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Three dimensional (3d) point data is used in industry for measurement and reverse engineering. Precise point data is usually acquired with triangulating laser scanners or high precision structured light scanners. Lower precision point data is acquired by real-time structured light devices or by stereo matching with multiple cameras. The basic principle of all these methods is the so-called triangulation of 3d coordinates from two dimensional (2d) camera images.
This dissertation contributes a method for multi-camera stereo matching that uses a system of four synchronized cameras. A GPU based stereo matching method is presented to achieve a high quality reconstruction at interactive frame rates. Good depth resolution is achieved by allowing large disparities between the images. A multi level approach on the GPU allows a fast processing of these large disparities. In reverse engineering, hand-held laser scanners are used for the scanning of complex shaped objects. The operator of the scanner can scan complex regions slower, multiple times, or from multiple angles to achieve a higher point density. Traditionally, computer aided design (CAD) geometry is reconstructed in a separate step after the scanning. Errors or missing parts in the scan prevent a successful reconstruction. The contribution of this dissertation is an on-line algorithm that allows the reconstruction during the scanning of an object. Scanned points are added to the reconstruction and improve it on-line. The operator can detect the areas in the scan where the reconstruction needs additional data.
First, the point data is thinned out using an octree based data structure. Local normals and principal curvatures are estimated for the reduced set of points. These local geometric values are used for segmentation using a region growing approach. Implicit quadrics are fitted to these segments. The canonical form of the quadrics provides the parameters of basic geometric primitives.
An improved approach uses so called accumulated means of local geometric properties to perform segmentation and primitive reconstruction in a single step. Local geometric values can be added and removed on-line to these means to get a stable estimate over a complete segment. By estimating the shape of the segment it is decided which local areas are added to a segment. An accumulated score estimates the probability for a segment to belong to a certain type of geometric primitive. A boundary around the segment is reconstructed using a growing algorithm that ensures that the boundary is closed and avoids self intersections.
This PhD-Thesis deals with the calculation and application of a new class of invariants, that can be used to recognize patterns in tensor fields (i.e. scalar fields, vector fields und matrix fields), and by the composition of scalar fields with delta-functions also to point-clouds.
In the first chapter an overview over already existing invariants is given.
In the second chapter the general definition of the new invariants is given:
starting with a tensor field a set of moment tensor is created via folding in tensor-product manner with different orders of the tensor product of the positional vector. From these, rotational invariant values are calculated via contraction of tensor products. An algorithm to get a complete and independent set of invariants from a given moment tensor set is described. Furthermore methods to make these sets of invariants invariant against translation, rotation, scaling, and affine transformation.
In the third chapter, a method to optimize the calculation of these sets of invariants is described: every invariant can be modeled as undirected graph comprising multiple sub-graphs representing partially contracted tensor products of the moment tensors.
The composition of the sets of invariants is optimized by a clever choice of the decomposition into sub-graphs, all paths creating a hyper-graph of sub-graphs where each node describes a composition step. Finally, C++-source-code is created, which optimized using the symmetry of the different tensors and tensor-products, and a comparison of the effort to other calculation methods of invariants is given.
The fourth chapter describes the application of the invariants to object recognition in point-clouds from 3D-scans. To do this, the invariants of sub-sets of point-clouds are stored for every known object. Afterwards, invariants are calculated from an unknown point-cloud and tried to find them in the database to assign it to one of the known objects. Benchmarks using three 3D-object databases are made testing time and recognition rate.
The study addresses the effect of multiple jet passes and other parameters namely feedrate, water pressure and standoff distance in waterjet peening of metallic
surfaces. An analysis of surface integrity was used to evaluate the performance of
different parameters in the process. An increase in the number of jet passes and
pressure leads to a higher roughness and more erosion and also a higher hardness.
In contrast, the feedrate shows a reverse effect on those surface characteristics.
There exists a specific value of standoff distance that results in the maximum surface
roughness, erosion as well as hardness. Analysis of the surface microstructure gave
a good insight into the mechanism material removal process involving initial and
evolved damage. Also, the waterjet peening process was optimized based on the
design of experiment approach. The developed empirical models had shown
reasonable correlations between the measured and predicted responses. A proper selection of waterjet peening parameters can be formulated to be used in practical
works.
Mechanical ventilation of patients with severe lung injury is an important clinical treatment to ensure proper lung oxygenation and to mitigate the extent of collapsed lung regions. While current imaging technologies such as Computed Tomography (CT) and chest X-ray allow for a thorough inspection of the thorax, they are limited to static pictures and exhibit several disadvantages, including exposure to ionizing radiation and high cost. Electrical Impedance Tomography (EIT) is a novel method to determine functional processes inside the thorax such as lung ventilation and cardiac activity. EIT reconstructs the internal electrical conductivity distribution within the thorax from voltage measurements on the body surface. Conductivity changes correlate with important clinical parameters such as lung volume and perfusion. Current EIT systems and algorithms use simplified or generalized thorax models to solve the reconstruction problem, which reduce image quality and anatomical significance. In this thesis, the development of a clinically relevant workflow to compute sophisticated three-dimensional thorax models from patient-specific CT data is described. The method allows medical experts to generate a multi-material segmentation in an interactive and fast way, while a volumetric mesh is computed automatically from the segmentation. The significantly improved image quality and anatomical precision of EIT images reconstructed with these 3D models is reported, and the impact on clinical applicability is discussed. In addition, three projects concerning quantitative CT (qCT) measurements and multi-modal 3D visualization are presented, which demonstrate the importance and productivity of interdisciplinary research groups including computer scientists and medical experts. The results presented in this thesis contribute significantly to clinical research efforts to pave the way towards improved patient-specific treatments of lung injury using EIT and qCT.
The heart is reported to show a net consumption of lactate. This may contribute up to 15% to the total body lactate disposal. In this work, the consumption of lactate was shown for the first
time on the single cell level with the new FRET-based lactate sensor Laconic.
Research published until today, almost exclusively reports the monocarboxylate transporter 1
(MCT1) as the transporter responsible for myocardial lactate uptake. As this membrane
transporter transports lactate together with H+ in a stoichiometry of 1:1, lactate transport is
coupled to pH regulation. Consequently, interactions of MCT1 and acid/base regulating proteins
(carbonic anhydrases (CAs and sodium bicarbonate co-transporters (NBCs)) are described in
the oocyte expression system, skeletal muscle and cancer cells.
In this work it is shown that activity of extracellular CA increases lactate uptake into mouse
cardiomyocytes by 27% and lactate induced JA/B by 42.8% to 46.2%. This effect is most likely
mediated via NBC/CA interaction because inhibition of extracellular CA reduces HCO3--
dependent acid extruding JA/B by 53.3% to 78.4%. This may link lactate uptake to cellular
respiration. When lactate was applied in medium gassed with 100% N2, lactate induced
acidification was 12.6% faster than in medium gassed with 100% O2. Thus, CO2 produced on
the pathway transferring redox energy from substrates like glucose and lactate to ADP and
phosphate via oxidative phosphorylation, may support further lactate uptake. The findings of
this work suggest an auto regulation of lactate uptake via CO2 release in ventricular mouse
cardiomyocytes.
Researchers and analysts in modern industrial and academic environments are faced with a daunting amount of multivariate data. While there has been significant development in the areas of data mining and knowledge
discovery, there is still the need for improved visualizations and generic solutions. The state-of-the-art in visual analytics and exploratory data visualization is to incorporate more profound analysis methods while focusing on improving interactive abilities, in order to support data analysts in gaining new insights through visual exploration and hypothesis building.
