homoaromáticas

The aromaticity index is an important tool for the investigation of aromatic molecules. This work consists on new applications of the aromaticity index developed by teacher Caio Lima Firme, so-called D3BIA (density, delocalization, degeneracy-based index of aromaticity). It was investigated its correlation with other well-known aromaticity indexes, such as HOMA (harmonic oscillator model of aromaticity), NICS (nucleus independent chemical shielding), PDI (para-delocalization index), magnetic susceptibility (), and energetic factor in the study of aromaticity of acenes and homoaromatic species based on bisnoradamantanyl cage. The density functional theory (DFT) was used for optimization calculations and for obtaining energetic factors associated with aromaticity and indexes HOMA and NICS. From quantum theory of atoms in molecules (QTAIM) it was obtained the indexes D3BIA, PDI and . For acenes, when the over-mentioned indexes were applied it was observed no correlation except for D3BIA and HOMA (R2=0.752). For bisnoradamantenyl dication and its derivatives, it was obtained a good correlation between D3BIA and NICS. Moreover, it was evaluated solely one of the factors used on D3BIA calculation, the delocalization index uniformity (DIU), so as to investigate its possible influence on stability of chemical species. Then, the DIU was compared with the formation Gibbs free energy of some pairs of carbocations, isomers or not, which each pair had small difference in point group symmetry and no difference among other well-known stability factors. The obtained results indicate that DIU is a new stability factor related to carbocations, that is, the more uniform the electron density delocalization, the more stable the is carbocation. The results of this work validate D3BIA and show its importance on the concept of aromaticity, indicating that it can be understood from degeneracy of atoms belonging the aromatic site, the electronic density in the aromatic site and the degree of uniformity of electron delocalization

Estudo teórico das propriedades químicas e físicas envolvendo o elemento 118

Pós-graduação em Ciência e Tecnologia de Materiais - FC

A irracionalidade e transcendência do número π

Pós-graduação em Matemática em Rede Nacional - IBILCE

A irracionalidade e transcendência do número e

Pós-graduação em Matemática em Rede Nacional - IBILCE

Modelamento do transporte eletrônico em dispositivos moleculares

No presente trabalho, simulamos as propriedades de transporte e espectro de absorção do composto orgânico Vermelho de Etila. Este é o primeiro estudo teórico de um indicador específico de pH utilizado como nanodispositivo, com base na teoria quântica e no modelo de transporte não-difuso. A distribuição de carga ao longo da molécula é determinada através da técnica, Ab initio, como uma função de um campo elétrico externo. Baseado em um modelo de multiníveis ressonantes também calculamos a corrente como função da tensão de polarização. O acúmulo de carga e a corrente apresentam comportamento semelhante, como a condução do tipo ressonante e curvas carga-tensão e corrente-tensão assimétricas. Os principais resultados sugerem que o sistema presente poderia funcionar como um transistor molecular bi-direcional. Estendemos esta metodologia de análise para outro dispositivo molecular, mas composto de três terminais. Para este sistema, nossa descoberta principal é a resistência diferencial negativa (RDN) na carga Q como uma função do campo elétrico externo. Para explicar este efeito RDN, aplicamos um modelo capacitivo fenomenológico, também baseado em um sistema de multiníveis localizados (que podem ser os LUMOs – Lowest Unoccupied Molecular Orbital – Orbitais moleculares desocupados mais baixos). A capacitância descreve, por efeito de carregamento, a causa do bloqueio de Coulomb (BC) no transporte. Mostramos que o efeito BC dá origem a uma RDN para um conjunto adequado de parâmetros fenomenológicos como: taxa de tunelamento e energia de carregamento. O perfil da RDN obtida nas duas metodologias, ab initio e fenomenológica, estão em comum acordo.

