京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第18783号 / 理博第4041号 / 新制||理||1582(附属図書館) / 31734 / 京都大学大学院理学研究科物理学・宇宙物理学専攻 / (主査)教授 佐々 真一, 准教授 篠本 滋, 准教授 武末 真二 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

A resonant microwave cavity technique was employed to study the dielectric behavior of some polar and non-polar liquids near the phase transition temperatures at microwave frequencies of 7.2, 9.2 and 10.1 GHz. The Slater perturbation equations for a resonant microwave cavity are briefly discussed to show that the above technique can be used to determine both the real and imaginary parts of dielectric response. Abrupt changes in dielectric response were observed near the phase transition temperatures for the polar liquids studied in this investigation. The dielectric relaxation phenomenon in liquids has been treated as a chemical rate process and the abrupt change in the dielectric response of the liquids near phase transition temperatures is shown to be related to the dramatic changes in the free energy of activation of the molecules. Some values of the free energy of activation were deduced for the various compounds from data obtained in this investigation.

No description available.

Shape Memory Alloys (SMA’s) are intermetallic materials (chemical compounds of two or more elements) that are able to sustain a residual deformation after the application of a large stress, but they “remember” the original shape to which they creep back, without the application of any external force, after they are heated above a certain critical temperature. A general one-dimensional dynamic mathematical model is presented which accounts for thermal coupling, time-dependent distributed and boundary inputs and internal variables. Well-posedness is obtained using an abstract formulation in an appropriate Hilbert space and explicit decay rates for the associated linear semigroup are derived. Numerical experiments using finite-dimensional approximations are performed for the case in which the thermodynamic potential is given in the Landau-Devonshire form. The sensitivity of the solutions with respect to the model parameters is studied. Finally, an alternative approach to the stress-strain laws is presented which is able to capture the dependence on the strain history. / Ph. D.

Accurate modeling of structural ensembles is essential for understanding molecular function, predicting molecular interactions, refining molecular potentials, protein engineering, drug discovery, and more. Here, we enhance molecular modeling through Bayesian Inference of Conformational Populations (BICePs), a highly versatile algorithm for reweighting simulated ensembles with experimental data. By incorporating replica-averaging, improved likelihood functions to better address systematic errors, and adopting variational optimization schemes, the utility of this algorithm in the refinement and validation of both structural ensembles and empirical models is unmatched. Utilizing a set of diverse experimental measurements, including NOE distances, chemical shifts, and vicinal J-coupling constants, we evaluated nine force fields for simulating the mini-protein chignolin, highlighting BICePs’ capability to correctly identify folded conformations and perform objective model selection. Additionally, we demonstrate how BICePs automates the parameterization of molecular potentials and forward models—computational frameworks that generate observable quantities—while properly accounting for all sources of random and systematic error. By reconciling prior knowledge of structural ensembles with solution-based experimental observations, BICePs not only offers a robust approach for evaluating the predictive accuracy of molecular models but also shows significant promise for future applications in computational chemistry and biophysics. / Chemistry