In the research field of exploratory data visualization, this thesis contributes new approaches in dimension reduction that tackle a number of shortcomings in state-of-the-art methods, such as interpretability and ambiguity. By combining methods from several disciplines, we describe how ambiguity can be countered effectively by visualizing coordinate values within a lower-dimensional embedding, thereby focusing on the display of the structural composition of high-dimensional data and on an intuitive depiction of inherent global relationships. We also describe how properties and alignment of high-dimensional manifolds can be analyzed in different levels of detail by means of a self-embedding hierarchy of local projections, each using full degree of freedom, while keeping the global context.
To the application field of air quality research, the thesis provides novel means for the research of aerosol source contributions. Triggered by this particularly challenging application problem, we instigate a new research direction in the area of visual analytics by describing a methodology to model-based visual analysis that (i) allows the scientist to be “in the loop” of computations and (ii) enables him to verify and control the analysis process, in order to steer computations towards physical meaning. Careful reflection of our work in this application has led us to derive key design choices that underlie and transcend beyond application-specific solutions. As a result, we describe a general design methodology to computing parameters of a pre-defined analytical model that map to multivariate data. Core applications areas that can benefit from our approach are within engineering disciplines, such as civil, chemical, electrical, and mechanical engineering, as well as in geology, physics, and biology.
This thesis, whose subject is located in the field of algorithmic commutative algebra and algebraic geometry, consists of three parts.
The first part is devoted to parallelization, a technique which allows us to take advantage of the computational power of modern multicore processors. First, we present parallel algorithms for the normalization of a reduced affine algebra A over a perfect field. Starting from the algorithm of Greuel, Laplagne, and Seelisch, we propose two approaches. For the local-to-global approach, we stratify the singular locus Sing(A) of A, compute the normalization locally at each stratum and finally reconstruct the normalization of A from the local results. For the second approach, we apply modular methods to both the global and the local-to-global normalization algorithm.
Second, we propose a parallel version of the algorithm of Gianni, Trager, and Zacharias for primary decomposition. For the parallelization of this algorithm, we use modular methods for the computationally hardest steps, such as for the computation of the associated prime ideals in the zero-dimensional case and for the standard bases computations. We then apply an innovative fast method to verify that the result is indeed a primary decomposition of the input ideal. This allows us to skip the verification step at each of the intermediate modular computations.
The proposed parallel algorithms are implemented in the open-source computer algebra system SINGULAR. The implementation is based on SINGULAR's new parallel framework which has been developed as part of this thesis and which is specifically designed for applications in mathematical research.
In the second part, we propose new algorithms for the computation of syzygies, based on an in-depth analysis of Schreyer's algorithm. Here, the main ideas are that we may leave out so-called "lower order terms" which do not contribute to the result of the algorithm, that we do not need to order the terms of certain module elements which occur at intermediate steps, and that some partial results can be cached and reused.
Finally, the third part deals with the algorithmic classification of singularities over the real numbers. First, we present a real version of the Splitting Lemma and, based on the classification theorems of Arnold, algorithms for the classification of the simple real singularities. In addition to the algorithms, we also provide insights into how real and complex singularities are related geometrically. Second, we explicitly describe the structure of the equivalence classes of the unimodal real singularities of corank 2. We prove that the equivalences are given by automorphisms of a certain shape. Based on this theorem, we explain in detail how the structure of the equivalence classes can be computed using SINGULAR and present the results in concise form. The probably most surprising outcome is that the real singularity type \(J_{10}^-\) is actually redundant.
ABSTRACT
"Spin and orbital contribution to the magnetic moment of transition metal clusters and complexes"
The spin and orbital contributions to the magnetic moments of isolated iron \(Fe_n^+\) \((7 ≤ n ≤ 18)\), cobalt \(Co_n^+\) \((8 ≤ n ≤ 22)\) and nickel \(Ni_n^+\) \((7 ≤ n ≤ 17)\) clusters were investigated. An experimental access to both contributions is possible by the application of x-ray magnetic circular dichroism (XMCD) spectroscopy. XMCD spectroscopy is based on x-ray absorption spectroscopy (XAS). It exploits the fact that for a magnetic sample the resonant absorption cross sections for negative and positive circular polarized x-rays differ for the transition from a spin orbit split ground state to the valence level. The resulting dichroic effects contain the information about the magnetism of the investigated sample. It can be extracted from the experimental spectrum via application of the so called sum rules. However, only the projections of the magnetic moments onto the quantization axis are experimentally accessible which corresponds to the magnetization of the sample.
We developed a method to apply XMCD spectroscopy to isolated clusters in the gas phase. A modified Fourier Transform Ion Cyclotron Resonance (FT-ICR) mass spectrometer was used to record the XA spectra in Total Ion Yield (TIY) mode, i.e. by recording the fragmentation intensity of the clusters in dependence of x-ray energy. The clusters can be considered to be a superparamagnetic ensemble. Thus, the magnetization follows a Langevin curve. The intrinsic magnetic moments can be calculated by Langevin correction of the experimental magnetic moments because the cluster temperature and the magnetic field are known.
The spin and the orbital magnetic moments are enhanced compared to the respective bulk values for all three investigated elements. The enhancement of the orbital contribution is more pronounced, by about a factor 3 - 4 compared to the bulk, than for the spin magnetic moment. However, if compared to the atomic value, both contributions are quenched. The orbital magnetic moment only amounts to about 10 - 15 % of the atomic value while the spin retains about 80 % of its atomic value. If the magnetic moments found for the clusters are put into perspective with respect to the atomic and bulk values by means of scaling laws, it becomes evident that both contributions follow different interpolations between the atomic and bulk value. The spin follows the well-known trend
\(n^{-1/3} = 1/(cluster radius)\) (n = number of atoms per cluster, assumption of a spherical particle). This trend relates to the ratio of surface to inner atoms in spherical particle. Hence, our interpretation is that the spin magnetic moment seems to follow the surface area of the cluster. On the other hand, the orbital magnetic moment follows \(1/n = 1/(cluster volume)\).
First XA spectra recorded with circularly polarized x-rays of a Single Molecule Magnet (SMM) \([Fe_4Ln_2(N_3)_4(Htea)_4(piv_6)]\) (Ln = Gd, Tb; \(H_3tea\) = triethanolamine, Hpiv = pivalic acid) are presented.
This thesis provides a fully automatic translation from synchronous programs to parallel software for different architectures, in particular, shared memory processing (SMP) and distributed memory systems. Thereby, we exploit characteristics of the synchronous model of computation (MoC) to reduce communication and to improve available parallelism and load-balancing by out-of-order (OOO) execution and data speculation.
Manual programming of parallel software requires the developers to partition a system into tasks and to add synchronization and communication. The model-based approach of development abstracts from details of the target architecture and allows to make decisions about the target architecture as late as possible. The synchronous MoC supports this approach by abstracting from time and providing implicit parallelism and synchronization. Existing compilation techniques translate synchronous programs into synchronous guarded actions (SGAs) which are an intermediate format abstracting from semantic problems in synchronous languages. Compilers for SGAs analyze causality problems, ensure logical correctness and the absence of schizophrenia problems. Hence, SGAs are a simplified and general starting point and keep the synchronous MoC at the same time. The instantaneous feedback in the synchronous MoC makes the mapping of these systems to parallel software a non-trivial task. In contrast, other MoCs such as data-flow processing networks (DPNs) directly match with parallel architectures. We translate the SGAs into DPNs,which represent a commonly used model to create parallel software. DPNs have been proposed as a programming model for distributed parallel systems that have communication paths with unpredictable latencies. The purely data-driven execution of DPNs does not require a global coordination and therefore DPNs can be easily mapped to parallel software for architectures with distributed memory. The generation of efficient parallel code from DPNs challenges compiler design with two issues: To perfectly utilize a parallel system, the communication and synchronization has to be kept low, and the utilization of the computational units has to be balanced. The variety of hardware architectures and dynamic execution techniques in processing units of these systems make a statically balanced distributed execution impossible.
