The adsorption of cationic and zwitterionic surfactants is studied in aqueous electrolyte solutions. A Maxwell relation is applied to Atomic Force Microscopy (AFM) data to obtain changes in surfactant adsorption as a function of the separation between two glass surfaces. In addition, self-consistent field theory (SCF) is used to calculate the adsorption profiles and interaction energies when two solid surfaces are brought into close proximity. Addition of surfactant is shown to affect the surface forces when lateral surfactant chain interactions are significant. The surfactant adsorbs and desorbs in response to over-lapping electric double-layers, with the adsorption being affected at larger solid-solid separations when the double-layer force is longer ranged. Furthermore, elimination off the surface charge or net surfactant charge eliminates adsorption with decreased solid-solid separation. The magnitude of the changes in surfactant adsorption at decreased separations is shown to scale with the chain length of the surfactant. Surfactant adsorption exceeds that required to regulate the surface charge according to the constant potential boundary condition in Poisson-Boltzmann theory. An equation of state including short-ranged (contact) tail interactions is proposed to describe both the adsorption of surfactant and the surface forces at small separations, where the double-layers overlap. Furthermore, SCF calculations show confinement-induced phase transitions when the surfactant layers on opposite surfaces merge. These phase transitions lead to further surfactant adsorption and a corresponding attractive force. / Ph. D.

The development of the semi-empirical atomistic potential called the embedded atom method (EAM) has allowed for the efficient modeling of solid-state environments, at a lower computational cost than afforded by density functional theory (DFT). This offers the capability of EAM to model the energetics of solid-state phases of varying coordination, including defects, such as vacancies and self-interstitials. This dissertation highlights the development and application of two EAMs: a Ti potential constructed with the multi-state modified embedded atom method (MS-MEAM), and a Ni potential constructed with the fragment Hamiltonian (FH) method. Both potentials exhibit flexibility in the description of different solid-states phases and applications. This dissertation also outlines two applications of DFT. First, a study of structure and stability for solid-state forms of NixCy (in which x and y are integers) is investigated using plane-wave DFT. A ground state phase for Ni2C is elucidated and compared to known and hypothesized forms of NixCy. Also, a set of correlation consistent basis sets, previously constructed using the B3LYP and BLYP density functionals, are studied. They are compared to the well-known to the correlation consistent basis sets that were constructed with higher-level ab initio methodologies through computations of enthalpies of formation and combustion enthalpies. The computational accuracy with regard to experiment is reported.

Questo lavoro si compone di due parti. La prima parte, costituita dal capitolo primo, fornisce una comparazione teorica di due teorie economiche in ambito di dottrina monetaria, ovvero la teoria New Keynesiana e quella Post Keynesiana. Nella seconda parte, viene ideato e implementato attraverso il software un modello teorico macroeconomico di impostazione Post Keynesiana. L’argomento di analisi è il processo di cartolarizzazione – illustrato nel capitolo 2 – che è stato al centro della crisi finanziaria che ha colpito gli Stati Uniti nel 2007-2009. L’obiettivo del lavoro è quello di analizzare, attraverso la costruzione di un modello – esposto nel capitolo 3 – che utilizza la metodologia Stock-Flow Consistent, i collegamenti tra il settore finanziario e il mercato delle case al fine di stabilire la natura della crisi: si è trattato di una crisi trainata dalla finanza o dal comportamento delle famiglie? La novità del nostro lavoro consiste nella descrizione dettagliata nell’ambito dell’approccio Stock-Flow Consistent del comportamento delle banche private, assumendo una gestione attiva di bilancio da parte delle banche di investimento. / This work is basically divided into two parts. The first part – chapter 1 – provides a comparison between two theory of monetary economics: New Keynesian and Post Keynesian. The second part is represented by the elaboration and implementation of a theoretical macroeconomic model, grounded in Post Keynesian theory. The subject under investigation is the securitization process – illustrated in chapter 2 – which has been at the centre of the 2007-2009 crisis in the United States. The aim is to analyze, through the construction of an elaborate model – in chapter 3 – the links between the financial sector and the housing market and to assess the nature of the crisis: was the 2007-2009 financial crisis a households-led or a finance-led crisis? The novelty of our work is represented by the detailed description in the Stock-Flow Consistent approach of the private banking sector, assuming that investment banks carry out an active management of their balance sheets.