Diese Arbeit zielt darauf ab, die raumzeitlichen Regelmäßigkeiten an Übergängen aufzudecken, die in saisonalen Klima- und Ingenieursystemen beobachtet werden, indem moderne Methoden der komplexen Systemwissenschaft verwendet werden. Das erste System ist der indische Sommermonsun - eine Regenzeit, deren jährliche Schwankungen das Leben und den Wohlstand von mehr als einer Milliarde Menschen auf dem indischen Subkontinent beeinflussen und die Wirtschaft des von der Landwirtschaft abhängigen Landes stark beeinträchtigen. Insbesondere die Kenntnis des zeitlichen Ablaufs des Übergangs vom Vormonsun zum Monsun ist für die Planung landwirtschaftlicher Aktivitäten dringend erforderlich. Die Vorhersage des Monsunzeitpunkts über dem indischen Kontinent bleibt jedoch eine große wissenschaftliche Herausforderung. Das zweite ist ein Verbrennungssystem, das anfällig für ein katastrophales Phänomen namens thermoakustische Instabilität ist, das verhindert, dass das Verbrennungssystem unter klimafreundlichen Bedingungen betrieben wird. Eine solche Brennkammer ist typisch für Energie- und Antriebssysteme wie Gasturbinentriebwerke, Boiler und Raketen. Zu verstehen, wann der Übergang zur thermoakustischen Instabilität auftritt und wie dieser Übergang unterdrückt werden kann, sind Schlüsselfragen für die Entwicklung klimafreundlicher Motoren. Diese Dissertation liefert ein neues Verständnis des indischen Sommermonsuns und der thermoakustischen Instabilität durch auf statistischer Physik basierende Ansätze, die verborgene Merkmale in diesen Systemen nahe ihren jeweiligen Übergängen aufdecken. / This thesis aims to reveal the spatiotemporal regularities at transitions observed in seasonal climate and engineering systems by utilizing modern methods of complex systems science. The first system is the Indian Summer Monsoon - a rainy season whose yearly variability affects the life and prosperity of more than a billion people in the Indian subcontinent and strongly impacts the economy of the agriculture-dependent country. In particular, knowledge of the timing of the transition from pre-monsoon to monsoon is greatly needed for the planning of agriculture activities. However, the prediction of monsoon timing over the Indian continent remains a significant scientific challenge. The second is a combustion system prone to a catastrophic phenomenon called thermoacoustic instability, which prevents the combustion system from being operated in climate-friendly conditions. Such a combustor is typical in power and propulsion systems such as gas turbine engines, boilers, and rockets. Understanding when the transition to thermoacoustic instability occurs and how to suppress this transition are key questions for developing climate-friendly engines. This thesis provides a new understanding of the Indian Summer Monsoon and thermoacoustic instability through statistical physics-based approaches that reveal hidden features in these systems near their respective transitions.

Die große Menge an Datensätzen, die in den letzten Jahren verfügbar wurden, hat es ermöglicht, sowohl menschlich-getriebene als auch biologische komplexe Systeme in einem beispiellosen Ausmaß empirisch zu untersuchen. Parallel dazu ist die Vorhersage und Kontrolle epidemischer Ausbrüche für Fragen der öffentlichen Gesundheit sehr wichtig geworden. In dieser Arbeit untersuchen wir einige wichtige Aspekte von Diffusionsphänomenen und Ausbreitungsprozeßen auf Netzwerken. Wir untersuchen drei verschiedene Probleme im Zusammenhang mit Ausbreitungsprozeßen im überkritischen Regime. Zunächst untersuchen wir die Reaktionsdiffusion auf Ensembles zufälliger Netzwerke, die durch die beobachteten Levy-Flugeigenschaften der menschlichen Mobilität charakterisiert sind. Das zweite Problem ist die Schätzung der Ankunftszeiten globaler Pandemien. Zu diesem Zweck leiten wir geeignete verborgene Geometrien netzgetriebener Streuprozeße, unter Nutzung der Random-Walk-Theorie, her und identifizieren diese. Durch die Definition von effective distances wird das Problem komplexer raumzeitlicher Muster auf einfache, homogene Wellenausbreitungsmuster reduziert. Drittens führen wir durch die Einbettung von Knoten in den verborgenen Raum, der durch effective distances im Netzwerk definiert ist, eine neuartige Netzwerkzentralität ein, die ViralRank genannt wird und quantifiziert, wie nahe ein Knoten, im Durchschnitt, den anderen Knoten im Netzwerk ist. Diese drei Studien bilden einen einheitlichen Rahmen zur Charakterisierung von Diffusions- und Ausbreitungsprozeßen, die sich auf komplexen Netzwerken allgemein abzeichnen, und bieten neue Ansätze für herausfordernde theoretische Probleme, die für die Bewertung künftiger Modelle verwendet werden können. / The large amount of datasets that became available in recent years has made it possible to empirically study humanly-driven, as well as biological complex systems to an unprecedented extent. In parallel, the prediction and control of epidemic outbreaks have become very important for public health issues. In this thesis, we investigate some important aspects of diffusion phenomena and spreading processes unfolding on networks. We study three different problems related to spreading processes in the supercritical regime. First, we study reaction-diffusion on ensembles of random networks characterized by the observed Levy-flight properties of human mobility. The second problem is the estimation of the arrival times of global pandemics. To this end, we derive and identify suitable hidden geometries of network-driven spreading processes, leveraging on random-walk theory. Through the definition of network effective distances, the problem of complex spatiotemporal patterns is reduced to simple, homogeneous wave propagation patterns. Third, by embedding nodes in the hidden space defined by network effective distances, we introduce a novel network centrality, called ViralRank, which quantifies how close a node is, on average, to the other nodes. These three studies constitute a unified framework to characterize diffusion and spreading processes unfolding on complex networks in very general settings, and provide new approaches to challenging theoretical problems that can be used to benchmark future models.