The synchronous MoC is still reflected in our generated DPNs, which exhibits characteristics that allow optimizations concerning the previously mentioned issues. In particular, we apply a general communication reduction and OOO execution to achieve a dynamically balanced execution which is inspired from hardware design.
The present work investigated three important constructs in the field of psychology: creativity, intelligence and giftedness. The major objective was to clarify some aspects about each one of these three constructs, as well as some possible correlations between them. Of special interest were: (1) the relationship between creativity and intelligence - particularly the validity of the threshold theory; (2) the development of these constructs within average and above-average intelligent children and throughout grade levels; and (3) the comparison between the development of intelligence and creativity in above-average intelligent primary school children that participated in a special program for children classified as “gifted”, called Entdeckertag (ET), against an age-class- and-IQ matched control group. The ET is a pilot program which was implemented in 2004 by the Ministry for Education, Science, Youth and Culture of the state of Rhineland-Palatinate, Germany. The central goals of this program are the early recognition of gifted children and intervention, based on the areas of German language, general science and mathematics, and also to foster the development of a child’s creativity, social ability, and more. Five hypotheses were proposed and analyzed, and reported separately within five chapters. To analyze these hypotheses, a sample of 217 children recruited from first to fourth grade, and between the ages of six and ten years, was tested for intelligence and creativity. Children performed three tests: Standard Progressive Matrices (SPM) for the assessment of classical intelligence, Test of Creative Thinking – Drawing Production (TCT-DP) for the measurement of classical creativity, and Creative Reasoning Task (CRT) for the evaluation of convergent and divergent thinking, both in open problem spaces. Participants were divided according to two general cohorts: Intervention group (N = 43), composed of children participating in the Entdeckertag program, and a non-intervention group (N = 174), composed of children from the regular primary school. For the testing of the hypotheses, children were placed into more specific groups according to the particular hypothesis that was being tested. It could be concluded that creativity and intelligence were not significantly related and the threshold theory was not confirmed. Additionally, intelligence accounted for less than 1% of the variance within creativity; moreover, scores on intelligence were unable to predict later creativity scores. The development of classical intelligence and classical creativity throughout grade levels also presented a different pattern; intelligence grew increasingly and continually, whereas creativity stagnated after the third grade. Finally, the ET program proved to be beneficial for classical intelligence after two years of attendance, but no effect was found for creativity. Overall, results indicate that organizations and institutions such as schools should not look solely to intelligence performance, especially when aiming to identify and foster gifted or creative individuals.
In the first part of this thesis we study algorithmic aspects of tropical intersection theory. We analyse how divisors and intersection products on tropical cycles can actually be computed using polyhedral geometry. The main focus is the study of moduli spaces, where the underlying combinatorics of the varieties involved allow a much more efficient way of computing certain tropical cycles. The algorithms discussed here have been implemented in an extension for polymake, a software for polyhedral computations.
In the second part we apply the algorithmic toolkit developed in the first part to the study of tropical double Hurwitz cycles. Hurwitz cycles are a higher-dimensional generalization of Hurwitz numbers, which count covers of \(\mathbb{P}^1\) by smooth curves of a given genus with a certain fixed ramification behaviour. Double Hurwitz numbers provide a strong connection between various mathematical disciplines, including algebraic geometry, representation theory and combinatorics. The tropical cycles have a rather complex combinatorial nature, so it is very difficult to study them purely "by hand". Being able to compute examples has been very helpful
in coming up with theoretical results. Our main result states that all marked and unmarked Hurwitz cycles are connected in codimension one and that for a generic choice of simple ramification points the marked cycle is a multiple of an irreducible cycle. In addition we provide computational examples to show that this is the strongest possible statement.
Safety analysis is of ultimate importance for operating Nuclear Power Plants (NPP). The overall
modeling and simulation of physical and chemical processes occuring in the course of an accident
is an interdisciplinary problem and has origins in fluid dynamics, numerical analysis, reactor tech-
nology and computer programming. The aim of the study is therefore to create the foundations
of a multi-dimensional non-isothermal fluid model for a NPP containment and software tool based
on it. The numerical simulations allow to analyze and predict the behavior of NPP systems under
different working and accident conditions, and to develop proper action plans for minimizing the
risks of accidents, and/or minimizing the consequences of possible accidents. A very large number
of scenarios have to be simulated, and at the same time acceptable accuracy for the critical param-
eters, such as radioactive pollution, temperature, etc., have to be achieved. The existing software
tools are either too slow, or not accurate enough. This thesis deals with developing customized al-
gorithm and software tools for simulation of isothermal and non-isothermal flows in a containment
pool of NPP. Requirements to such a software are formulated, and proper algorithms are presented.
The goal of the work is to achieve a balance between accuracy and speed of calculation, and to
develop customized algorithm for this special case. Different discretization and solution approaches
are studied and those which correspond best to the formulated goal are selected, adjusted, and when
possible, analysed. Fast directional splitting algorithm for Navier-Stokes equations in complicated
geometries, in presence of solid and porous obstales, is in the core of the algorithm. Developing
suitable pre-processor and customized domain decomposition algorithms are essential part of the
overall algorithm amd software. Results from numerical simulations in test geometries and in real
geometries are presented and discussed.
For many decades, the search for language classes that extend the
context-free laguages enough to include various languages that arise in
practice, while still keeping as many of the useful properties that
context-free grammars have - most notably cubic parsing time - has been
one of the major areas of research in formal language theory. In this thesis
we add a new family of classes to this field, namely
position-and-length-dependent context-free grammars. Our classes use the
approach of regulated rewriting, where derivations in a context-free base
grammar are allowed or forbidden based on, e.g., the sequence of rules used
in a derivation or the sentential forms, each rule is applied to. For our
new classes we look at the yield of each rule application, i.e. the
subword of the final word that eventually is derived from the symbols
introduced by the rule application. The position and length of the yield
in the final word define the position and length of the rule application and
each rule is associated a set of positions and lengths where it is allowed
to be applied.
We show that - unless the sets of allowed positions and lengths are really
complex - the languages in our classes can be parsed in the same time as
context-free grammars, using slight adaptations of well-known parsing
algorithms. We also show that they form a proper hierarchy above the
context-free languages and examine their relation to language classes
defined by other types of regulated rewriting.
We complete the treatment of the language classes by introducing pushdown
automata with position counter, an extension of traditional pushdown
automata that recognizes the languages generated by
position-and-length-dependent context-free grammars, and we examine various
closure and decidability properties of our classes. Additionally, we gather
the corresponding results for the subclasses that use right-linear resp.
left-linear base grammars and the corresponding class of automata, finite
automata with position counter.
Finally, as an application of our idea, we introduce length-dependent
stochastic context-free grammars and show how they can be employed to
improve the quality of predictions for RNA secondary structures.
This thesis is devoted to the modeling and simulation of Asymmetric Flow Field Flow Fractionation, which is a technique for separating particles of submicron scale. This process is a part of large family of Field Flow Fractionation techniques and has a very broad range of industrial applications, e. g. in microbiology, chemistry, pharmaceutics, environmental analysis.
Mathematical modeling is crucial for this process, as due to the own nature of the process, lab ex- periments are difficult and expensive to perform. On the other hand, there are several challenges for the mathematical modeling: huge dominance (up to 106 times) of the flow over the diffusion, highly stretched geometry of the device. This work is devoted to developing fast and efficient algorithms, which take into the account the challenges, posed by the application, and provide reliable approximations for the quantities of interest.
