Purpose: To model the time evolution of active caspase-3 protein expression in a healthy lens, and in a lens exposed to UVR-300 nm (UVR-B). To develop an automated method to classify the fluorescent signal of biomarkers in the lens epithelial cells. Methods: Six-week old Sprague-Dawley rats were used. Firstly, expression of active caspase-3 was studied in the lens epithelium of healthy rats. Secondly, rats were unilaterally exposed in vivo to 1 kJ/m2 UVR-B for 15 minutes. At 0.5, 8, 16, and 24 hours after the UVR-B exposure, the exposed and the contralateral non-exposed lenses were removed. Immunohistochemistry was done on three mid-sagittal sections from each lens. The florescent labelling for active caspase-3 in each lens section was counted three times. The time evolution of active caspase-3 expression in response to UVR-B exposure was modelled as a function of cell position in the lens epithelium. An automated objective method was developed to quantify the lens epithelial cells and to classify the fluorescent signal of active caspase-3. Active caspase-3 was selected as a model signal. Results: Active caspase-3 was abundant in the anterior pole of the normal lenses. Spatial distribution of active caspase-3 labelling in the lens epithelium was fitted to a logistic model. The probability of active caspase-3 expression was higher in the UVR-B exposed lenses (95% CI = 0.12 ± 0.01). There was no difference in the expression of active caspase-3 between the 0.5 and the 24 hours groups or between the 8 and the 16 hours groups. A difference was noted, when comparing the 0.5 and 24 hours groups with the 8 and 16 hours groups (Test statistic 7.01, F1;36;0.95= 4.11). Exposure to UVR-B has an impact on the average probability of labelling for active caspase-3 as a function of cell position. The probability of labelling as a function of cell number also varied as a function of time after UVR-B exposure. The automated method counted the lens epithelial cells and estimated the proportion of active caspase-3 labelling in the lens epithelium. Conclusions: Active caspase-3 is present in the healthy lens epithelial cells. Active caspase-3 exhibits higher expression at the anterior pole of the lens and the expression decreases towards the periphery. After UVR-B exposure, the expression of active caspase-3 in the lens epithelium increases with a peak of expression occurring around 16 hours after exposure. The average probability of labelling in the lens epithelium is dependent on both the UVR-B exposure and the time period elapsed after the exposure. The automated method enables objective and fast quantification of lens epithelial cells and the expression of fluorescent signal in the lens cells.

El alto grado de automatización adquirido en las plantas químicas durante las últimas décadas hace que las tareas de supervisión sean ahora más complejas y delicadas. Esta supervisión requiere de sistemas y herramientas sofisticadas que puedan sacar provecho de los módulos de adquisición de información instalados en planta. Así, el preciso seguimiento de las variables de proceso o la fácil operatividad de los procesos, gracias a los sistemas de control regulatorio actuales, son aspectos relevantes que deben ser contemplados a la hora de dar una respuesta global a las desviaciones del régimen normal de operación.Esta tesis presenta un enfoque global para la gestión de situaciones anormales en plantas químicas. En esta propuesta se contempla el flujo completo de información requerido para responder efectivamente a cualquier situación anormal que se pueda presentar. Mediante esta visión global, primeramente se identifican todos los módulos de planta involucrados en la gestión de fallos; luego se focalizan esfuerzos en mejorar las técnicas que estos módulos usan para su operación; por último, se aprovechan algunas de las sinergias descubiertas mediante esta visión global de la gestión de eventos anormales.De esta forma, el primer capítulo esetablece un primer acercamiento general a las motivaciones y ámbito de las tesis, describiendo rasgos fundamentales en la evolución de la industria química durante los últimos años