In this thesis, several development steps for the incremental method are presented. At first, the extension of the incremental scheme to other quantities than the energy is advanced in terms of molecular dipole moments. In this context, a revised error correction as well as the template localization for the treatment of aromatic systems are introduced. As a second enhancement, a new implementation of the template localization ensures a higher stability of this algorithm step and, thus, of the incremental scheme. Finally, pair natural orbitals (PNOs) are utilized in the incremental method with the aim of an increased efficiency. The PNO approach is re-assessed in context of the incremental expansion leading to both small incremental and PNO local errors for reaction, intermolecular interaction and cluster binding energies. The higher efficiency due to the twofold reduction of the computational efforts by the PNO and the incremental approaches is demonstrated for molecular clusters. Additionally, the complete basis set (CBS) limit is targetted by using the efficient MP2-based focal-point approach to the incremental scheme (with and without PNOs). Finally, based on these improvements of the performance, the PNO-based incremental scheme is applied to support a computational study regarding the modelling of the reaction mechanism for the base-catalyzed twin polymerization.

Die Wurzelwasseraufnahme aus dem Boden wird durch die Rhizosphäre beeinflusst. Die Rhizosphäre ist eine dünne Bodenschicht, die sich um Wurzeln herum bildet. Die Rhizosphäre wird durch Mucilage beeinflusst. Mucilage ist ein polymeres Gel, was von Wurzeln abgesondert wird und vor allem die hydraulischen Eigenschaften der Rhizosphäre verändert. Wenn es im Kontakt mit Wasser ist, kann Mucilage große Mengen an Wasser aufnehmen, aber wenn es trocken ist, wird seine Oberfläche hydrophob. Hier konzentrieren wir uns auf den Effekt von Mucilage auf die hydraulischen Eigenschaften des Bodens. Zunächst präsentieren wir experimentelle und numerische Studien, die die hydraulischen Prozesse in der Rhizosphäre nach der Bewässerung von trockenem Boden beschreiben. Bei Mucilagekonzentrationen, die niedriger als ein gewisser Schwellwert waren, konnte Wasser durch die Rhizosphärenschicht fließen, über dieser Konzentration wurde die Schicht wasserundurchlässig während der ersten Minuten bis zu Stunden nach Bewässerung. Wir präsentieren eine analytische Abschätzung der Mucilagekonzentration an der Perkolationsschwelle als Funktion von mittlerer Teilchengröße und Bodenwasserpotential nach Bewässerung. Die Abschätzung wurde an Hand von Experimenten des kapillaren Aufstiegs in Bodensäulen validiert. Wir entwickelten ein effektives Model um zu beschreiben, wir Mucilage die hydraulischen Funktionen des Bodens verändert: (a) Quell- und Trocknungsprozesse von Mucilage resultieren in Nicht-Gleichgewichtsdynamiken zwischen Wassergehalt und Wasserpotential, (b) die Präsenz von Mucilage im Boden reduziert das Wasserpotential bei einem gegebenen Wassergehalt und (c) Mucilage ist viskos und reduziert dadurch die hydraulische Leitfähigkeit des Bodens bei einem gegebenen Wassergehalt. In Experimenten mit Boden-Mucilage-Mischungen testeten wir das Model und wandten es an, um Beobachtungen von früheren Experimenten mit echten Pflanzen zu simulieren, die veränderte hydraulische Dynamiken in der Rhizophäre zeigen. Im Anhang dieser Arbeit sind zwei Studien zur Wärmeausbreitung von Erdkabeln. Hier können hydraulische Dynamiken autreten, die dem radialen Wasserfluss zu einer einzelnen Wurzel ähneln.