We present a new Multilevel Monte Carlo method for estimating the distribution functions on a compact interval, which are of the main interest for Asymmetric Flow Field Flow Fractionation. Error estimates for this method in terms of computational cost are also derived.
We optimize the flow control at the Focusing stage under the given constraints on the flow and present an important ingredients for the further optimization, such as two-grid Reduced Basis method, specially adapted for the Finite Volume discretization approach.
Pedestrian Flow Models
(2014)
There have been many crowd disasters because of poor planning of the events. Pedestrian models are useful in analysing the behavior of pedestrians in advance to the events so that no pedestrians will be harmed during the event. This thesis deals with pedestrian flow models on microscopic, hydrodynamic and scalar scales. By following the Hughes' approach, who describes the crowd as a thinking fluid, we use the solution of the Eikonal equation to compute the optimal path for pedestrians. We start with the microscopic model for pedestrian flow and then derive the hydrodynamic and scalar models from it. We use particle methods to solve the governing equations. Moreover, we have coupled a mesh free particle method to the fixed grid for solving the Eikonal equation. We consider an example with a large number of pedestrians to investigate our models for different settings of obstacles and for different parameters. We also consider the pedestrian flow in a straight corridor and through T-junction and compare our numerical results with the experiments. A part of this work is devoted for finding a mesh free method to solve the Eikonal equation. Most of the available methods to solve the Eikonal equation are restricted to either cartesian grid or triangulated grid. In this context, we propose a mesh free method to solve the Eikonal equation, which can be applicable to any arbitrary grid and useful for the complex geometries.
This thesis combines mass spectrometric studies on ionic dicarboxylic acids and transition metal cluster adsorbate complexes. IR-MPD spectra of protonated and deprotonated aliphatic and aromatic dicarboxylic acids provide insights in the nature of intramolecular hydrogen bonding. Investigations of their fragmentation behavior are supported by MP2 calculations. Prior work on cobalt transition metal clusters is extended to iron and nickel and three cobalt alloys have been studied.
Perceptual grouping is an integral part of visual object recognition. It organizes elements within our visual field according to a set of heuristics (grouping principles), most of which are not well understood. To identify their temporal processing dynamics (i.e., to identify whether they rely on neuronal feedforward or recurrent activation), we introduce the primed flanker task that is based on a firm empirical and theoretical background. In three sets of experiments, participants responded to visual stimuli that were either grouped by (1) similarity of brightness, shape, or size, (2) symmetry and closure, or (3) Good Gestalt. We investigated whether these grouping cues were effective in rapid visuomotor processing (i.e., in terms of response times, error rates, and priming effects) and whether the results met theory-driven indicators of feedforward processing. (1) In the first set of experiments with similarity cues, we varied subjective grouping strength and found that stronger grouping in the targets enhanced overall response times while stronger grouping in the primes enhanced priming effects in motor responses. We also obtained differences between rapid visuomotor processing and the subjective impression with cues of brightness and shape but not with cues of brightness and size. These results show that the primed flanker task is an objective measure for comparing different feedforward-transmitted groupings. (2) In the second set of experiments, we used the task to study grouping by symmetry and grouping by closure that are more complex than similarity cues. We obtained results that were mostly in accordance with a feedforward model. Some other factors (line of view, orientation of the symmetry axis) were irrelevant for processing of symmetry cues. Thus, these experiments suggest that closure and (possibly) viewpoint-independent symmetry cues are extracted rapidly during the first feedforward wave of neuronal processing. (3) In the third set of experiments, we used the task to study grouping by Good Gestalt (i.e., visual completion in occluded shapes). By varying the amount of occlusion, we found that the processing was in accordance with a feedforward model only when occlusion was very limited. Thus, these experiments suggest that Good Gestalt is not extracted rapidly during the first feedforward wave of neuronal processing but relies on recurrent activation. I conclude (1) that the primed flanker task is an excellent tool to identify and compare the processing characteristics of different grouping cues by behavioral means, (2) that grouping strength and other factors are strongly modulating these processing characteristics, which (3) challenges a dichotomous classification of grouping cues based on feedforward vs. recurrent processing (incremental grouping theory, Roelfsema, 2006), and (4) that a focus on temporal processing dynamics is necessary to understand perceptual grouping.
In this thesis we studied and investigated a very common but a long existing noise problem and we provided a solution to this problem. The task is to deal with different types of noise that occur simultaneously and which we call hybrid. Although there are individual solutions for specific types one cannot simply combine them because each solution affects the whole speech. We developed an automatic speech recognition system DANSR ( Dynamic Automatic Noisy Speech Recognition System) for hybrid noisy environmental noise. For this we had to study all of speech starting from the production of sounds until their recognition. Central elements are the feature vectors on which pay much attention. As an additional effect we worked on the production of quantities for psychoacoustic speech elements.
The thesis has four parts:
1) The first part we give an introduction. The chapter 2 and 3 give an overview over speech generation and recognition when machines are used. Also noise is considered.
2) In the second part we describe our general system for speech recognition in a noisy environment. This is contained in the chapters 4-10. In chapter 4 we deal with data preparation. Chapter 5 is concerned with very strong noise and its modeling using Poisson distribution. In the chapters 5-8 we deal with parameter based modeling. Chapter 7 is concerned with autoregressive methods in relation to the vocal tract. In the chapters 8 and 9 we discuss linear prediction and its parameters. Chapter 9 is also concerned with quadratic errors, the decomposition into sub-bands and the use of Kalman filters for non-stationary colored noise in chapter 10. There one finds classical approaches as long we have used and modified them. This includes covariance mehods, the method of Burg and others.
3) The third part deals firstly with psychoacoustic questions. We look at quantitative magnitudes that describe them. This has serious consequences for the perception models. For hearing we use different scales and filters. In the center of the chapters 12 and 13 one finds the features and their extraction. The fearures are the only elements that contain information for further use. We consider here Cepstrum features and Mel frequency cepstral coefficients(MFCC), shift invariant local trigonometric transformed (SILTT), linear predictive coefficients (LPC), linear predictive cepstral coefficients (LPCC), perceptual linear predictive (PLP) cepstral coefficients. In chapter 13 we present our extraction methods in DANSR and how they use window techniques And discrete cosine transform (DCT-IV) as well as their inverses.
4) The fourth part considers classification and the ultimate speech recognition. Here we use the hidden Markov model (HMM) for describing the speech process and the Gaussian mixture model (GMM) for the acoustic modelling. For the recognition we use forward algorithm, the Viterbi search and the Baum-Welch algorithm. We also draw the connection to dynamic time warping (DTW). In the rest we show experimental results and conclusions.
When stimulus and response overlap in a choice-reaction task, enhanced performance can be observed. This effect, the so-called Stimulus-Response Compatibility (SRC) has been shown to appear for a variety of different stimulus features such as numerical or physical size, luminance, or pitch height. While many of these SRC effects have been investigated in an isolated manner, only fewer studies focus on possible interferences when more than one stimulus dimension is varied. The present thesis investigated how the SRC effect of pitch heights, the so-called SPARC effect (Spatial Pitch Associations of Response Codes), is influenced by additionally varied stimulus information. In Study 1, the pitch heights of presented tones were varied along with timbre categories under two different task and pitch range conditions and with two different response alignments. Similarly, in Study 2, pitch heights as well as numerical values were varied within sung numbers under two different task conditions. The results showed simultaneous SRC effects appearing independently of each other in both studies: In Study 1, an expected SRC effect of pitch heights with horizontal responses (i.e., a horizontal SPARC effect) was observed. More interestingly, an additional and unexpected SRC effect of timbre with response sides presented itself independently of this SPARC effect. Similar results were obtained in Study 2: Here, an SRC effect for pitch heights (SPARC) and an SRC effect for numbers (i.e., SNARC or Spatial Numerical Associations of Response Codes, respectively) were observed and again the effects did not interfere with each other. Thus, results indicate that SPARC with horizontal responses does not interfere with SRC effects of other, simultaneously varied stimulus dimensions. These findings are discussed within the principle of polarity correspondence and the dimensional overlap model as theoretical accounts for SRC effects. In sum, it appears that the different types of information according to varied stimulus dimensions enter the decision stage of stimulus processing from separate channels.