Ziel dieser Arbeit ist die Analyse zweier physikalischer Prozesse, die stattfinden wenn ein festes polymeres Medium in Kontakt mit einer Gas-Atmosphäre kommt: 1) ein Sorptionsprozess, d.h. die Gasmoleküle dringen in den Feststoff ein und 2) ein Diffusionsprozess, d.h. die Gasmoleküle bewegen sich danach innerhalb des Feststoffes. Der Sorptionsprozess wird als Model analysiert, das in engem Zusammenhang mit dem Dual Mode Model steht. Wir gewinnen die Abhängigkeit der Konzentration vom Druck der Gasphase, die, wie im Gas-Polymer-Matrix model vorhergesagt, durch eine Lambertsche W-Funktion ausgedrückt werden kann und dadurch von der Vorhersage des Dual Sorption Mode Models abweicht. Die Lambertsche Funktion stellt einen universelle Verhalt dar. Ein Fitting von realen Daten zeigt, dass die Lambert-Funktion die Daten gleichermaßen gut modelliert. Das Diffusionsproblem wird mittels eines Gitter-Modells mit zufälligen Knotenenergien und Übergangsraten analysiert. Die Analogie zwischen dem effektiven Diffusionskoeffizienten und der makroskopischen Leitfähigkeit eines zufälligen Widerstandsnetzwerks ermöglicht es, mögliche Quellen für anomale Diffusion in einer solchen Umgebung zu finden. Die Eigenschaften der effektiven Diffusionskonstanten werden diskutiert. Das System wird durch Teilchendiffusion auf einem Ternär-Gitter modelliert, wo die Gitterplätze blockiert werden, die von Polymerteilen besetzt sind. In Abwesenheit von Wechselwirkungen zeigt der Diffusionskoeffizient nur eine schwache Abhängigkeit von der Polymerlänge und sein Verhalten ähnelt stark dem der gewöhnlichen Knotenperkolation. In Anwesenheit von Wechselwirkungen zeigt der Diffusionskoeffizient ein nicht-triviales Verhalten, abhängig vom Vorzeichen der Wechselwirkung und davon, ob die Poren und die Hüllen perkolieren oder nicht. Die analytischen Ergebnisse zeigen eine qualitative Übereinstimmung mit Ergebnissen aus Monte-Carlo Simulationen / Aim of this work is to analyze two physical processes that take place whenever a solid polymeric medium is put in contact with a gas atmosphere. gas molecules first penetrate the solid through a sorption process and then wander within it giving rise to a diffusion one. The sorption process is studied within a model which is very close in spirit to the dual mode model. We obtain the dependence of the penetrant concentration on the pressure of the gas phase and find that this is expressed via the Lambert W-function, as proposed by the gas-polymer matrix model, being a different functional form than the one proposed by dual sorption mode. The Lambert function represents therefore a general universal behavior. Fitting the existing data shows that the Lambert function fits the data equally well. The diffusion problem is analyzed by using a lattice approach with random site energies and random transition rates. A relation between the effective diffusion coefficient and the macroscopic conductivity in a random resistor network allows for elucidating all the possible sources of anomalous diffusion in such an environment. Properties of the effective diffusion constant are further discussed. The system is modeled by a particle diffusion on a ternary lattice where the sites occupied by polymer segments are blocked, the ones forming the hull of the chains correspond to the places at which the interaction takes place, and the rest are voids. In the absence of interaction the diffusion coefficient shows only a weak dependence on the polymer chain length and its behavior strongly resembles usual site percolation. In presence of interactions the diffusion coefficient shows a non-trivial behavior depending on the sign of interaction and on whether the voids and the hulls of the chains percolate or not. The analytical results obtained within the effective medium approximation are in qualitative agreement with those of Monte Carlo simulations.