Soil freezing/thawing is of importance in the transport of water, heat and solute, with coupled effects. Due to complexity in soil freezing/thawing, uncertainty could be influential in both experimentation and simulation work in frozen soils. Solute and water in frozen soil could reduce the freezing point, resulting in uncertainty in simulation water, heat and solute processes as well as in estimation of frozen soil evaporation. High salinity and groundwater level could result in high soil evaporation during wintertime. Seasonal courses in energy and water balance on surface have shown to be influential to soil water and heat dynamics, as well as in salt accumulation during wintertime. Water and solute accumulated during freezing period resulted in high evaporation during thawing period and enhanced surface salinization. Diurnal changes in surface energy partitioning resulted in significant cycle of freezing/thawing as well as in evaporation/condensation in surface layer, which could in turn affect atmosphere. Uncertainties in experiments and simulations were detectable in investigation of seasonally frozen soils with limited methods and simplified representations of reality in two agricultural fields in northern China. Soil water and solute contents have shown to be more uncertain than soil temperatures in both measurements and simulations. The combination of experiments with process-based model (CoupModel) has proven to be useful in understanding freezing/thawing processes and in identification of uncertainty, when Monte-Carlo based methods were used for evaluation of simulations. Correlations between parameters and model performance indices needed to be taken into account carefully in calibration of the process-based model. Parameters related to soil hydraulic processes and surface energy processes were more sensitive when using different datasets for calibration. In using multiple model performance indicators for multi-objective evaluation, the trade-offs between them have shown to be a source of uncertainty in calibration. More proper representations of the reality in model (e.g., soil hydraulic and thermal properties) and more detailed measurements (e.g., soil liquid water content and solute concentration) as input would be efficient in reducing uncertainty. Relationships between groundwater, soil and climate change would be of high interest for better understanding of cold regions water and energy balance. / 土壤冻融过程对于水热及溶质的运移具有十分重要的影响，并对于寒旱区水文过程的研究有着深远意义。在冻土中，溶质的存在导致冰点降低，改变土壤冻融规律，进而影响冻融土壤水热运移。冻融土壤地表水分及能量平衡的季节性变化规律对土壤水热运移及盐分的积累影响较大。同时，土壤冻融的水热平衡日变化规律对表层土壤水热过程影响较为强烈，并进而影响地表的气象变化。试验研究表明，高溶质含量及浅埋深地下水条件为地表的蒸发提供了便利条件，因为高溶质含量土壤冰点降低，同一负温条件下的液态含水量增大，为蒸发提供了可利用水分；而浅埋深地下水对冻融期水盐的表聚提供的方便，进而有助于融化期地表水分的大量蒸发及下层土层水分的大量向上补给。例如，当地下水初始埋深设置在1.5 m时，对于初始含盐量分别为0.2%，0.4% 和0.6% g/g的冻融试验组，冻融期累积蒸发量分别为51.0，96.6和114.0 mm。同样的增加趋势在其它初始地下水埋深设置试验组里也被验证，且初始地下水埋深越浅，累积蒸发量也越大。对于利用有限的试验数据及简化的数值模型对冻融土壤水热及溶质研究，由于试验及模型的不确定性，会造成结果的不确定性。而通过利用不确定性分析的方法将试验结果与数值模型结合起来可以较好地理解土壤冻融过程及处理不确定性，并进而为改进试验方法及完善数值模型提供参考。模型不确定分析结果表明，模型参数之间，及参数与模型模拟效果评价因子之间存在较强的相关性，会造成模拟结果的不确定性。而不同模拟方法的结果对比表明，在进行冻融土壤水热及溶质模拟时，建立更为完善的考虑更为详细的过程的数值模型可以提高模型的模拟效率，减小模拟结果的不确定性。同时，试验数据的不确定性也显示出了对模拟结果的显著影响。精确的试验数据及更为科学的试验方法有助于减少模拟结果的不确定性。在减少模拟结果的不确定性上也有重要作用。同时，由于寒区水文过程的复杂性及在气候变化过程中的重要性，有必要进一步开展寒区地下水，土壤水热盐与气候变化关系的研究，以便于制定更为合理的寒区水资源管理策略。 / Frysning och tining är av betydelse för kopplade flöden av vatten, värme och lösta ämnen i mark. Komplexiteten i sambanden mellan lösta ämnen, ofruset vatten och fryspunkten skapar en osäkerhet vid simuleringar av processer för både vatten, värme och lösta ämnen i marken samt för avdunstningen från markytan. Årtidsberoende mönster i energi- och vattenbalansen för markytan påverkar värme- och vattendynamiken i marken samt ackumulering av salter under vintern. Dygnsvariationer i energibalansens uppdelning vid markytan ger upphov till frysning/tining samt avdunstning och kondensation i ytliga lager som har återkopplingar också till tillstånden i atmosfärens ytskikt. Osäkerheter i både experiment och i simuleringar spårades i undersökningar av säsongstyrd frysning av mark i två provincer av norra Kina. Begräningar i metodik och förenklingar av naturens komplexitet kunde klargöras. Kombinationen av experiment och processbaserad modellering med CoupModel var lyckosam för föreståelsen av frysning/tining och kunde klargöra osäkerhet med hjälp av Monte Carlo teknik. Korrelation mellan parametrar och prestanda hos modellen var en viktig del av kalibreringsproceduren. En förbättrad processbeskrivning av marken och minskad parameterosäkerhet kan erhållas om också mer detaljerade mätningar inbegrips i framtida studier. Sambanden mellan grundvatten, mark och klimatförändringar är av största intresse för en bättre kunna beskriva kalla regioners vatten- och energibalanser. / <p>QC 20160329</p>