The recognition of day-to-day activities is still a very challenging and important research topic. During recent years, a lot of research has gone into designing and realizing smart environ- ments in different application areas such as health care, maintenance, sports or smart homes. As a result, a large amount of sensor modalities were developed, different types of activity and context recognition services were implemented and the resulting systems were benchmarked using state-of-the-art evaluation techniques. However, so far hardly any of these approaches have found their way into the market and consequently into the homes of real end-users on a large scale. The reason for this is, that almost all systems have one or more of the following characteristics in common: expensive high-end or prototype sensors are used which are not af- fordable or reliable enough for mainstream applications; many systems are deployed in highly instrumented environments or so-called "living labs", which are far from real-life scenarios and are often evaluated only in research labs; almost all systems are based on complex system con- figurations and/or extensive training data sets, which means that a large amount of data must be collected in order to install the system. Furthermore, many systems rely on a user and/or environment dependent training, which makes it even more difficult to install them on a large scale. Besides, a standardized integration procedure for the deployment of services in existing environments and smart homes has still not been defined. As a matter of fact, service providers use their own closed systems, which are not compatible with other systems, services or sensors. It is clear, that these points make it nearly impossible to deploy activity recognition systems in a real daily-life environment, to make them affordable for real users and to deploy them in hundreds or thousands of different homes.
This thesis works towards the solution of the above mentioned problems. Activity and context recognition systems designed for large-scale deployment and real-life scenarios are intro- duced. Systems are based on low-cost, reliable sensors and can be set up, configured and trained with little effort, even by technical laymen. It is because of these characteristics that we call our approach "minimally invasive". As a consequence, large amounts of training data, that are usu- ally required by many state-of-the-art approaches, are not necessary. Furthermore, all systems were integrated unobtrusively in real-world/similar to real-world environments and were evalu- ated under real-life, as well as similar to real-life conditions. The thesis addresses the following topics: First, a sub-room level indoor positioning system is introduced. The system is based on low-cost ceiling cameras and a simple computer vision tracking approach. The problem of user identification is solved by correlating modes of locomotion patterns derived from the trajectory of unidentified objects and on-body motion sensors. Afterwards, the issue of recognizing how and what mainstream household devices have been used for is considered. Based on a low-cost microphone, the water consumption of water-taps can be approximated by analyzing plumbing noise. Besides that, operating modes of mainstream electronic devices were recognized by using rule-based classifiers, electric current features and power measurement sensors. As a next step, the difficulty of spotting subtle, barely distinguishable hand activities and the resulting object interactions, within a data set containing a large amount of background data, is addressed. The problem is solved by introducing an on-body core system which is configured by simple, one-time physical measurements and minimal data collections. The lack of large training sets is compensated by fusing the system with activity and context recognition systems, that are able to reduce the search space observed. Amongst other systems, previously introduced approaches and ideas are revisited in this section. An in-depth evaluation shows the impact of each fusion procedure on the performance and run-time of the system. The approaches introduced are able to provide significantly better results than a state-of-the-art inertial system using large amounts of training data. The idea of using unobtrusive sensors has also been applied to the field of behavior analysis. Integrated smartphone sensors are used to detect behavioral changes of in- dividuals due to medium-term stress periods. Behavioral parameters related to location traces, social interactions and phone usage were analyzed to detect significant behavioral changes of individuals during stressless and stressful time periods. Finally, as a closing part of the the- sis, a standardization approach related to the integration of ambient intelligence systems (as introduced in this thesis) in real-life and large-scale scenarios is shown.
This thesis is devoted to the computational aspects of intersection theory and enumerative geometry. The first results are a Sage package Schubert3 and a Singular library schubert.lib which both provide the key functionality necessary for computations in intersection theory and enumerative geometry. In particular, we describe an alternative method for computations in Schubert calculus via equivariant intersection theory. More concretely, we propose an explicit formula for computing the degree of Fano schemes of linear subspaces on hypersurfaces. As a special case, we also obtain an explicit formula for computing the number of linear subspaces on a general hypersurface when this number is finite. This leads to a much better performance than classical Schubert calculus.
Another result of this thesis is related to the computation of Gromov-Witten invariants. The most powerful method for computing Gromov-Witten invariants is the localization of moduli spaces of stable maps. This method was introduced by Kontsevich in 1995. It allows us to compute Gromov-Witten invariants via Bott's formula. As an insightful application, we computed the numbers of rational curves on general complete intersection Calabi-Yau threefolds in projective spaces up to degree six. The results are all in agreement with predictions made from mirror symmetry.
According to the domain specific models of speech perception, speech is supposed to be processed distinctively compared to non-speech. This assumption is supported by many studies dealing with the processing of speech and non-speech stimuli. However, the complexity of both stimulus classes is not matched in most studies, which might be a confounding factor, according to the cue specific models of speech perception. One solution is spectrally rotated speech, which has already been used in a range of fMRI and PET studies. In order to be able to investigate the role of stimulus complexity, vowels, spectrally rotated vowels and a second non-speech condition with two bands of sinusoidal waves, representing the first two formants of the vowels, were used in the present thesis. A detailed description of the creation and the properties of the whole stimulus set are given in Chapter 2 (Experiment 1) of this work. These stimuli were used to investigate the auditory processing of speech and non-speech sounds in a group of dyslexic adults and age matched controls (Experiment 2). The results support the assumption of a general auditory deficit in dyslexia. In order to compare the sensory processing of speech and non-speech in healthy adults on the electrophysiological level, stimuli were also presented within a multifeature oddball paradigm (Experiment 3). Vowels evoked a larger mismatch negativity (MMN) compared to both non-speech stimulus types. The MMN evoked by tones and spectrally rotated tones were compared in Experiment 4, to investigate the role of harmony. No difference in the area of MMN was found, indicating that the results found in Experiment 3 were not moderated by the harmonic structure of the vowels. All results are discussed in the context of the domain and cue specific models of speech perception.
An huge amount of computational models and programming languages have been proposed
for the description of embedded systems. In contrast to traditional sequential programming
languages, they cope directly with the requirements for embedded systems: direct support for
concurrent computations and periodic interaction with the environment are only some of the
features they offer. Synchronous languages are one class of languages for the development of
embedded systems and they follow the fundamental principle that the execution is divided into
a sequence of logical steps. Thereby, each step follows the simplification that the computation
of the outputs is finished directly when the inputs are available. This rigorous abstraction leads
to well-defined deterministic parallel composition in general, and to deterministic abortion
and suspension in imperative synchronous languages in particular. These key features also
allow to translate programs to hardware and software, and also formal verification techniques
like model checking can be easily applied.
Besides the advantages of imperative synchronous languages, also some drawbacks can
be listed. Over-synchronization is an effect being caused by parallel threads which have to
synchronize for each execution step, even if they do not communicate, since the synchronization
is implicitly forced by the control-flow. This thesis considers the idea of clock refinement to
introduce several abstraction layers for communication and synchronization in addition to the
existing single-clock abstraction. Thereby, clocks can be refined by several independent clocks
so that a controlled amount of asynchrony between subsequent synchronization points can be
exploited by compilers. The declarations of clocks form a tree, and clocks can be defined within
the threads of the parallel statement, which allows one to do independent computations based
on these clocks without synchronizing the threads. However, the synchronous abstraction is
kept at each level of the abstraction.