We present two possible thermodynamical approaches towards a derivation of a model, proposed by Korteweg at the beginning of the 20th century, that is suitable to describe phase transitions liquid-vapor with non-sharp interfaces. The first approach (Dunn, Serrin (1985)) is based on classical rational continuum thermodynamics. The second approach (Heida, Málek (2010)) stems from the principles of classical nonequilibrium continuum thermodynamics. We compare both approaches in favor of the second one. The considered constitutive equation for the Cauchy stress is nonlinear. Nonlinearity and higher order derivatives of the density makes the analysis of relevant problems for the Navier-Stokes- Korteweg (NSK) fluid more difficult in comparison to problems concerning Navier-Stokes equations. Special attention is devoted to the appropriate choice of the boundary conditions. We also investigate the influence of compressibility on the stability of bubbles by comparing numerical simulations for compressible NSK fluid and its incompressible variant. Instabilities observed for a compressible NSK fluid are due to the pressure that has a different meaning for incompressible fluid. Powered by TCPDF (www.tcpdf.org)

The research presented in this thesis was carried out as part of a collaboration between the groups of Dr Tanja van Mourik at the School of Chemistry, University of St Andrews and Professor Jonathan Tennyson at the Department of Physics and Astronomy at University College London. This thesis presents State-Averaged Complete Active Space Self Consistent Field (SA-CASSCF) calculations on nucleic acid bases, deoxyribose and phosphoric acid H₃PO₄). In the case of uracil, for comparison, Multireference Configuration Interaction calculations were also performed. The SA-CASSCF orbitals were subsequently used in R-matrix electron scattering calculations using the close-coupling model. Of major importance for obtaining accurate SA-CASSCF results is the choice of the active space and the number of calculated states. Properties such as the electronic energy, number of configurations, excitation energy and dipole moment were considered in the choice of active space. Electron-collision calculations were performed on two of the most stable isomers of phosphoric acid, a weakly dipolar form with all OH groups pointing up and a strongly dipolar form where one OH group points down. A broad shape resonance at about 7 eV was found for both isomers. Ten-state close-coupling calculations suggest the presence of narrow, Feshbach resonances in a similar energy region. Elastic and electronically inelastic cross sections were calculated for both isomers. The R-matrix calculations on uracil were done by the group from UCL. R-matrix calculations are currently being done on guanine. Scattering calculations on the other DNA bases will be performed in the near future.

In this thesis we present solutions of spontaneous compactifications of D=11, N=1 supergravity on parallelizable manifolds S^1, S^3 and S^7. In Freund-Rubin compactifications one usually obtains AdS vacua in 4D, these solutions usually sets the fermionic VEV's to zero. However giving them non zero VEV's allows us to define torsion given by the fermionic bilinears that essentially flattens the geometry giving us a vanishing cosmological constant on M_4. We further give an analysis of the consistent truncation of the bosonic sector of D=11 supergravity on a S^3 manifold and relate this to other known consistent truncation compactifications. We also consider the squashed S^7 where we check for surviving supersymmetries by analyzing the generalised holonomy, this compactification is of interest in phenomenology.

