Electron localization function at the correlated level

The electron localization function (ELF) has been proven so far a valuable tool to determine the location of electron pairs. Because of that, the ELF has been widely used to understand the nature of the chemical bonding and to discuss the mechanism of chemical reactions. Up to now, most applications of the ELF have been performed with monodeterminantal methods and only few attempts to calculate this function for correlated wave functions have been carried out. Here, a formulation of ELF valid for mono- and multiconfigurational wave functions is given and compared with previous recently reported approaches. The method described does not require the use of the homogeneous electron gas to define the ELF, at variance with the ELF definition given by Becke. The effect of the electron correlation in the ELF, introduced by means of configuration interaction with singles and doubles calculations, is discussed in the light of the results derived from a set of atomic and molecular systems

Estructura computacional i aplicacions de la semblança molecular quàntica

La tesis tracta diferents aspectes relacionats amb el càlcul de la semblança quàntica, així com la seva aplicació en la racionalització i predicció de l'activitat de fàrmacs. Es poden destacar dos progressos importants en el desenvolupament de noves metodologies que faciliten el càlcul de les mesures de semblança quàntica. En primer lloc, la descripció de les molècules mitjançant les funciones densitat aproximades PASA (Promolecular Atomic Shell Approximation) ha permès descriure amb suficient precisió la densitat electrònica dels sistemes moleculars analitzats, reduint substancialment el temps de càlcul de les mesures de semblança. En segon lloc, el desenvolupament de tècniques de superposició molecular específiques de les mesures de semblança quàntica ha permès resoldre el problema de l'alineament en l'espai dels compostos comparats. El perfeccionament d'aquests nous procediments i algoritmes matemàtics associats a les mesures de semblança molecular quàntica, ha estat essencial per poder progressar en diferents disciplines de la química computacional, sobretot les relacionades amb les anàlisis quantitatives entre les estructures moleculars i les seves activitats biològiques, conegudes amb les sigles angleses QSAR (Quantitative Structure-Activity Relationships). Precisament en l'àrea de les relacions estructura-activitat s'han presentat dues aproximacions fonamentades en la semblança molecular quàntica que s'originen a partir de dues representacions diferents de les molècules. La primera descripció considera la densitat electrònica global de les molècules i és important, entre altres, la disposició dels objectes comparats en l'espai i la seva conformació tridimensional. El resultat és una matriu de semblança amb les mesures de semblança de tots els parells de compostos que formen el conjunt estudiat. La segona descripció es fonamenta en la partició de la densitat global de les molècules en fragments. S'utilitzen mesures d'autosemblança per analitzar els requeriments bàsics d'una determinada activitat des del punt de vista de la semblança quàntica. El procés permet la detecció de les regions moleculars que són responsables d'una alta resposta biològica. Això permet obtenir un patró amb les regions actives que és d'evident interès per als propòsits del disseny de fàrmacs. En definitiva, s'ha comprovat que mitjançant la simulació i manipulació informàtica de les molècules en tres dimensions es pot obtenir una informació essencial en l'estudi de la interacció entre els fàrmacs i els seus receptors macromoleculars.

Number of particle creation and decoherence in the nonideal dynamical Casimir effect at finite temperature

In this work we investigate the dynamical Casimir effect in a nonideal cavity by deriving an effective Hamiltonian. We first compute a general expression for the average number of particle creation, applicable for any law of motion of the cavity boundary, under the only restriction of small velocities. We also compute a general expression for the linear entropy of an arbitrary state prepared in a selected mode, also applicable for any law of motion of a slow moving boundary. As an application of our results we have analyzed both the average number of particle creation and linear entropy within a particular oscillatory motion of the cavity boundary. On the basis of these expressions we develop a comprehensive analysis of the resonances in the number of particle creation in the nonideal dynamical Casimir effect. We also demonstrate the occurrence of resonances in the loss of purity of the initial state and estimate the decoherence times associated with these resonances. Since our results were obtained in the framework of the perturbation theory, they are restricted, under resonant conditions, to a short-time approximation. (C) 2009 Elsevier Inc. All rights reserved.

A theoretical study on the XeF(2) molecule

A relativistic four-component study was performed for the XeF(2) molecule by using the Dirac-Coulomb (DC) Hamiltonian and the relativistic adapted Gaussian basis sets (RAGBSs). The comparison of bond lengths obtained showed that relativistic effects on this property are small (increase of only 0.01 angstrom) while the contribution of electron correlation, obtained at CCSD(T) or CCSD-T levels, is more important (increase of 0.05 angstrom). Electron correlation is also dominant over relativistic effects for dissociation energies. Moreover, the correlation-relativity interaction is shown to be negligible for these properties. The electron affinity, the first ionization potential and the double ionization potential are obtained by means of the Fock-space coupled cluster (FSCC) method, resulting in DC-CCSD-T values of 0.3 eV, 12.5 eV and 32.3 eV, respectively. Vibrational frequencies and some anharmonicity constants were also calculated under the four-component formalism by means of standard perturbation equations. All these molecular properties are, in general, ill satisfactory agreement with available experimental results. Finally, a partition in terms of charge-charge flux-dipole flux (CCFDF) contributions derived by means of the quantum theory of atoms in molecules (QTAIM) in non-relativistic QCISD(FC)/3-21G* calculations was carried out for XeF(2) and KrF(2). This analysis showed that the most remarkable difference between both molecules lies on the charge flux contribution to the asymmetric stretching mode, which is negligible in KrF(2) but important in XeF(2). (c) 2008 Elsevier B.V. All rights reserved.