Clock refinement is introduced in this thesis as an extension to the imperative synchronous
language Quartz. Therefore, new program statements are introduced which allow to define
a new clock as a refinement of an existing one and to finish a step based on a certain clock.
Examples are considered to show the impact of the behavior of the new statements to
the already existing statements, before the semantics of this extension is formally defined.
Furthermore, the thesis presents a compile algorithm to translate programs to an intermediate
format, and to translate the intermediate format to a hardware description. The advantages
obtained by the new modeling feature are finally evaluated based on examples.
Enhanced information processing of phobic natural images in participants with specific phobias
(2014)
From an evolutionary point of view, it can be assumed that visual processing and rapid detection of potentially dangerous stimuli in the environment (e.g., perilous animals) is highly adaptive for all humans. In the present dissertation, I address three research questions; (1) Is information processing of threatening stimuli enhanced in individuals with specific phobias? (2) Are there any differences between the different types of phobia (e.g., spider phobia vs. snake phobia)? (3) Is the frequently reported attentional bias of individuals with specific phobias - which may contribute to an enhancement in information processing – also detectable in a prior entry paradigm? In Experiments 1 to 3 of the present thesis non-anxious control, spider-fearful, snake-fearful, and blood-injection-injury-fearful participants took part in the study. We applied in each experiment a response priming paradigm which has a strong theoretical (cf. rapid-chase theory; Schmidt, Niehaus, & Nagel, 2006; Schmidt, Haberkamp, Veltkamp et al., 2011) as well as empirical background (cf. Schmidt, 2002). We show that information processing in fearful individuals is indeed enhanced for phobic images (i.e., spiders for spider-fearful participants; injuries for blood-injury-injection(BII)-fearful individuals). However, we found marked differences between the different types of phobia. In Experiment 1 and 2 (Chapter 2 and 3), spiders had a strong and specific influence in the group of spider-fearful individuals: Phobic primes entailed the largest priming effects, and phobic targets accelerated responses, both effects indicating speeded response activation by phobic images. In snake-fearful participants (Experiment 1, Chapter 2), this processing enhancement for phobic material was less pronounced and extended to both snake and spider images. In Experiment 3 (Chapter 4), we demonstrated that early information processing for pictures of small injuries is also enhanced in BII-fearful participants, even though BII fear is unique in that BII-fearful individuals show opposite physiological reactions when confronted with the phobic stimulus compared to individuals with animal phobias. These results show that already fast visuomotor responses are further enhanced in spider- and BII-fearful participants. Results give evidence that responses are based on the first feedforward sweep of neuronal activation proceeding through the visuomotor system. I propose that the additional enhancement in spider- and BII-fearful individuals depend on a specific hardwired binding of elementary features belonging to the phobic object in fearful individuals (i.e., effortless recognition of the respective phobic object via hardwired neuronal conjunctions). I suggest that these hardwired conjunctions developed due to long-term perceptual learning processes. We also investigate the frequently reported attentional bias of phobic individuals and showed that this bias is detectable in temporal order judgments using a prior entry paradigm. I assume that perceptual learning processes might also strengthen the attentional bias, for example, by providing a more salient bottom-up signal that draws attention involuntarily. In sum, I conclude that (1) early information processing of threatening stimuli is indeed enhanced in individuals with specific phobias but that (2) differences between divers types of phobia exist (i.e., spider- and BII-fearful participants show enhanced information of the respective phobic object; though, snake-fearful participants show no specific information processing enhancement of snakes); (3) the frequently reported attentional bias of spider-fearful individuals is also detectable in a prior entry paradigm.
In 2006 Jeffrey Achter proved that the distribution of divisor class groups of degree 0 of function fields with a fixed genus and the distribution of eigenspaces in symplectic similitude groups are closely related to each other. Gunter Malle proposed that there should be a similar correspondence between the distribution of class groups of number fields and the distribution of eigenspaces in ceratin matrix groups. Motivated by these results and suggestions we study the distribution of eigenspaces corresponding to the eigenvalue one in some special subgroups of the general linear group over factor rings of rings of integers of number fields and derive some conjectural statements about the distribution of \(p\)-parts of class groups of number fields over a base field \(K_{0}\). Where our main interest lies in the case that \(K_{0}\) contains the \(p\)th roots of unity, because in this situation the \(p\)-parts of class groups seem to behave in an other way like predicted by the popular conjectures of Henri Cohen and Jacques Martinet. In 2010 based on computational data Malle has succeeded in formulating a conjecture in the spirit of Cohen and Martinet for this case. Here using our investigations about the distribution in matrixgroups we generalize the conjecture of Malle to a more abstract level and establish a theoretical backup for these statements.
In the present work, the phase transitions in different Fe/FeC systems were studied by using the molecular dynamics simulation and the Meyer-Entel interaction potential (also the Johnson potential for Fe-C interaction). Fe-bicrystal, thin film, Fe-C bulk and Fe-C nanowire systems were investigated to study the behaviour of the phase transition, where the energetics, dynamics and transformations pathways were analysed.
Continuum Mechanical Modeling of Dry Granular Systems: From Dilute Flow to Solid-Like Behavior
(2014)
In this thesis, we develop a granular hydrodynamic model which covers the three principal regimes observed in granular systems, i.e. the dilute flow, the dense flow and the solid-like regime. We start from a kinetic model valid at low density and extend its validity to the granular solid-like behavior. Analytical and numerical results show that this model reproduces a lot of complex phenomena like for instance slow viscoplastic motion, critical states and the pressure dip in sand piles. Finally we formulate a 1D version of the full model and develop a numerical method to solve it. We present two numerical examples, a filling simulation and the flow on an inclined plane where the three regimes are included.
The work presented in this thesis discusses the thermal and power management of multi-core processors (MCPs) with both two dimensional (2D) package and there dimensional (3D) package chips. The power and thermal management/balancing is of increasing concern and is a technological challenge to the MCP development and will be a main performance bottleneck for the development of MCPs. This thesis develops optimal thermal and power management policies for MCPs. The system thermal behavior for both 2D package and 3D package chips is analyzed and mathematical models are developed. Thereafter, the optimal thermal and power management methods are introduced.
Nowadays, the chips are generally packed in 2D technique, which means that there is only one layer of dies in the chip. The chip thermal behavior can be described by a 3D heat conduction partial differential equation (PDE). As the target is to balance the thermal behavior and power consumption among the cores, a group of one dimensional (1D) PDEs, which is derived from the developed 3D PDE heat conduction equation, is proposed to describe the thermal behavior of each core. Therefore, the thermal behavior of the MCP is described by a group of 1D PDEs. An optimal controller is designed to manage the power consumption and balance the temperature among the cores based on the proposed 1D model.
3D package is an advanced package technology, which contains at least 2 layers of dies stacked in one chip. Different from 2D package, the cooling system should be installed among the layers to reduce the internal temperature of the chip. In this thesis, the micro-channel liquid cooling system is considered, and the heat transfer character of the micro-channel is analyzed and modeled as an ordinary differential equation (ODE). The dies are discretized to blocks based on the chip layout with each block modeled as a thermal resistance and capacitance (R-C) circuit. Thereafter, the micro-channels are discretized. The thermal behavior of the whole system is modeled as an ODE system. The micro-channel liquid velocity is set according to the workload and the temperature of the dies. Under each velocity, the system can be described as a linear ODE model system and the whole system is a switched linear system. An H-infinity observer is designed to estimate the states. The model predictive control (MPC) method is employed to design the thermal and power management/balancing controller for each submodel.