Economic policy in the EU faces a trilemma of solving three challenges simultaneously - growth, distribution, and the environment. In order to assess policies that address these issues simultaneously, economic models need to account for both sector-sector and sector-environment feedbacks within a single framework.This paper presents a multi-sectoral stock-flow consistent (SFC) macro model where a demand-driven economy consisting of multiple institutional sectors - firms, energy, households, government, and financial - interacts with the environment. The model is calibrated for the EU region and five policy scenarios are evaluated; low consumption, a capital stock damage function, carbon taxes, higher share of renewable energy, and technological shocks to productivity. Policy outcomes are tracked on overall output, unemployment, income and income distributions, energy, and emission levels. Results show that investment in mitigation technologies allows for absolute decoupling and ensures that the above three issues can be solved simultaneously. / Series: WWWforEurope

O uso de sistemas multiprocessados para a resolução de problemas que demandam um grande poder computacional tem se tornado cada vez mais comum. Porém a conversão de programas seqüenciais para programas concorrentes ainda não é uma tarefa trivial. Dentre os fatores que tornam esta tarefa difícil, destacamos a inexistência de um paradigma único e consolidado para a construção de sistemas computacionais paralelos e a existência de várias plataformas de programação para o desenvolvimento de programas concorrentes. Nos dias atuais ainda é impossível isentar o programador da especificação de como o problema será particionado entre os vários processadores. Para que o programa paralelo seja eficiente, o programador deve conhecer a fundo aspectos que norteiam a construção do hardware computacional paralelo, aspectos inerentes à arquitetura onde o software será executado e à plataforma de programação concorrente escolhida. Isto ainda não pode ser mudado. O ganho que podemos obter é na implementação do software paralelo. Esta tarefa pode ser trabalhosa e demandar muito tempo para a depuração, pois as plataformas de programação não possibilitam que o programador abstraia dos elementos de hardware. Tem havido um grande esforço na criação de ferramentas que otimizem esta tarefa, permitindo que o programador se expresse mais fácil e sucintamente quanto à para1elização do programa. O presente trabalho se baseia na avaliação dos aspectos ligados à implementação de software concorrente utilizando uma plataforma de portabilidade chamada High Performance Fortran, aplicado a um problema específico da física: o cálculo da estrutura de bandas de heteroestruturas semicondutoras. O resultado da utilização desta plataforma foi positivo. Obtivemos um ganho de performance superior ao esperado e verificamos que o compilador pode ser ainda mais eficiente do que o próprio programador na paralelização de um programa. O custo inicial de desenvolvimento não foi muito alto, e pode ser diluído entre os futuros projetos que venham a utilizar deste conhecimento pois após a fase de aprendizado, a paralelização de programas se torna rápida e prática. A plataforma de paralelização escolhida não permite a paralelização de todos os tipos de problemas, apenas daqueles que seguem o paradigma de paralelismo por dados, que representam uma parcela considerável dos problemas típicos da Física. / The employment of multiprocessor systems to solve problems that demand a great computational power have become more and more usual. Besides, the conversion of sequential programs to concurrent ones isn\'t trivial yet. Among the factors that makes this task difficult, we highlight the nonexistence of a unique and consolidated paradigm for the parallel computer systems building and the existence of various programming platforms for concurrent programs development. Nowadays it is still impossible to exempt the programmer of the specification about how the problem will be partitioned among the various processors. In order to have an efficient parallel program the programmer have to deeply know subjects that heads the parallel hardware systems building, the inherent architecture where the software will run and the chosen concurrent programming platform. This cannot be changed yet. The gain is supposed to be on the parallel software implementation. This task can be very hard and consume so much time on debugging it, because the programming platforms do not allow the programmer to abstract from the hardware elements. It has been a great effort in the development of tools that optimize this task, allowing the programmer to work easily and briefly express himself concerning the software parallelization. The present work is based on the evaluation of aspects linked to the concurrent software implementation using a portability platform called High Performance Fortran, applied to a physics specific problem: the calculus of semiconductor heterostructures? valence band structure. The result of the use of this platform use was positive. We obtained a performance gain superior than we expected and we could assert that the compiler is able to be more effective than the programmer on the paralelization of a program. The initial development cost wasn\'t so high and it can be diluted between the next projects that would use the acquired knowledge, because after the learning phase, the programs parallelization task becomes quick and practical. The chosen parallelization platform does not allow the parallelization of all kinds of problems, but just the ones that follow the data parallelism paradigm that represents a considerable parcel of tipical Physics problems.

