No presente trabalho, efetuamos um extensivo estudo das propriedades eletrônicas e estruturais de nanofios de silcio (Si NWs) utilizando simulações computacionais totalmente ab-initio (metodo do DFT). Mostramos que nestes sistemas, diferentes facetas podem ser eletronicamente ativas ou inativas nos estados de borda dependendo apenas da maneira como os átomos de superfície se ligam aos átomos mais internos. Estes efeitos são causados pelo confinamento quântico nos fios, e por isso podem ser estendidas para outros tipos de fios semicondutores. Nossos resultados podem ser utilizados para guiar o processo de manufatura de sensores baseados em nanofios. Efetuamos cálculos ab-initio de transporte eletrônico nos nanofios com radicais de NH2 adsorvidos em diferentes facetas. Estas análises indicam que há diferenças entre a resposta do sistema a perturbações em superfícies distintas que são eletronicamente ativas. Em certas circunstâncias que serão discutidas, o nível de impureza gera centros espalhadores que reduzem o transporte eletrônico de maneira mais uniforme, enquanto em outros casos as quedas na transmitância são extremamente agudas, com perfil lembrando ressonâncias de fano. Investigamos ainda dopagem de Si NWs com boro e fósforo. Mostramos que estas impurezas se distribuem de maneira razoavelmente uniforme em sítios internos e superficiais dos fios. Embora o confinamento quântico tenda a tornar os níveis de impureza significativamente mais profundos nos fios que no cristal de Si, mostramos que rapidamente, para diâmetros acima de 30°A, dopagem com características de bulke recuperada. Efeitos associados as diferentes superfícies nas quais as impurezas estão localizadas também foram identificados, e acordo com nossas constatações anteriores. Estudamos outra importante impureza em nanofios de Si, que é o ouro, que é utilizado como catalisador no crescimento destes fios. Nossas analises indicam que ha uma forte tendência para estes átomos serem incorporados em sítios superficiais, onde eles não introduzem estados próximos ao gap de energia. Isso indica que ouro pode ser utilizado para catalisar estes fios sem afetar suas propriedades eletrônicas. Por fim analisamos as propriedades eletrônicas de heteroestruturas filiformes de silicio-germânio. Dispositivos eletrônicos baseados nestes materiais têm apresentado propriedades superiores a de equivalentes em arquitetura planar ou mesmo dispositivos baseados em outros nanofios. Nossas análises indicam que estes materiais podem apresentar tão variadas que os tornam candidatos `a diversas implementações tecnológicas, desde detectores de alta sensibilidade e grande liberdade de manipulação até materiais de propriedades eletrônicas robustas e pouco sujeitas a indesejáveis perturbações. / We have performed an extensive study on the electronic and structural properties of silicon nanowires (NWs) using parameter free computational simulations (DFT). We show that in Si NWs, surfaces whose atoms are connected to inner ones perpendicularly to the wires axes become electronically inactive at the band edges. However, when these bonds are oriented along the growth axes the surface states contribute significantly to the formation of the HOMO and LUMO, even for relatively large wires (diameters > 30 °A). This is the dimension of the smallest experimental as-grown wires. These effects are caused by the fact that the electronic wave function is confined in the two directions perpendicular to the wires axes but it is not along it. Therefore, these conclusions can be extended to other types of semiconductor NWs, grown along different directions, with different facets and even surface reconstructions. These results can be used to guide actual implementations of NW based chemical and biological sensors, in a fashion that is now being followed by experimentalists. Following this work, we have investigated the electronic transport in these NWs with a NH2 radical adsorbed on different types of facets. These investigations not only confirm our previous conclusions but also indicate different effects associated with impurities adsorbed on distinct active surfaces. In some cases, the impurity level induces scattering centres that reduce the transport in an uniform way, whereas on other types of facets the decrease in the eletronic transport is sharp, suggesting the occurence of fano resonance.