Chromonic liquid crystals are a relatively new class of lyotropic liquid crystals. In an effort to understand this lyotropic phase better, studies on the phase behavior, defects formed in these systems and characterization of the order were performed. We studied three chromonic liquid crystal materials in nematic and biphasic regions: Sunset Yellow FCF (SSY, a food dye), a cationic perylene diimide derivative (PDI, a conducting dye) and cromolyn sodium (DSCG, a drug). For SSY chromonics in the nematic region, order parameters ( and ) were obtained by polarized Raman measurements. Using the order parameters the flow behavior was predicted and was found to be non-flow aligning. A comprehensive viscoelastic property set of SSY chromonics was obtained by studying the statics and dynamics of defects during the formation of planar aligned monodomain. Applications of PDI thin films as vapor sensors were explored; anisotropic electronic properties of oriented PDI films show good conductivity along the columns presumably arising from the overlap between the ? systems. In the biphasic region, growth and fluctuation of SSY tactoids and interesting patterns of biphasic DSCG under capillary geometry were observed; elastic properties and surface tension were estimated based on the shape of DSCG tactoids. Polymer dispersed lyotropic chromonic liquid crystals with different drop shapes and director configurations were also fabricated using various water-soluble polymers.

We propose a mathematical procedure to derive a stochastic parameterization for the bulk warm cloud micro-physical properties of collision and coalescence. Unlike previous bulk parameterizations, the stochastic parameterization does not assume any particular droplet size distribution, all parameters have physical meanings which are recoverable from data, all equations are independently derived making conservation of mass intrinsic, the auto conversion parameter is finely controllable, and the resultant parameterization has the flexibility to utilize a variety of collision kernels. This new approach to modelling the kinetic collection equation (KCE) decouples the choice of a droplet size distribution and a collision kernel from a cloud microphysical parameterization employed by the governing climate model. In essence, a climate model utilizing this new parameterization of cloud microphysics could have different distributions and different kernels in different climate model cells, yet employ a single parameterization scheme. This stochastic bulk model is validated theoretically and empirically against an existing bulk model that contains a simple enough (toy) collision kernel such that the KCE can be solved analytically. Theoretically, the stochastic model reproduces all the terms of each equation in the existing model and precisely reproduces the power law dependence for all of the evolving cloud properties. Empirically, values of stochastic parameters can be chosen graphically which will precisely reproduce the coefficients of the existing model, save for some ad-hoc non-dimensional time functions. Furthermore values of stochastic parameters are chosen graphically. The values selected for the stochastic parameters effect the conversion rate of mass cloud to rain. This conversion rate is compared against (i) an existing bulk model, and (ii) a detailed solution that is used as a benchmark. The utility of the stochastic bulk model is extended to include hydrodynamic and turbulent collision kernels for both clean and polluted clouds. The validation and extension compares the time required to convert 50\% of cloud mass to rain mass, compares the mean rain radius at that time, and used detailed simulations as benchmarks. Stochastic parameters can be chosen graphically to replicate the 50\% conversion time in all cases. The curves showing the evolution of mass conversion that are generated by the stochastic model with realistic kernels do not match corresponding benchmark curves at all times during the evolution for constant parameter values. The degree to which the benchmark curves represent ground truth, i.e. atmospheric observations, is unknown. Finally, among alternate methods of acquiring parameter values, getting a set of sequential values for a single parameter has a stronger physical foundation than getting one value per parameter, and a stochastic simulation is preferable to a higher order detailed method due to the presence of bias in the latter. / Graduate / 0725 0608 0405 / davidc@uvic.ca