Estruturas semicondutoras com dopagem planar são sistemas de considerável interesse tanto para a a pesquisa básica como para a aplicação em dispositivos. Neste trabalho caracterizamos estruturas semicondutoras com dopagem planar tipo n ou p, utilizando técnicas de espectroscopia ótica tais como fotoluminescencência (PL) e fotoluminescência-excitação (PLE). As amostras foram crescidas com a técnica de Epitaxia por Feixe Molecular (BEM, Molecular Beam Epitaxy) no Laboratório de Novos Materiais Semicondutores (LNMS) do IFUSP, com exceção das amostras com dopagem planar tipo p que foram crescidas nos laboratórios do Departamento de Física da Universidade Federal de Minas Gerais. Investigamos as propriedades eletrônicas de super-redes de GaAs com dopagem planar de silício, em função da concentração dos átomos dopantes, mantendo-se fixa a distância entre os planos de dopagem. Através da comparação de nossos resultados experimentais com os de cálculos autoconsistentes da estrutura eletrônica das super-redes, identificamos a origem de todas as emissões observadas nos espectros de PL. As emissões principais (denominada bandas B) foram identificadas como oriundas do processo de recombinação radiativa dos portadores do gás bidimensional de elétrons (2DEG) com buracos fotogerados na banda de valência. Outras emissões (denominadas bandas A) foram associadas com o processo de recombinação dos elétrons do 2DEG com impurezas de Carbono. Analisamos também amostras de poços quânticos de InGaAs/GaAs com dopagem planar de Silício. Nestes sistemas, devido à presença de impurezas (que atuam como centros de espalhamento) e variações na composição da liga de InGaAs (que dão origem à localização de buracos), transições com e /ou sem conservação de quase-momento envolvendo estados de buraco estendidos e/ou localizados constituem os possíveis processos de recombinação radiativa entre os elétrons do 2DEG e os buracos fotogerados. Neste trabalho, investigamos os processos de recombinação dos elétrons do 2DEG com os buracos gerados por excitação ótica comparando a forma de linha dos espectros experimentais e teóricos de PL. Estruturas semicondutoras de GaAs contendos um único plano de átomos de Berílio (dopagem tipo p ) também foram analisadas neste trabalho. Os resultados de nossas investigações evidenciam a existência de um potencial fotoinduzido, que confina os elétrons fotogerados. O processo de formação deste potencial é discutido neste trabalho. / Delta-doped semiconductor structures are systems of considerable interest for basic research and device applications. In this work, we performed the characterization of n or p-type semiconductor structures, using spectroscopic tecniques as photoluminescence (PL), photoluminescence-excitation (PLE) and selective photoluminescence (SPL). The samples were grown by Molecular Beam Epitaxy (BEM) at LNMS (Laboratório de Novos Materias Semicondutores) of IFUSP anda t Physical Department of UFMG. The electronic structure of Silicon delta-doped GaAs super-lattices with different donor concentrations in the delta-doped layer and a fixed distance between adjacent Si-doped layers was investigated. Though the comparison o four experimental results with the superlattices electronic structure calculated self-consistently we identified the origino f all observed in PL spectra structures. The principal emissions (denominated as bands B) are due to recombination of two-dimensional electron gás (due to delta doping) with photocreated holes in Valence band. Other spectral features (denominated as bands A) were associated with recombination of two dimensional electron gás and Carbon impurity. We analyzed PL spectra of InGaAs/GaAs quantum well samples with Silicon delta doping. In this systems recombination of electrons from two-dimensional gas with photocreated holes through the transitions with or without quase-momentum conservation were observed in PL spectra. Comparing experimental and theoretical lineshape, we are able to determine optical transitions in which holes in localize dor extended states took part. Localization of holes in Valence band is due to fluctuations in dopant distribution in the delta-doped layer. Moreover, GaAs with Beryllium delta doping (p-type) were analyzed in this work . Results o four investigation shown the existence of a photoinduced potential, which confine photocreated electrons in strutures of this type. Formation processo f this potential is discussed in this work.