abstract: Autonomic closure is a new general methodology for subgrid closures in large eddy simulations that circumvents the need to specify fixed closure models and instead allows a fully- adaptive self-optimizing closure. The closure is autonomic in the sense that the simulation itself determines the optimal relation at each point and time between any subgrid term and the variables in the simulation, through the solution of a local system identification problem. It is based on highly generalized representations of subgrid terms having degrees of freedom that are determined dynamically at each point and time in the simulation. This can be regarded as a very high-dimensional generalization of the dynamic approach used with some traditional prescribed closure models, or as a type of “data-driven” turbulence closure in which machine- learning methods are used with internal training data obtained at a test-filter scale at each point and time in the simulation to discover the local closure representation. In this study, a priori tests were performed to develop accurate and efficient implementations of autonomic closure based on particular generalized representations and parameters associated with the local system identification of the turbulence state. These included the relative number of training points and bounding box size, which impact computational cost and generalizability of coefficients in the representation from the test scale to the LES scale. The focus was on studying impacts of these factors on the resulting accuracy and efficiency of autonomic closure for the subgrid stress. Particular attention was paid to the associated subgrid production field, including its structural features in which large forward and backward energy transfer are concentrated. More than five orders of magnitude reduction in computational cost of autonomic closure was achieved in this study with essentially no loss of accuracy, primarily by using efficient frame-invariant forms for generalized representations that greatly reduce the number of degrees of freedom. The recommended form is a 28-coefficient representation that provides subgrid stress and production fields that are far more accurate in terms of structure and statistics than are traditional prescribed closure models. / Dissertation/Thesis / Doctoral Dissertation Aerospace Engineering 2019

abstract: The goal of this paper was to do an analysis of two-dimensional unsplit mass and momentum conserving Finite Volume Methods for Advection for Volume of Fluid Fields with interfaces and validating their rates of convergence. Specifically three unsplit transport methods and one split transport method were amalgamated individually with four Piece-wise Linear Reconstruction Schemes (PLIC) i.e. Unsplit Eulerian Advection (UEA) by Owkes and Desjardins (2014), Unsplit Lagrangian Advection (ULA) by Yang et al. (2010), Split Lagrangian Advection (SLA) by Scardovelli and Zaleski (2003) and Unsplit Averaged Eulerian-Lagrangian Advection (UAELA) with two Finite Difference Methods by Parker and Youngs (1992) and two Error Minimization Methods by Pilliod Jr and Puckett (2004). The observed order of accuracy was first order in all cases except when unsplit methods and error minimization methods were used consecutively in each iteration, which resulted in second-order accuracy on the shape error convergence. The Averaged Unsplit Eulerian-Lagrangian Advection (AUELA) did produce first-order accuracy but that was due to a temporal error in the numerical setup. The main unsplit methods, Unsplit Eulerian Advection (UEA) and Unsplit Lagrangian Advection (ULA), preserve mass and momentum and require geometric clipping to solve two-phase fluid flows. The Unsplit Lagrangian Advection (ULA) can allow for small divergence in the velocity field perhaps saving time on the iterative solver of the variable coefficient Poisson System. / Dissertation/Thesis / Masters Thesis Mechanical Engineering 2019