La tomographie optique diffuse (TOD) est une technique d’imagerie médicale relativement récente qui utilise la lumière dans le proche infrarouge pour acquérir des images in vivo de façon non invasive. Cette technique est en utilisation croissante par de nombreux chercheurs et biologistes et plusieurs équipes dans le monde travaillent sur le développement de scanners par TOD y compris notre groupe de recherche (groupe TomOptUS). Le Centre d’imagerie moléculaire de Sherbrooke dispose d’un appareil pour imagerie optique sur petit animal développé par la compagnie Quidd, soit le QOS (Quidd Optical imaging System). Cet appareil est utilisé par des biologistes et chercheurs pour diverses études précliniques sur modèles animaux (souris) de maladies humaines comme le cancer. Le QOS est entièrement contrôlé par ordinateur à l’aide d’un logiciel sophistiqué (le QOSoft) qui permet d’obtenir des images en fluorescence et en bioluminescence. Il est toutefois limité en ne permettant d’acquérir que des images planaires de la lumière sortant d’un animal ; il ne permet pas la tomographie, à savoir obtenir des images tridimensionnelles (3D) des sources fluorescentes ou bioluminescentes situées en profondeur à l’intérieur de l’animal. Bien que le QOS offre une grande flexibilité en terme d’angle d’acquisition d’images autour de l’animal avec sa caméra montée sur un bras rotatif, il a une sensibilité limitée pour de l’imagerie en profondeur, notamment parce qu’il fonctionne en mode épiillumination (détection de la lumière du même côté que l’injection de la lumière excitatrice dans l’animal) et aussi à cause de la sensibilité limitée de sa caméra. Afin d’augmenter les capacités tomographiques et la sensibilité du QOS, ainsi que le contraste des images qu’il fournit, le présent projet propose des développements logiciels intégrés au QOSoft. Ces ajouts logiciels au niveau du contrôle d’instrumentation et de l’interface graphique permettent d’intégrer une caméra EMCCD à ultra-haute sensibilité et ultra-faible bruit pour remplacer la caméra CCD refroidie existante ainsi qu’un module d’illumination laser rotatif. Ce module d’illumination, développé par le groupe TomOptUS, permet l’imagerie en mode transillumination ainsi que toutes les configurations intermédiaires jusqu’à l’épi-illumination. Ce module permet en outre d’injecter une densité de puissance lumineuse supérieure à celle possible avec la configuration actuelle du QOS. Le QOS et son logiciel mis à jour avec les ajouts faisant l’objet du présent projet sont validés par des expériences de fluorescence et de bioluminescence sur fantômes et animaux vivants.

Thesis (MScEng (Electrical and Electronic Engineering))--University of Stellenbosch, 2005. / Due to a more densely packed frequency spectrum, there is an increasing demand for narrow band filters with asymmetrical transfer function characteristics. The resulting coupling matrices contain both positive and negative couplings, cross couplings and individual resonator frequency offsets.

There is an intense, worldwide effort to develop durable lithium ion batteries with high energy and power densities for a wide range of applications, including electric and hybrid electric vehicles. For improvement of battery technology understanding the capacity fading mechanism in batteries is of utmost importance. Novel electrode material and improved electrode designs are needed for high energy- high power batteries with less capacity fading. Furthermore, for applications such as automotive applications, precise cycle-life prediction of batteries is necessary. One of the critical challenges in advancing lithium ion battery technologies is fracture and decrepitation of the electrodes as a result of lithium diffusion during charging and discharging operations. When lithium is inserted in either the positive or negative electrode, there is a volume change associated with insertion or de-insertion. Diffusion-induced stresses (DISs) can therefore cause the nucleation and growth of cracks, leading to mechanical degradation of the batteries. With different mathematical models we studied the behavior of diffusion induces stresses and effects of electrode shape, size, concentration dependent material properties, pre-existing cracks, phase transformations, operating conditions etc. on the diffusion induced stresses. Thus we develop tools to guide the design of the electrode material with better mechanical stability for durable batteries. Along with mechanical degradation, chemical degradation of batteries also plays an important role in deciding battery cycle life. The instability of commonly employed electrolytes results in solid electrolyte interphase (SEI) formation. Although SEI formation contributes to irreversible capacity loss, the SEI layer is necessary, as it passivates the electrode-electrolyte interface from further solvent decomposition. SEI layer and diffusion induced stresses are inter-dependent and affect each-other. We study coupled chemical-mechanical degradation of electrode materials to understand the capacity fading of the battery with cycling. With the understanding of chemical and mechanical degradation, we develop a simple phenomenological model to predict battery life. On the experimental part we come up with a novel concept of using liquid metal alloy as a self-healing battery electrode. We develop a method to prepare thin film liquid gallium electrode on a conductive substrate. This enabled us to perform a series of electrochemical and characterization experiments which certify that liquid electrode undergo liquid-solid-liquid transition and thus self-heals the cracks formed during de-insertion. Thus the mechanical degradation can be avoided. We also perform ab-initio calculations to understand the equilibrium potential of various lithium-gallium phases.