Silvino Jacques: interseções no mito do bandoleiro

Pós-graduação em Letras - IBILCE

A study of the dynamics of quantum correlations

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Potenciais singulares na equação de Schrodinger unidimensional via transformada de Laplace

The present work has as its goal to treat well known and interesting unidimensional cases from quantum mechanics through an unusual approach within this eld of physics. The operational method of Laplace transform, in spite of its use by Erwin Schrödinger in 1926 when treating the radial equation for the hydrogen atom, turned out to be forgotten for decades. However, the method has gained attention again for its use as a powerful tool from mathematical physics applied to the quantum mechanics, appearing in recent works. The method is specially suitable to the approach of cases where we have potential functions with even parity, because this implies in eigenfunctions with de ned parity, and since the domain of this transform ranges from 0 to ∞, it su ces that we nd the eigenfunction in the positive semi axis and, with the boundary conditions imposed over the eigenfunction at the origin plus the continuity (discontinuity) of the eigenfunction and its derivative, we make the odd, even or both parity extensions so we can get the eigenfunction along all the axis. Factoring the eigenfunction behavior at in nity and origin, we take the due care with the points that might bring us problems in the later steps of the solving process, thus we can manipulate the Schrödinger's Equation regardless of time, so that way we make it convenient to the application of Laplace transform. The Chapter 3 shows the methodology that must be followed in order to search for the solutions to each problem

Política, Território, Poder e a Agroindustrialização em assentamentos de reforma agrária no Rio Grande do Sul

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Nanotecnologia e nanociência em livros didáticos de física do nível médio: discursos sobre a tecnologia e a educação científica e tecnológica

In this contribution, we analyze conceptual approaches to nanotechnology and nanoscience in recent issues of secondary education of Brazilian physics textbooks. We analyzed fifteen collections of Physics textbooks of recent editions, however, only two books, belonging to different collections incorporate considerations about nanotechnology and nanoscience in their approaches. We focus our analysis on three aspects, namely: the place dedicated to approaches to nanoscience and nanotechnology, notions about technology and its contributions to critical scientific education. This is a qualitative research; it was used as conceptual approaches the Philosophy of Technology, The Discourse Analysis (DA) and Science, Technology, Society (STS) concepts. We found that in two examined textbooks the approaches to nanoscience and nanotechnology is a complementary description of modern physics, associated with quantum theory. In this context, the concepts of nanoscience and nanotechnology focus superficially in the genesis of the field and some possible areas of applications. It was not identified in all textbooks warnings about the potential risks to human health and the environment from the use of nanotechnology and nanoscience. We understand that textbooks approaches about nanotechnology and nanoscience round a instrumental technological perspective, however keep away from the scientific and technological critical education.

Tempos de tunelamento

Pós-graduação em Física - IFT

Estudo teórico de intermediários tetraédricos acidez / basicidade e estereosseletividade enzimáticos

The present work aimed first, the theoretical study of tetrahedral intermediate stability formed from carbonyl addition reactions using the second (MP2) and third (MP3) order Møller–Plesset perturbation theory. Linear correlations between electronic energy difference of reactions with Wiberg Indexes and C-O bond lengths were obtained, and was observed that the stability of adducts formed depends directly of electronic density involved between these atoms. The knowing of electronic parameters of these structures has an important hole due to the large use on reactions that in his course forms this tetrahedral intermediate. Employing the ONIOM (B3LYP:AMBER) methodology, was evaluated the stereoselectivity of a enzymatic reaction between CAL B enzyme and a long chain ester. In this study, were obtained the electronic energies of ground state and intermediate state of transesterification rate-determing step from two possible proquirals faces Re and Si. The objective was study the enantioselectivity of CAL B and rationalizes it using quantum theory of atoms in molecules (QTAIM). A theoretical study employing inorganic compounds was performed using ab initio CBS-QB3 method aiming to find a link between thermodynamic and equilibrium involving acids and bases. The results observed showed an excellent relationship between difference in Gibbs free energy, ΔG of acid dissociation reaction and ΔG of hydrolysis reaction of the corresponding conjugate base. It was also observed, a relationship between ΔG of hydrolysis reaction of conjugate acids and their corresponding atomic radius showing that stability plays an important role in hydrolysis reactions. The importance of solvation in acid/base behavior when compared to theoretical and experimental ΔG´s also was evaluated.