y los requerimientos asociados al nuevo modelo de supervisión. El segundo capítulo resume las técnicas y aplicaciones actuales para reducir el riesgo de incidencias y accidentes en procesos químicos. Este resumen se centra principalmente en aquellas metodologías más empleadas en la literatura y aquellas con más aceptación en ambientes industriales. Una vez analizado el estado del arte en la supervisión de procesos, se propone un enfoque global de gestión de eventos anormales en el tercer capítulo, que presenta los eslabones de la cadena de gestión de eventos anormales, los cuales serán abordados en detalle en los capítulos restantes.De esta forma, el capítulo 4 se centra en la mejora de los sistemas de adquisición de datos y su posterior tratamiento mediante reconciliación con modelos del proceso. Los capítulos 5, 6, 7 y 8 se dedican al estudio de la parte central de cualquier sistema de respuesta a eventos anormales, el módulo de diagnóstico. El capítulo 5 formaliza el problema de diagnosis y estandariza los índices de evaluación de funcionamiento de los sistemas de diagnóstico. Los capítulo 6 y 7 preentan dos nuevos sistemas de diagnosis basados en el uso de datos históricos. El primero desarrollado en el capítulo 6, implementa un algoritmo de aprendizaje llamada "Máquinas de soporte vectorial" (SVM) adoptando un enfoque "MultiEtiqueta" que permite el diagnóstico eficaz de fallos simultáneos. El segundo sistema (capítulo 7) integra un módulo de detección basado en un modelo de Análisis de Componentes Principales y un módulo de diagnóstico basado en reglas "si-entonces". Como compendio de la diagnosis, el capítulo 8 estudia las fuerzas y debilidades de los sistemas de diagnóstico propuestos y propone una integración de módulos de diagnóstico complementarios que supera el rendimiento de cualquiera de los sistemas por separado.Los capítulos 9 y 10 están centrados en la toma efectiva de decisiones frente a desviaciones del régimen normal de operación. El capítulo 9 presenta una metodología novedosa de integración de conocimiento del proceso en línea y fuera de línea, que permite generar información sustancial de soporte al operador en la toma de decisiones. El capítulo 10 se centra también en la toma de decisiones, mostrando las sinergias generadas al integrar el sistema de diagnosis con otros módulos de planta. En este capítulo el sistema global de gestión de eventos anormales es complementado con un módulo de optimización en línea. De esta forma el nuevo soporte a la toma de decisiones frente a perturbaciones no sólo tiene en cuenta aspectos relacionados con la seguridad sino también con la economía de la planta. Además, la integración permite que la técnica de optimizaicón empleada sea más fiable en su aplicación.Todos los capítulos incluyen una primera parte teórica seguida de una segunda parte centrada en la validación académica e industrail. Aquellos temas que exceden el alcance de estas tesis, son comentados y propuestos como trabajo futuro en el capítulo 11. / The hight automation acquired in chemical industry during last decades has made supervision a delicate and complex task. Therefore, current plants supervision require of sophisticated systems and tools that can create profit from the information installed modules. Thus, the precise tracking of process variables or the high plant operability, achieved by the current regulatory control, are aspects that must be contemplated when the plant has to give a global response against deviations from normal operating regime. This thesis presents a global approach for the management of abnormal situations in chemical plants. In this proposal the complete flow of information required to respond to any nonstandard situation is considered. This global approach incorporates several key aspects: first, all the plant modules that are necessary in the faults management are presented; secondly, this thesis focuses on improving the techniques used in each of these modules so far. Lastly, synergies discovered by the proposed global approach are used to develop novel and promising solutions to address process safety and optimization difficulties.