The models and controllers developed in this thesis are verified by simulation experiments via MATLAB. The IBM cell 8 cores processor and water micro-channel cooling system developed by IBM Research in collaboration with EPFL and ETHZ are employed as the experiment objects.
Regular physical activity is essential to maintain or even improve an individual’s health. There exist various guidelines on how much individuals should do. Therefore, it is important to monitor performed physical activities during people’s daily routine in order to tell how far they meet professional recommendations. This thesis follows the goal to develop a mobile, personalized physical activity monitoring system applicable for everyday life scenarios. From the mentioned recommendations, this thesis concentrates on monitoring aerobic physical activity. Two main objectives are defined in this context. On the one hand, the goal is to estimate the intensity of performed activities: To distinguish activities of light, moderate or vigorous effort. On the other hand, to give a more detailed description of an individual’s daily routine, the goal is to recognize basic aerobic activities (such as walk, run or cycle) and basic postures (lie, sit and stand).
With recent progress in wearable sensing and computing the technological tools largely exist nowadays to create the envisioned physical activity monitoring system. Therefore, the focus of this thesis is on the development of new approaches for physical activity recognition and intensity estimation, which extend the applicability of such systems. In order to make physical activity monitoring feasible in everyday life scenarios, the thesis deals with questions such as 1) how to handle a wide range of e.g.
everyday, household or sport activities and 2) how to handle various potential users. Moreover, this thesis deals with the realistic scenario where either the currently performed activity or the current user is unknown during the development and training
phase of activity monitoring applications. To answer these questions, this thesis proposes and developes novel algorithms, models and evaluation techniques, and performs thorough experiments to prove their validity.
The contributions of this thesis are both of theoretical and of practical value. Addressing the challenge of creating robust activity monitoring systems for everyday life the concept of other activities is introduced, various models are proposed and validated. Another key challenge is that complex activity recognition tasks exceed the potential of existing classification algorithms. Therefore, this thesis introduces a confidence-based extension of the well known AdaBoost.M1 algorithm, called ConfAdaBoost.M1. Thorough experiments show its significant performance improvement compared to commonly used boosting methods. A further major theoretical contribution is the introduction and validation of a new general concept for the personalization of physical activity recognition applications, and the development of a novel algorithm (called Dependent Experts) based on this concept. A major contribution of practical value is the introduction of a new evaluation technique (called leave-one-activity-out) to simulate when performing previously unknown activities in a physical activity monitoring system. Furthermore, the creation and benchmarking of publicly available physical activity monitoring datasets within this thesis are directly benefiting the research community. Finally, the thesis deals with issues related to the implementation of the proposed methods, in order to realize the envisioned mobile system and integrate it into a full healthcare application for aerobic activity monitoring and support in daily life.
The noise issue in manufacturing system is widely discussed from legal and health aspects. Regarding the existing laws and guidelines, various investigation methods are implemented in industry. The sound pressure level can be measured and reduced by using established approaches in reality. However, a straightforward and low cost approach to study noise issue using existing digital factory models is not found.
This thesis attempts to develop a novel concept for sound pressure level investigation in a virtual environment. With this, the factory planners are able to investigate the noise issue during factory design and layout planning phase.
Two computer aided tools are used in this approach: acoustic simulation and virtual reality (VR). The former enables the planner to simulate the sound pressure level by given factory layout and facility sound features. And the latter provides a visualization environment to view and explore the simulation results. The combination of these two powerful tools provides the planners a new possibility to analyze the noise in a factory.
To validate the simulations, the acoustic measurements are implemented in a real factory. Sound pressure level and sound intensity are determined respectively. Furthermore, a software tool is implemented using the introduced concept and approach. With this software, the simulation results are represented in a Cave Automatic Virtual Environment (CAVE).
This thesis describes the development of the approach, the measurement of sound features, the design of visualization framework, and the implementation of VR software. Based on this know-how, the industry users are able to design their own method and software for noise investigation and analysis.
Backward compatibility of class libraries ensures that an old implementation of a library can safely be replaced by a new implementation without breaking existing clients.
Formal reasoning about backward compatibility requires an adequate semantic model to compare the behavior of two library implementations.
In the object-oriented setting with inheritance and callbacks, finding such models is difficult as the interface between library implementations and clients are complex.
Furthermore, handling these models in a way to support practical reasoning requires appropriate verification tools.
This thesis proposes a formal model for library implementations and a reasoning approach for backward compatibility that is implemented using an automatic verifier. The first part of the thesis develops a fully abstract trace-based semantics for class libraries of a core sequential object-oriented language. Traces abstract from the control flow (stack) and data representation (heap) of the library implementations. The construction of a most general context is given that abstracts exactly from all possible clients of the library implementation.
Soundness and completeness of the trace semantics as well as the most general context are proven using specialized simulation relations on the operational semantics. The simulation relations also provide a proof method for reasoning about backward compatibility.
The second part of the thesis presents the implementation of the simulation-based proof method for an automatic verifier to check backward compatibility of class libraries written in Java. The approach works for complex library implementations, with recursion and loops, in the setting of unknown program contexts. The verification process relies on a coupling invariant that describes a relation between programs that use the old library implementation and programs that use the new library implementation. The thesis presents a specification language to formulate such coupling invariants. Finally, an application of the developed theory and tool to typical examples from the literature validates the reasoning and verification approach.
Polychlorinated dibenzo-p-dioxins, dibenzofurans, and polychlorinated biphenyls are persistent environmental pollutants which ubiquitously occur as complex mixtures and accumulate in the food and feed chain due to their high lipophilic properties. Of the 419 possible congeners, only 29 share a common mechanism of action and cause similar effects, the so called dioxin-like compounds. Dioxin-like compounds evoke a broad spectrum of biochemical and toxic responses, i.e. enzyme induction, dermal toxicity, hepatotoxicity, immunotoxicity, carcinogenicity as well as adverse effects on reproduction, development, and the endocrine system in laboratory animals and in humans. Most, if not all, of the aforementioned responses, are mediated by the aryl hydrocarbon receptor. In the present work, the elicited biochemical effects of a selection of dioxin-like compounds and the non dioxin-like PCB 153 were examined in mouse (in vivo) and in human liver cell models (in vitro). Emphasis was given to the main contributors to the total toxic equivalents in human blood and tissues TCDD, 1-PnCDD, 4-PnCDF, PCB 118, PCB 126, and PCB 156, which likewise contribute about 90 % to the dioxin-like activity in the human food chain.
Three mouse in vivo studies were carried out aiming to characterize the alterations in hepatic gene expression as well as the induction of hepatic xenobiotic metabolizing enzymes after single oral dose. Based on the results obtained from mouse 3-day and 14-day studies, the seven test compounds can be categorized into three classes; the ones which are 'pure' AhR ligands (TCDD, 1-PnCDD, 4-PnCDF, and PCB 126) or solely CAR inducers (PCB 153), and the ones which are AhR/CAR mixed-type inducers (PCB 118, PCB 156). Moreover, the analysis of hepatic gene expression patterns after a single oral dose of either TCDD or PCB 153 revealed that the altered genes fundamentally differed. Profiling of significantly altered genes led to the conclusion that changes in gene expression were associated with different signalling pathways, in fact by AhR and CAR.