Depuis sa création le laboratoire PICM a toujours cherché à développer de nouvelles applications pour le silicium amorphe hydrogéné, a-Si:H. Les recherches effectuées ont mis en évidence que le a-Si:H est un matériau parfaitement adapté pour la détection des particules tout en étant résistant aux radiations. Il a en outre un faible coût de fabrication, il est compatible avec les technologies déjà existantes et il peut être déposé sur de grandes surfaces. Ainsi, malgré la faible mobilité locale des charges (30 cm2 V-1 s -1 ), le silicium a-Si:H est un matériau particulièrement intéressant pour la réalisation de pixels de détection de particules de haute énergie. Il nous a donc paru logique de nous intéresser, en collaboration avec le laboratoire LLR1 et dans le cadre de cette thèse, à la conception et à la réalisation expérimentale d'une structure empilée de pixels à base de silicium a-Si:H, comme élément de base d'un détecteur d'un calorimètre électromagnétique. Ainsi, les composants qui constituent la structure d'un tel pixel sont tout d'abord une diode PIN en silicium a-Si :H puis en superposition une résistance de polarisation et un condensateur de découplage. Avant de réaliser à proprement parler une telle structure et afin d'optimiser au mieux sa conception, il est indispensable de posséder des modèles comportementaux performants des différents composants. Ainsi, notre objectif primordial a été de concevoir un modèle physique bidimensionnel de la diode PIN à l'aide du progiciel SILVACO de calcul par éléments finis. Ce modèle physique bidimensionnel de la diode PIN en a-Si:H nous a permis d'étudier le problème de diaphonie entre pixels dans une structure matricielle de détecteurs. Nous avons ici plus particulièrement mis en évidence le courant de fuite ainsi que le courant généré dans le volume entre pixels voisins. La transposition de cette modélisation dans une approche comportementale de type SPICE, que nous avons réalisé ensuite, nous permet de garantir la portabilité du modèle vers d'autres simulateurs professionnels et surtout son intégration dans une structure électronique complète (diode PIN, résistance de polarisation, capacité de découplage et amplificateur bas bruit). Grâces à ces outils de modélisation, nous avons pu simuler des structures de diodes PIN en a-Si:H de différentes épaisseurs et de différentes dimensions. Ces simulations nous ont permis de prédire que les structures épaisses sont pertinentes pour la conception de détecteurs pixels pour la physique de haute énergie. Nous pouvons aussi envisagé des applications en astronomie, dans le domaine de l'imagerie médicale, dans l'analyse de la défaillance des circuits intégrés en silicium, etc. D'un point de vue technologique, nous nous sommes attachés à maîtriser l'ensemble de la chaîne de fabrication (tel que le bon choix des matériaux métalliques pour les électrodes, l'enchaînement des dépôts, la conception des masques et la lithographie en salle blanche). Ainsi, nous pouvons citer comme exemple, que le matériau optimal que nous proposons pour les électrodes des résistances et des capacités est le Titane, mais à cause de sa fonction de travail de sortie ce dernier est déconseillé pour la réalisation de diodes PIN.

<p>The main purpose of this thesis is to implement the Gauss--Legendre quadrature for the dispersion coefficient. This has been done and can be now be made with different number of points. The calculations with this implementation has shown that the relativistic impact on helium, neon, argon and krypton is largest for krypton, that has the highest charge of its nucleus. It was also seen that the polarizability of neon as a function of the imaginary angular frequency decreases monotonically from a static value.</p>

<p>The absorption properties of the Pt1 chromophore at room temperature have been studied. Stretch, bend and torsion parameters for Pt(II), P, C (type 1, 2 and 4) and H have been parameterized for use in the MM3 force field. Parameters were fitted to energies computed at the B3LYP level of theory. The parameterized model was used to perform molecular dynamics simulations at room temperature. This was done for several environments and for time periods of up to 200 ps. Absorption properties were computed for snapshots from the dynamics, from which average absorption spectra were created. A conformational broadening of around 40 nm was found in the theoretical spectra, which is in good agreement with experiments. Due to a lack of solvent-solute interactions and the use of a less extensive basis set, a systematic blue shift of 40 nm is evident in the computed spectra.</p>