In this thesis we analyse the high-order in time discontinuous Galerkin nite element method (DGFEM) for second-order in time linear abstract wave equations. Our abstract approximation analysis is a generalisation of the approach introduced by Claes Johnson (in Comput. Methods Appl. Mech. Engrg., 107:117-129, 1993), writing the second order problem as a system of fi rst order problems. We consider abstract spatial (time independent) operators, highorder in time basis functions when discretising in time; we also prove approximation results in case of linear constraints, e.g. non-homogeneous boundary data. We take the two steps approximation approach i.e. using high-order in time DGFEM; the discretisation approach in time introduced by D Schötzau (PhD thesis, Swiss Federal institute of technology, Zürich, 1999) to fi rst obtain the semidiscrete scheme and then conformal spatial discretisation to obtain the fully-discrete formulation. We have shown solvability, unconditional stability and conditional a priori error estimates within our abstract framework for the fully discretized problem. The skew-symmetric spatial forms arising in our abstract framework for the semi- and fully-discrete schemes do not full ll the underlying assumptions in D. Schötzau's work. But the semi-discrete and fully discrete forms satisfy an Inf-sup condition, essential for our proofs; in this sense our approach is also a generalisation of D. Schötzau's work. All estimates are given in a norm in space and time which is weaker than the Hilbert norm belonging to our abstract function spaces, a typical complication in evolution problems. To the best of the author's knowledge, with the approximation approach we used, these stability and a priori error estimates with their abstract structure have not been shown before for the abstract variational formulation used in this thesis. Finally we apply our abstract framework to the acoustic and an elasto-dynamic linear equations with non-homogeneous Dirichlet boundary data.

The climatology of precipitation asymmetries in Tropical Cyclones (TCs) and their relationship to TC intensity changes using 16 years of data from the Tropical Rainfall Measuring Mission (TRMM) satellite. TC Inner core precipitation asymmetries were quantified using the Fourier wavenumber decomposition method upon the pixel level data of 3,542 TRMM TMI overpasses. Composites of wavenumber–1 and wavenumber 1–6 total precipitation asymmetries were constructed to show the distribution pattern under different storm motion speed, vertical wind shear and the combined effects of varying vertical wind shear and storm motion. Results indicate that motion–relative total precipitation asymmetry is located down–motion. The phase of motion–relative maximum asymmetry shifts cyclonically by adding the wavenumber–2–6 asymmetry to wavenumber–1. Shear is more dominant than motion on the distribution of precipitation asymmetry. The analysis of combined effects of motion and shear shows when shear is weak, and shear is to the left of motion, the precipitation asymmetry is explained more by storm motion. The main contributor to the general asymmetry pattern is from the moderate and heavy precipitation. The wavenumber 2–6 energy localizes the maximum heavy precipitation asymmetry. The quantified wavenumber 1–6 asymmetries is also applied to differentiate between different intensity change categories and the asymmetry evolution of a rapidly intensifying storm. The precipitation asymmetry properties of rapid intensification (RI) and non–RI storms are examined. The dataset of 2,186 global tropical storms through category 2 hurricanes is divided by future 24–h intensity change and includes storms with at least moderately favorable environmental conditions. The normalized wavenumber 1–6 asymmetries, indicates quantitatively that the lower asymmetry of precipitation is most strongly correlated with future intensity change. The precipitation field of non–RI storms are more asymmetric than RI storms. The 595 sampled overpasses are classified into 14 categories in the timeline of an RI event from 48 hours before RI until RI ends. The decrease of normalized wavenumber 1–6 asymmetries in the inner core region of all four types of precipitation several hours before RI onset was quantitatively demonstrated to be critical for TC RI.

Doctor of Philosophy / Department of Physics / B.D. DePaola / In recent years, coherent excitation techniques have focused on the ability to efficiently prepare atomic or molecular systems into a selected state. Such population control plays a key role in cutting-edge research taking place today, such as in the areas of quantum information and laser-controlled chemical reactions. Stimulated Raman adiabatic passage (STIRAP) is a widely-used coherent excitation technique that provides a relatively robust control mechanism for efficiently exciting a target population into a desired state. While the technique is well proven, current experimental techniques yield little information on the population dynamics taking place throughout the excitation process, and experimentalists rely solely on final excited-state measurements to determine the efficiency of population transfer. This dissertation presents a unique diagnostic tool to measure multilevel coherent population transfer on a short (nanosecond) timescale. The technique described here uses magneto-optical trap recoil ion momentum spectroscopy (MOTRIMS) as a noninvasive probe of a coherently-controlled system. It provides extremely detailed information about the excitation process, and highlights some important characteristics seen in excited populations that would otherwise be misleading or completely overlooked if one were to use more traditional diagnostic techniques. This dissertation discusses both the theoretical and experimental results applied to three-level coherently excited target populations of Rb-87.