<p>Atomic physics plays an important role in determining the evolution stages in a wide range of laboratory and cosmic plasmas. Therefore, the main contribution to our ability to model, infer and control plasma sources is the knowledge of underlying atomic processes. Of particular importance are reliable low temperature dielectronic recombination (DR) rate coefficients.</p><p>This thesis provides systematically calculated DR rate coefficients of lithium-like beryllium and sodium ions via ∆n = 0 doubly excited resonant states. The calculations are based on complex-scaled relativistic many-body perturbation theory in an all-order formulation within the single- and double-excitation coupled-cluster scheme, including radiative corrections.</p><p>Comparison of DR resonance parameters (energy levels, autoionization widths, radiative transition probabilities and strengths) between our theoretical predictions and the heavy-ion storage rings experiments (CRYRING-Stockholm and TSRHeidelberg) shows good agreement.</p><p>The intruder state problem is a principal obstacle for general application of the coupled-cluster formalism on doubly excited states. Thus, we have developed a technique designed to avoid the intruder state problem. It is based on a convenient partitioning of the Hilbert space and reformulation of the conventional set of pairequations. The general aspects of this development are discussed, and the effectiveness of its numerical implementation (within the non-relativistic framework) is selectively illustrated on autoionizing doubly excited states of helium.</p>

The telecommunications market is one of the large rapidly growing fields in today’s power supply industry due to the increasing demand for telecom distributed power supply (DPS) systems. The half-bridge LLC (Inductor-Inductor-Capacitor) resonant converter is currently the most attractive topology for the design and implementation of 24V/48V DC telecom power converters. The current doubler rectifier (CDR) converter topology was invented and described in the early 1950s which can offer the unique characteristic of halving the output voltage while doubling the output current compared to a standard rectifier. In this thesis, the current doubler converter topology with its unique characteristic is evaluated as a complementary solution to improve the LLC resonant converter performance, especially for the low output voltage and high output current telecommunication applications. A novel half-bridge LLC resonant current doubler converter (LLC-CDR) is proposed in this thesis which can offer several performance benefits compared to conventional LLC-standard rectifier design . The unique characteristics of the LLC-CDR topology can offer significant improvements by transformation of a 48V converter into a 24V converter with the same power density. This thesis introduces a new SPICE-based simulation model to analyse the operation of this novel LLC-CDR converter circuit design. This model can be used to define the critical component parameters for the LLC -CDR circuit output inductor values. It can also be used to predict the circuit overall performance under different load conditions. Both time-domain based transient simulation analysis and frequency-domain based AC analysis provided by this simulation model showed favourable results in comparison to bench measurement results on a prototype. The model provides a valuable insight to reveal some of the unique characteristics of this LLC -CDR topology. It demonstrates a proof of concept that the conventional LLC resonant converter can be easily redesigned for low voltage, high current applications by using the LLC-CDR topology without requiring a new design for the LLC resonant stage components and the power transformer. A new magnetic integration solution was proposed to significantly improve the overall performance in the LLC-CDR topology that had not been published before. The LLC-CDR converter hardware prototypes with two output inductors coupled and uncoupled configurations were extensively modelled, constructed and bench tested.Test results demonstrated the suitability of an integrated coupled inductors design for the novel LLC-CDR converter application. The integrated coupled inductors design can significantly improve the LLC-CDR converter frequency-domain based AC simulation analysis results. In addition, these results also illustrate the potential benefit of how the magnetic integration design in general could reduce the magnetic component size, cost, and weight compared to the uncoupled inductors design. Finally, a hardware prototype circuit was constructed based on a commercial 1800 W single phase telecom power converter to verify the operation of this novel half bridge LLC-CDR topology. The converter prototype successfully operated at both no load and full load conditions with the nominal output voltage halved from 48VDC to 24VDC, and doubled the output current to match the same output power density. It also demonstrates that the efficiency of this novel half bridge LLC –CDR is 92% compares to 90% of EATON’s commercial 24VDC LLC resonant converter, which can fulfill the research goals.

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