Solving physics problem in university physics education with a computational approach requires knowledge and skills in several domains, for example, physics, mathematics, programming, and modelling. These competences are in turn related to students' beliefs about these domains as well as about learning, and their motivation to learn. The purpose of this thesis was to investigate the role of university physics students' knowledge, beliefs and motivation when solving and visualizing a physics problem using a computational approach. The results showed that expert-like beliefs about physics and learning physics together with prior knowledge were important predictors of the quality of performance. Feelings corresponding to control and concentration, i.e., emotions that are expected to be good indicators of students' motivation were also good predictors of performance. However, intrinsic motivation, as indicated by enjoyment and interest, together with beliefs expressing students' personal interest and utility value, did not predict performance to any higher extent. Instead, my results indicate that integration and identification of expert-like beliefs about learning and concentration and control emotions during learning are more influential on the quality of performance. Thus, the results suggest that the development of students' epistemological beliefs is important for students' ability to learn from realistic problem-solving situations with many degrees of freedom in physics education. In order to investigate knowledge and beliefs structures network modeling has been applied as a novel tool for analysis. Students' epistemic frames are analyzed before and after the task in computational physics using a network analysis approach on interview transcripts, producing visual representations of mental models. The results show that students change their epistemic framing from a modelling task, with expectancies about learning programming, to a physics task, in which they are challenged to use physics principles and conservation laws in order to troubleshoot and understand their simulations. This implies that the task, even though it is not introducing any new physics, helped the students to develop a more consistent view of the importance of using physics principles in problem solving. When comparing students' framing with teachers,' it is shown that although teachers and students agree on the main features of simulation competence in physics, differences in their epistemic networks can be distinguished. For example, while teachers believe that numerical problem solving facilitates fundamental understanding of physics and mathematics, this is not obvious to students. This implies that university teachers need to be aware of these differences as well as students' beliefs in order to challenge students' expectations and to give support concerning the learning objectives of the assignment.

The X-ray absorption spectrum of silicon in of SiCl4 has been calculated for the LIII and LII edges. The resulting spectrum has been vibrationally resolved by considering the symmetric stretch vibrational mode and the results has been compared to experiment [4]. One peak from the experiment was found to be missing in the calculated vibrationally resolved spectrum. The other calculated peaks could be matched to the corresponding experimental peaks although significant basis set effects are present. An investigation of one peak beyond the Franck–Condon principle shows it to be a good approximation in the case of the studied system.