La physique de la matière condensée, et notamment les systèmes fortement corrélés, amènent à des problèmes parmi les plus stimulants et difficiles de la physique moderne. Dans ces systèmes, les interactions à plusieurs corps et les corrélations entre les particules quantiques ne peuvent être négligées, sinon, les modèles échoueraient simplement à capturer les mécanismes physiques en jeu et les phénomènes qui en découlent. En particulier, le travail présenté dans ce manuscrit traite du magnétisme quantique et aborde plusieurs questions distinctes à l'aide d'approches computationnelles et méthodes numériques à l'état de l'art. Les effets conjoints du désordre (i.e. impuretés) et des interactions sont étudiés concernant un matériau magnétique spécifique : plutôt qu'une phase de la matière dite localisée, attendue à fort champ magnétique, une phase ordonnée induite par le désordre lui-même est mise en lumière, avec une réapparition inattendue de la cohérence quantique dans ledit composé. Par ailleurs, la réponse dynamique d'aimants quantiques à une perturbation externe, comme celle mesurée dans des expériences de résonance magnétique nucléaire ou de diffusion inélastique de neutrons est étudiée. / Condensed matter physics, and especially strongly correlated systems provide some of the most challenging problems of modern physics. In these systems, the many-body interactions and correlations between quantum particles cannot be neglected; otherwise, the models would simply fail to capture the relevant physics at play and phenomena ensuing. In particular, the work presented in this manuscript deals with quantum magnetism and addresses several distinct questions through computational approaches and state-of-the-art numerical methods. The interplay between disorder (i.e. impurities) and interactions is studied regarding a specific magnetic compound, where instead of the expected many-body localized phase at high magnetic fields, a novel disorder-induced ordered state of matter is found, with a resurgence of quantum coherence. Furthermore, the dynamical response of quantum magnets to an external perturbation, such as it is accessed and measured in nuclear magnetic resonance and inelastic neutron scattering experiments is investigated.

Light-harvesting in nature is known to work differently than conventional man-made solar cells. Recent studies found electronic excitations, delocalised over several chromophores, and a soft, vibrating structural environment to be key schemes that might protect and direct energy transfer yielding increased harvest efficiencies even under adversary conditions. Unfortunately, testing realistic models of noise assisted transport at the quantum level is challenging due to the intractable size of the environmental wave function. I developed a powerful tree tensor network states (TTNS) method that finds an optimally compressed explicit representation of the combined electronic and vibrational quantum state. With TTNS it is possible to simulate exciton-phonon quantum dynamics from small molecules to larger complexes, modelled as an open quantum system with multiple bosonic environments. After benchmarking the method on the minimal spin-boson model by reproducing ground state properties and dynamics that have been reported using other methods, the vibrational quantum state is harnessed to investigate environmental dynamics and its correlation with the spin system. To enable simulations of realistic non-Born-Oppenheimer molecular quantum dynamics, a clustering algorithm and novel entanglement renormalisation tensors are employed to interface TTNS with ab initio density functional theory (DFT). A thereby generated model of a pentacene dimer containing 252 vibrational normal modes was simulated with TTNS reproducing exciton dynamics in agreement with experimental results. Based on the environmental state, the (potential) energy surfaces, underlying the observed singlet fission dynamics, were calculated yielding unprecedented insight into the super-exchange mediated avoided crossing mechanism that produces ultrafast and high yield singlet fission. This combination of DFT and TTNS is a step towards large scale material exploration that can accurately predict excited states properties and dynamics. Furthermore, application to biomolecular systems, such as photosynthetic complexes, may give valuable insights into novel environmental engineering principles for the design of artificial light-harvesting systems.