Contratos relacionais na indústria aeronáutica brasileira : um estudo empírico do modelo de parcerias de risco da Embraer

O presente trabalho é um estudo empírico das práticas contratuais adotadas pela EMBRAER posteriormente ao seu processo de privatização em 1994, e do arranjo contratual empregado para viabilizar a realização dos projetos de aeronaves responsáveis pelo ressurgimento da empresa ao final da década 1990. Aspecto fundamental da engenharia contratual empreendida foi a formação das chamadas Parcerias de Risco entre a Embraer e um grupo selecionado de fornecedores-chave visando o co-desenvolvimento das aeronaves. A análise das informações obtidas na pesquisa aponta a importância epistemológica de se utilizar novos instrumentos de análise que permitam compreender melhor as práticas contratuais empregadas e seu papel no desenvolvimento. Assim, utilizamos a teoria relacional dos contratos como lente teórica para analisar o modelo de parcerias de risco e, por meio dela, investigar qual o papel exercido pelos elementos relacionais no sucesso dos programas ERJ 145 e EMBRAER 170/190. A hipótese central que norteia o trabalho é a de que, no inovador arranjo contratual que envolveu a Embraer, fornecedores estrangeiros e o BNDES, a relação contratual foi construída por meio de mecanismos promissórios e não-promissórios de projeção de trocas, e os padrões de normatividade estabelecidos entre as partes transcenderam o contrato escrito. A contribuição da teoria relacional dos contratos para a análise de tais práticas possui duplo caráter. A primeiro contribuição é eminentemente descritiva, ao fornecer um instrumental teórico mais abrangente e poderoso para compreender a real dinâmica das práticas contratuais em análise. A segunda contribuição, de natureza normativa, consiste em explicitar aspectos relacionais que compõem, juntamente com os elementos promissórios, uma certa normatividade interna ao contrato que informa a conduta dos agentes ao longo da relação. Nos programas ERJ 145 e EMBRAER 170/90, procuramos demonstrar como a formulação de um arranjo contratual mais relacional em substituição ao tradicional conjunto de relações contratuais de fornecimento descontínuas, foi fundamental para o sucesso dos projetos e até mesmo para a sua própria viabilização. Nesse sentido, a teoria relacional dos contratos fornece categorias de análise que não apenas oferecem um ferramental teórico mais adequado para descrever relações como a do caso em estudo, mas também fornece, por meio de uma descrição mais rica e abrangente, lições sobre como desenhar contratos. Isto é importante para demonstrar como a problemática das dimensões implícitas do contratos transcende o campo da teoria contratual e da justiça contratual e apresenta-se de grande relevância para a agenda de pesquisa em Direito e Desenvolvimento.

Estudo teórico QTAIM e DFT dos compostos de coordenação: efeito quelato, titanocenos e ligação química

This work is a study of coordination compounds by quantum theory of atoms in molecules (QTAIM), based on the topological analysis of the electron density of molecular systems, both theoretically and experimentally obtained. The coordination chemistry topics which were studied are the chelate effect, bent titanocene and chemical bond in coordination complexes. The chelate effect was investigated according to topological and thermodynamic parameters. The exchange of monodentate ligands on polydentate ligands from same transition metal increases the stability of the complex both from entropy and enthalpy contributions. In some cases, the latter had a higher contribution to the stability of the complex in comparison with entropy. This enthalpic contribution is explained according to topological analysis of the M-ligand bonds where polidentate complex had higher values of electron density of bond critical point, Laplacian of electron density of bond critical point and delocalization index (number of shared electrons between two atoms). In the second chapter, was studied bent titanocenes with bulky cyclopentadienyl derivative π-ligand. The topological study showed the presence of secondary interactions between the atoms of π-ligands or between atoms of π-ligand and -ligand. It was found that, in the case of titanocenes with small difference in point group symmetry and with bulky ligands, there was an nearly linear relationship between stability and delocalization index involving the ring carbon atoms (Cp) and the titanium. However, the titanocene stability is not only related to the interaction between Ti and C atoms of Cp ring, but secondary interactions also play important role on the stability of voluminous titanocenes. The third chapter deals with the chemical bond in coordination compounds by means of QTAIM. The quantum theory of atoms in molecules so far classifies bonds and chemical interactions in two categories: closed shell interaction (ionic bond, hydrogen bond, van der Waals interaction, etc) and shared interaction (covalent bond). Based on topological parameters such as electron density, Laplacian of electron density, delocalization index, among others, was classified the chemical bond in coordination compounds as an intermediate between closed shell and shared interactions