Estruturas semicondutoras com dopagem planar são sistemas de considerável interesse tanto para a a pesquisa básica como para a aplicação em dispositivos. Neste trabalho caracterizamos estruturas semicondutoras com dopagem planar tipo n ou p, utilizando técnicas de espectroscopia ótica tais como fotoluminescencência (PL) e fotoluminescência-excitação (PLE). As amostras foram crescidas com a técnica de Epitaxia por Feixe Molecular (BEM, Molecular Beam Epitaxy) no Laboratório de Novos Materiais Semicondutores (LNMS) do IFUSP, com exceção das amostras com dopagem planar tipo p que foram crescidas nos laboratórios do Departamento de Física da Universidade Federal de Minas Gerais. Investigamos as propriedades eletrônicas de super-redes de GaAs com dopagem planar de silício, em função da concentração dos átomos dopantes, mantendo-se fixa a distância entre os planos de dopagem. Através da comparação de nossos resultados experimentais com os de cálculos autoconsistentes da estrutura eletrônica das super-redes, identificamos a origem de todas as emissões observadas nos espectros de PL. As emissões principais (denominada bandas B) foram identificadas como oriundas do processo de recombinação radiativa dos portadores do gás bidimensional de elétrons (2DEG) com buracos fotogerados na banda de valência. Outras emissões (denominadas bandas A) foram associadas com o processo de recombinação dos elétrons do 2DEG com impurezas de Carbono. Analisamos também amostras de poços quânticos de InGaAs/GaAs com dopagem planar de Silício. Nestes sistemas, devido à presença de impurezas (que atuam como centros de espalhamento) e variações na composição da liga de InGaAs (que dão origem à localização de buracos), transições com e /ou sem conservação de quase-momento envolvendo estados de buraco estendidos e/ou localizados constituem os possíveis processos de recombinação radiativa entre os elétrons do 2DEG e os buracos fotogerados. Neste trabalho, investigamos os processos de recombinação dos elétrons do 2DEG com os buracos gerados por excitação ótica comparando a forma de linha dos espectros experimentais e teóricos de PL. Estruturas semicondutoras de GaAs contendos um único plano de átomos de Berílio (dopagem tipo p ) também foram analisadas neste trabalho. Os resultados de nossas investigações evidenciam a existência de um potencial fotoinduzido, que confina os elétrons fotogerados. O processo de formação deste potencial é discutido neste trabalho. / Delta-doped semiconductor structures are systems of considerable interest for basic research and device applications. In this work, we performed the characterization of n or p-type semiconductor structures, using spectroscopic tecniques as photoluminescence (PL), photoluminescence-excitation (PLE) and selective photoluminescence (SPL). The samples were grown by Molecular Beam Epitaxy (BEM) at LNMS (Laboratório de Novos Materias Semicondutores) of IFUSP anda t Physical Department of UFMG. The electronic structure of Silicon delta-doped GaAs super-lattices with different donor concentrations in the delta-doped layer and a fixed distance between adjacent Si-doped layers was investigated. Though the comparison o four experimental results with the superlattices electronic structure calculated self-consistently we identified the origino f all observed in PL spectra structures. The principal emissions (denominated as bands B) are due to recombination of two-dimensional electron gás (due to delta doping) with photocreated holes in Valence band. Other spectral features (denominated as bands A) were associated with recombination of two dimensional electron gás and Carbon impurity. We analyzed PL spectra of InGaAs/GaAs quantum well samples with Silicon delta doping. In this systems recombination of electrons from two-dimensional gas with photocreated holes through the transitions with or without quase-momentum conservation were observed in PL spectra. Comparing experimental and theoretical lineshape, we are able to determine optical transitions in which holes in localize dor extended states took part. Localization of holes in Valence band is due to fluctuations in dopant distribution in the delta-doped layer. Moreover, GaAs with Beryllium delta doping (p-type) were analyzed in this work . Results o four investigation shown the existence of a photoinduced potential, which confine photocreated electrons in strutures of this type. Formation processo f this potential is discussed in this work.