In this thesis, we investigated modes of intraseasonal variability (ISV) observed in the Indian monsoon rainfall and how these modes modulate rainfall over India. We identified a decreasing trend in the intensity of low-frequency intraseasonal mode with increasing strength in synoptic variability over India. We also made an attempt to understand the reason for these observed trends using numerical simulations. In the first part of the thesis, satellite rainfall estimates are used to understand the spatiotem-poral structures of convection in the intraseasonal timescale and their intensity during boreal sum-mer over south Asia. Two dominant modes of variability with periodicities of 10–20-days (high-frequency) and 20–60-days (low-frequency) are found, with the latter strongly modulated by sea surface temperature. The 20–60-day mode shows northward propagation from the equatorial In-dian Ocean linked with eastward propagating modes of convective systems over the tropics. The 10–20-day mode shows a complex space-time structure with a northwestward propagating anoma-lous pattern emanating from the Indonesian coast. This pattern is found to be interacting with a structure emerging from higher latitudes propagating southeastwards. This could be related to ver-tical shear of zonal wind over northern India. The two modes exhibit variability in their intensity on the interannual time scale and contribute a significant amount to the daily rainfall variability in a season. The intensities of the 20–60-day and 10–20-day modes show significantly strong inverse and direct relationship, respectively, with the all-India June–September rainfall. This study also establishes that the probability of occurrence of substantial rainfall over central India increases significantly if the two intraseasonal modes simultaneously exhibit positive anomalies over the region. There also exists a phase-locking between the two modes. In the second part of the thesis, we investigated the changing nature of these intraseasonal modes over Indian region, and their association with extreme rainfall events using ground based observed rainfall. We found that the relative strength of the northward propagating 20–60-day mode has a significant decreasing trend during the past six decades, possibly attributed to the weakening of large-scale circulation in the region during monsoon. This reduction is compensated by a gain in synoptic-scale (3–9 days) variability. The decrease in the low-frequency ISV is associated with a significant decreasing trend in the percentage of extreme events during the active phase of the monsoon. However, this decrease is balanced by a significant increasing trend in the percentage of extreme events in break phase. We also find a significant rise in occurrence of extremes during early- and late-monsoon months, mainly over the eastern coastal regions of India. We do not observe any significant trend in the high-frequency ISV. In the last part of the thesis, we used numerical simulations to understand the observed changes in the ISV features. Using the atmospheric component of a global climate model (GCM), we have performed two experiments: control experiment (CE) and heating experiment (HE). The CE is the default simulation for 10 years. In HE, we prescribed heating in the atmosphere in such a way that it mimics the conditions for extreme rainfall events as observed over central India during June– September. Heating is prescribed primarily during the break phase of the 20–60-day mode. This basically increases the number of extremes, majority of which are in break phase. The design of the experiment reflects the observed current scenario of increased extreme events during breaks. We found that the increased extreme events in the HE decreased the intensity of the 20–60-day mode over the Indian region. This reduction is associated with a reduction of rainfall in active phase and increase in the length of break phase. A reduction in the seasonal mean over India is also observed. The reduction of active phase rainfall is linked with an increased stability of the atmosphere over central India. Lastly, we propose a possible mechanism for the reduction of rainfall in active phase. We found that there is a significant reduction in the strength of the vertical easterly shear over the northern Indian region during break–active transition phase. This basically weakens the conditions for the growth of Rossby wave instability, thereby elongating break phase and reducing the rainfall intensity in the following active phase. This study highlights the redistribution of rainfall intensity among periodic (low-frequency) and non-periodic (extreme) modes in a changing climate scenario, which is further tested in a modeling study. The results presented in this thesis will provide a pathway to understand, using observations and numerical model simulations, the ISV and its relative contribution to the Indian summer monsoon. It can also be used for model evaluation.