The work presented in this thesis concerns the dynamics in π-conjugated hydrocarbon systems. Due to the molecular bonding structure of these systems there exists a coupling between the electronic system and the phonons of the lattice. If this interaction, which is referred to as the electron-phonon (e-ph) coupling, is sufficiently strong it may cause externally introduced charge carriers to self-localize in a polarization cloud of lattice distortions. These quasi-particles are, if singly charged, termed polarons, the localization length of which, aside from the e-ph coupling strength, also depend upon the structural and energetic disorder of the system. In disordered systems localization is strong and transport is facilitated by nonadiabatic hopping of charge carriers from one localized state to the next, whereas in well-ordered systems, where extended states are formed, adiabatic transport models apply.Despite great academic efforts a unified model for charge transport in π-conjugated systems is still lacking and further investigations are necessary to uncover the basic physics at hand in these systems. The call for such efforts has been the main guidelines for the work presented in this thesis and are related to the topics of papers I-IV. In order to capture the coupled electron-lattice dynamics, we use a methodological approach where we obtain the time-dependence of the electronic degrees of freedom from the solutions to the time-dependent Schrödinger equation and determine the ionic motion in the evolving charge density distribution by simultaneously solving the lattice equation of motion within the potential field of the ions. The Hamiltonian used to describe the system is derived from an extension of the famous Su-Schrieffer-Heeger (SSH) model extended to three-dimensional systems.In papers I-III we explore the impact of phenylene ring torsion on delocalization and transport properties in poly(para-phenylene vinylene) (PPV). The physics that we are particularly interested in relates to the reduced electron transfer integral strength across the interconnection between the phenylene rings and the vinylene groups upon ring torsion. Keeping this in mind, we demonstrate in paper I the impact of static ring torsion on intrachain mobility and provide a detailed analysis of the influence of the potential barriers (due to consecutive ring torsion) on the nature of charge carrier propagation. In paper II we extend our initial approach to include also the dynamics of ring torsion. We show that without any externally applied electric field, this type of dynamics is the dominant property controlling intrachain propagation, but that when an external electric field is applied, charge carriers may traverse the potential barriers through a process that involves nonadiabatic effects and a temporary delocalization of the polaron state. Finally, in paper III we study the impact of the lattice dynamics on the electron localization properties in PPV and show that the phenylene ring torsion modes couples strongly to the electronic wave function which gives rise to electron localization at room temperature.In papers IV and V we focus on the dynamics of molecular crystals using a stack of pentacene molecules in the single crystal configuration as a model system, but study, in paper IV, the transport as a function of the intermolecular interaction strength, J. We observe a smooth transition from a nonadiabatic to an adiabatic polaron drift process over the regime 20&lt;J&lt;120 meV. For intermolecular interaction strengths above J≈120 meV the polaron is no longer stable and transport becomes band-like. In paper V, finally, we study the internal conversion processes in these systems, which is the dominant relaxation channel from higher lying states. This process involves the transfer of energy from the electronic system to the lattice. Our results show that this process is strongly nonadiabatic and that the relaxation time associated with large energy excitations is limited by transitions made between states of different bands. / I dagens samhälle är elektroniken ett allt viktigare och större inslag i vår vardag. Vi ser på TV, talar i mobiltelefoner, och arbetar på datorer. I hjärtat av denna teknologi finner vi diskreta komponenter och integrerade kretsar utformade främst för att styra strömmen av elektroner genom halvledande material. Traditionellt sett har kisel eller olika former av legeringar använts som det aktiva materialet i dessa komponenter och kretsar, men under de senaste 20 åren har såväl transistorer som solceller och lysdioder realiserats där det aktiva materialet är organiskt, d.v.s., kolbaserat.Vi befinner oss för tillfället mitt uppe i det kommersiella genombrottet för organisk elektronik. Redan idag säljs många MP3-spelare och mobiltelefoner med små skärmar där varje pixelelementen utgörs av organiska ljusemitterande dioder (OLEDs), men teknologin håller redan på att introduceras i mer storskaliga produkter som datorskärmar och TV-apparater som därigenom skulle kunna göras energieffektivare, tunnare, flexiblare och på sikt också billigare. Andra tekniska tillämpningsområden för organisk elektronik som förutspås en lysande framtid är RFID-märkning, organiska solceller, och elektronik tryckt på papper, men även smarta textiler och bioelektronik har stor utvecklingspotential.Den kanske största utmaningen kvarstår dock, att skapa elektroniska kretsar och komponenter uppbyggda kring enskilda molekyler, s.k. molekylär elektronik. Mycket snart närmar vi oss den fysikaliska gränsen för hur små komponenter som vi kan realisera med traditionella icke-organiska material som kisel och en stor drivkraft bakom forskningen på halvledande organiska material har varit just visionen om molekylär elektronik som inte är mer än några miljondelars milimeter stora. För detta ändamål krävs en mycket nogrann kontroll av tillverkningsprocesserna liksom en detaljförståelse för hur molekylerna leder ström och hur denna förmåga kan manipuleras för att realisera såväl traditionella som nya komponenter.I denna avhandling presenteras en översikt av den fysik som möjliggör ledningsförmåga hos särskilda klasser av organiska material, s.k. π-konjugerade system, samt de forskningsresultat som utgör mitt bidrag till denna disciplin. En av utmaningarna på området är den komplexitet som de organiska materialen erbjuder: laddningsprocesserna påverkas nämligen av en rad olika faktorer såsom laddningstäthet, temperatur, pålagd spänning, samt molekylernas former och inbördes struktur. I detta arbete har jag utifrån en vidareutveckling av existerande modeller genom numeriska datasimuleringar undersökt effekten av de senare tre faktorerna på elektronstrukturen, laddnigstransporten och energidissipation i denna klass av material. / Center of Organic Electronics (COE)

Time-dependent molecular properties are important for the experimental characterization of molecular materials. We show how these properties can be calculated, for optical and x-ray frequencies, using novel quantum chemical methods. For xray absorption there are important relativistic effects appearing, due to the high velocity electrons near the atomic nuclei. These effects are treated rigorously within the four-component static exchange approximation. We also show how electron correlation can be taken into account in the calculation of x-ray absorption spectra, in time-dependent density functional theory based on the complex polarization propagator approach. The methods developed have been applied to systems of experimental interest|molecules in the gas phase and adsorbed on metal surfaces. The effects of molecular vibrations have been take into account both within and beyond the harmonic approximation.