Estudo teórico aplicado ao petróleo: estabilidade dos alcenos e recuperação terciária

The present work aims to study the theoretical level of some processes employed in the refining of petroleum fractions and tertiary recovery of this fluid. In the third chapter, we investigate a method of hydrogenation of oil fractions by QTAIM (Quantum Theory of Atoms in Molecules) and thermodynamic parameters. The study of hydrogenation reactions, and the stability of the products formed, is directly related to product improvement in the petrochemical refining. In the fourth chapter, we study the theoretical level of intermolecular interactions that occur in the process of tertiary oil recovery, or competitive interactions involving molecules of non-ionic surfactants, oil and quartz rock where oil is accumulated. Calculations were developed using the semiempirical PM3 method (Parametric Model 3). We studied a set of ten non-ionic surfactants, natural and synthetic origin. The study of rock-surfactant interactions was performed on the surface of the quartz (001) completely hydroxylated. Results were obtained energetic and geometric orientations of various surfactants on quartz. QTAIM was obtained through the analysis of the electron density of interactions, and thus, providing details about the formation of hydrogen bonds and hydrogen-hydrogen systems studied. The results show that the adsorption of ethoxylated surfactants in the rock surface occurs through the hydrogen bonding of the type CH---O, and surfactants derivatives of polyols occurs by OH---O bonds. For structures adsorption studied, the large distance of the surfactant to the surface together with the low values of charge density, indicate that there is a very low interaction, characterizing physical adsorption in all surfactants studied. We demonstrated that surfactants with polar group comprising oxyethylene units, showed the lowest adsorption onto the surface of quartz, unlike the derivatives of polyols

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

General structures of Hamiltonian hierarchies

Three dimensional exactly solvable quantum potentials for which an extra term of form 1/r(2) has been added are shown to maintain their functional form which allows the construction of the Hamiltonian hierarchy and the determination of the spectra of eigenvalues and eigenfunctions within the Supersymmetric Quantum Mechanics formalism. For the specific cases of the harmonic oscillator and the Coulomb potentials, known as pseudo-harmonic oscillator and pseudo-Coulomb potentials, it is shown here that the inclusion of the new term corresponds to rescaling the angular momentum and it is responsible for maintaining their exact solvability.

Duality of coordinates and matter fields in curved spacetime

We show that there exists a duality between the local coordinates and the solutions of the Klein-Gerdon equation in curved spacetime in the same sense as in the Minkowski spacetime. However, the duality in curved spacetime does not have the same generality as in flat spacetime and it holds only if the system satisfies certain constraints. We derive these constraints and the basic equations of duality and discuss the implications in the quantum theory. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Renormalized coordinate approach to the thermalization process

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Quasiprobability distribution functions for finite-dimensional discrete phase spaces: Spin-tunneling effects in a toy model

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Classical integrable N=1 and N=2 super sinh-Gordon models with jump defects

The structure of integrable field theories in the presence of jump defects is discussed in terms of boundary functions under the Lagrangian formalism. Explicit examples of bosonic and fermionic theories are considered. In particular, the boundary functions for the N = 1 and N = 2 super sinh-Gordon models are constructed and shown to generate the Backlund transformations for its soliton solutions. As a new and interesting example, a solution with an incoming boson and an outgoing fermion for the N = 1 case is presented. The resulting integrable models are shown to be invariant under supersymmetric transformation.

Dressing approach to the nonvanishing boundary value problem for the AKNS hierarchy

We propose an approach to the nonvanishing boundary value problem for integrable hierarchies based on the dressing method. Then we apply the method to the AKNS hierarchy. The solutions are found by introducing appropriate vertex operators that takes into account the boundary conditions.

Quantization of (2+1)-spinning particles and bifermionic constraint problem

This work is a natural continuation of our recent study in quantizing relativistic particles. There it was demonstrated that, by applying a consistent quantization scheme to the classical model of a spinless relativistic particle as well as to the Berezin-Marinov model of a 3 + 1 Dirac particle, it is possible to obtain a consistent relativistic quantum mechanics of such particles. In the present paper, we apply a similar approach to the problem of quantizing the massive 2 + 1 Dirac particle. However, we stress that such a problem differs in a nontrivial way from the one in 3 + 1 dimensions. The point is that in 2 + 1 dimensions each spin polarization describes different fermion species. Technically this fact manifests itself through the presence of a bifermionic constant and of a bifermionic first-class constraint. In particular, this constraint does not admit a conjugate gauge condition at the classical level. The quantization problem in 2 + 1 dimensions is also interesting from the physical viewpoint (e.g., anyons). In order to quantize the model, we first derive a classical formulation in an effective phase space, restricted by constraints and gauges. Then the condition of preservation of the classical symmetries allows us to realize the operator algebra in an unambiguous way and construct an appropriate Hilbert space. The physical sector of the constructed quantum mechanics contains spin-1/2 particles and antiparticles without an infinite number of negative-energy levels, and exactly reproduces the one-particle sector of the 2 + 1 quantum theory of a spinor field.