Supervisor at Deutsches Elektronen-Synchrotron (DESY) in Zeuthen: Dr. Habil. Karl Jansen / Mit Tensor Netzwerken (TN) untersuchen wir auf einem hexagonalen Gitter das Hubbard-Modell mit einem chemischen Potential. Wir zeigen, dass ein TN als Ansatz für die Zustände des Modells benutzt werden kann und präsentieren die berechneten Eigenschaften bei niedrigen Energien. Unser Algorithmus wendet eine imaginäre Zeitentwicklung auf einen fermionischen projected engangled pair state (PEPS) auf einem endlichen Gitter mit offenen Randbedingungen an. Der Ansatz kann auf einen spezifischen fermionischen Paritätssektor beschränkt werden, was es uns ermöglicht, den Grundzustand und den Zustand mit einem Elektron weniger zu simulieren. Mehrere in unserer Arbeit entwickelte Verbesserungen des Algorithmus führen zu einer erheblichen Steigerung der Effizienz und Genauigkeit. Wir messen Erwartungswerte mit Hilfe eines boundary matrix product state. Wir zeigen, dass Observablen in dieser Näherung mit einer weniger starken Trunkierung, als in der Literatur erwartet wird, berechnet werden können. Dies führt zu einer erheblichen Reduzierung der numerischen Kosten des Algorithmus. Für verschiedene Stärken der lokalen Wechselwirkung, sowie für mehrere chemische Potentiale berechnen wir die Energie, die Teilchenzahl und die Magnetisierung mit guter Genauigkeit. Wir zeigen die Abhängigkeit der Teilchenzahl vom chemischen Potential und berechnen die Energielücke. Wir demonstrieren die Skalierbarkeit zu großen Gittern mit bis zu 30 × 15 Gitterpunkten und machen Vorhersagen in einem Teil des Phasenraums, der für Monte-Carlo nicht zugänglich ist. Allerdings finden wir auch Limitierungen des Algorithmus aufgrund von Instabilitäten, die die Berechnungen im Paritätssektor behindern, welcher orthogonal zum Grundzustand ist. Wir diskutieren Ursachen und Indikatoren und schlagen Lösungen vor. Unsere Arbeit bestätigt, dass TN genutzt werden können, um den niederenergetischen Sektors des Modells zu erforschen. Dies eröffnet den Weg zu einem umfassenden Verständnis des Phasendiagramms. / Using tensor network (TN) techniques, we study the Hubbard model on a honeycomb lattice with a chemical potential, which models the electron structure of graphene. In contrast to Monte Carlo methods, TN algorithms do not suffer from the sign problem when a chemical potential is present. We demonstrate that a tensor network state can be used to simulate the model and present the calculated low energy properties of the Hubbard model. Our algorithm applies an imaginary time evolution to a fermionic projected entangled pair state (PEPS) on a finite lattice with open boundary conditions. The ansatz can be restricted to a specific fermionic parity sector which allows us to simulate the ground state and the state with one electron less. Several improvements of the algorithm developed in our work lead to a substantial performance increase of the efficiency and precision. We measure expectation values with a boundary matrix product state and show that observables can be calculated with a lower bond dimension of this approximation than expected from the literature. This decreases the numerical costs of the algorithm significantly. For varying onsite interactions and chemical potentials we calculate the energy, particle number and magnetization with good precision. We show the dependence of the particle number on the chemical potential and compute the single particle gap. We demonstrate the scalability to large lattices of up to 30 × 15 sites and make predictions in a part of the phase space that is not accessible to Monte Carlo methods. However, we also find limitations of the algorithm due to instabilities that spoil the calculations in the parity sector orthogonal to the ground state. We discuss the causes and indicators of such instabilities and propose solutions. Our work validates that TNs can be utilized to study the low energy properties of the Hubbard model on a honeycomb lattice with a chemical potential, thus opening the road to finally understand its phase diagram.