For investigating the role of the AhR in mediating biological responses, several experimental approaches were carried out, such as the analysis of blood plasma metabolites in Ahr knockout and wild-type mice. Genotype specifics and similarities were determined by HPLC-MS/MS analysis. Several plasma metabolites could be identified in both genotypes, but also differences were detected. Furthermore, an in vivo experiment was performed aiming to characterize AhR-dependent and -independent effects in female Ahr knockout and wild-type mice. For this purpose, mice received a single oral dose of TCDD and were killed 96 h later. Microarray analysis of mouse livers revealed that although the Ahr gene was knocked out in Ahr-/- mice, the quantity of affected genes were in the same order of magnitude as for Ahr+/+ mice, but the pattern of altered genes distinctly differed. In addition, the relative liver weights of TCDD-treated Ahr+/+ mice were significantly increased which led to the conclusion, that TCDD induced the development of hepatic steatosis in female Ahr wild-type.
The performed in vitro experiments aimed to characterize the effects elicited by selected DLCs and PCB 153 in human liver cell models by the use of HepG2 cells and primary human hepatocytes. In general, primary human hepatocytes were less responsive than HepG2 cells. This was not only observed in EC values derived from EROD assay, but also regarding microarray analysis in terms of differently regulated genes. In vitro REPs gained from both liver cell models widely confirmed the current TEFs, but some deviations occurred. The comparison of the TCDD-altered genes in both human cell types revealed that only a considerably small number of genes was in common up regulated by both human liver cell models, such as the established AhR-regulated highly inducible cytochrome P450s 1A1, 1A2, and 1B1 as well as other AhR target genes. Although the overlap was rather small, the TCDD-induced genes could be consistently associated with the broad spectrum of established dioxin-related biological responses. The gene expression pattern in primary human hepatocytes after treatment with selected DLCs (TCDD, 1-PnCDD, 4-PnCDF, and PCB 126) and PCB 153 was additionally characterized by microarray analysis. The highest response in terms of significantly altered genes was determined for TCDD, followed by 4-PnCDF, 1-PnCDD, and PCB 126, whereas exposure to PCB 153 did not evoke any significant changes in gene expression. The pattern of significantly altered genes was very homogenous among the four congeners. Genes associated with well-established DLC-related biological responses as well as novel dioxin-inducible target genes were identified, whereby an extensive overlap in terms of up regulated genes by all four DLCs occurred. In conclusion, the results from the in vitro experiments performed in primary human hepatocytes provided fundamental insight into the congeners' potencies and caused alterations in gene expression patterns. The obtained findings implicate that although the extent of enzyme inducibilities varied, the gene expression patterns are coincidental. Microarray analysis identified species-specific (mouse vs. human) as well as model-specific (in vitro vs. in vivo and transformed cells vs. untransformed cells) differences. In order to identify novel biomarkers for AhR activation due to treatment with dioxin-like compounds, five candidates were selected based on the microarray results i.e. ALDH3A1, TIPARP, HSD17B2, CD36, and AhRR. Eventually, ALDH3A1 turned out to be the most reliable and suitable marker for exposure to DLCs in both human liver cell models eliciting the highest mRNA inducibility among the five chosen candidates. In which way these species- and cell type-specific markers are involved in the dioxin-elicited toxic responses should be further characterized in vivo and in vitro.
This thesis is divided into two parts. Both cope with multi-class image segmentation and utilize
non-smooth optimization algorithms.
The topic of the first part, namely unsupervised segmentation, is the application of clustering
to image pixels. Therefore, we start with an introduction of the biconvex center-based clustering
algorithms c-means and fuzzy c-means, where c denotes the number of classes. We show that
fuzzy c-means can be seen as an approximation of c-means in terms of power means.
Since noise is omnipresent in our image data, these simple clustering models are not suitable
for its segmentation. To this end, we introduce a general and finite dimensional segmentation
model that consists of a data term stemming from the aforementioned clustering models plus a
continuous regularization term. We tackle this optimization model via an alternating minimiza-
tion approach called regularized c-centers (RcC). Thereby, we fix the centers and optimize the
segment membership of the pixels and vice versa. In this general setting, we prove convergence
in the sense of set-valued algorithms using Zangwill’s Theory [172].
Further, we present a segmentation model with a total variation regularizer. While updating
the cluster centers is straightforward for fixed segment memberships of the pixels, updating the
segment membership can be solved iteratively via non-smooth, convex optimization. Thereby,
we do not iterate a convex optimization algorithm until convergence. Instead, we stop as soon as
we have a certain amount of decrease in the objective functional to increase the efficiency. This
algorithm is a particular implementation of RcC providing also the corresponding convergence
theory. Moreover, we show the good performance of our method in various examples such as
simulated 2d images of brain tissue and 3d volumes of two materials, namely a multi-filament
composite superconductor and a carbon fiber reinforced silicon carbide ceramics. Thereby, we
exploit the property of the latter material that two components have no common boundary in
our adapted model.
The second part of the thesis is concerned with supervised segmentation. We leave the area
of center based models and investigate convex approaches related to graph p-Laplacians and
reproducing kernel Hilbert spaces (RKHSs). We study the effect of different weights used to
construct the graph. In practical experiments we show on the one hand image types that
are better segmented by the p-Laplacian model and on the other hand images that are better
segmented by the RKHS-based approach. This is due to the fact that the p-Laplacian approach
provides smoother results, while the RKHS approach provides often more accurate and detailed
segmentations. Finally, we propose a novel combination of both approaches to benefit from the
advantages of both models and study the performance on challenging medical image data.
In the last few years a lot of work has been done in the investigation of Brownian motion with point interaction(s) in one and higher dimensions. Roughly speaking a Brownian motion with point interaction is nothing else than a Brownian motion whose generator is disturbed by a measure supported in just one point.
The purpose of the present work is the introducing of curve interactions of the two dimensional Brownian motion for a closed curve \(\mathcal{C}\). We will understand a curve interaction as a self-adjoint extension of the restriction of the Laplacian to the set of infinitely often continuously differentiable functions with compact support in \(\mathbb{R}^{2}\) which are constantly 0 at the closed curve. We will give a full description of all these self-adjoint extensions.
In the second chapter we will prove a generalization of Tanaka's formula to \(\mathbb{R}^{2}\). We define \(g\) to be a so-called harmonic single layer with continuous layer function \(\eta\) in \(\mathbb{R}^{2}\). For such a function \(g\) we prove
\begin{align}
g\left(B_{t}\right)=g\left(B_{0}\right)+\int\limits_{0}^{t}{\nabla g\left(B_{s}\right)\mathrm{d}B_{s}}+\int\limits_{0}^{t}\eta\left(B_{s}\right)\mathrm{d}L\left(s,\mathcal{C}\right)
\end{align}
where \(B_{t}\) is just the usual Brownian motion in \(\mathbb{R}^{2}\) and \(L\left(t,\mathcal{C}\right)\) is the connected unique local time process of \(B_{t}\) on the closed curve \(\mathcal{C}\).
We will use the generalized Tanaka formula in the following chapter to construct classes of processes related to curve interactions. In a first step we get the generalization of point interactions in a second step we get processes which behaves like a Brownian motion in the complement of \(\mathcal{C}\) and has an additional movement along the curve in the time- scale of \(L\left(t,\mathcal{C}\right)\). Such processes do not exist in the one point case since there we cannot move when the Brownian motion is in the point.
By establishing an approximation of a curve interaction by operators of the form Laplacian \(+V_{n}\) with "nice" potentials \(V_{n}\) we are able to deduce the existence of superprocesses related to curve interactions.
The last step is to give an approximation of these superprocesses by a sytem of branching particles. This approximation gives a better understanding of the related mass creation.
The research presented in this PhD thesis is a contribution to the field of anion recognition in competitive aqueous solvent mixtures. Neutral anion receptors having a cage-type architecture have been developed on the basis of triply-linked bis(cyclopeptides) and their binding properties toward various inorganic anions have been studied.
The synthetic approaches chosen to assemble the targeted container molecules rely on dynamic chemistry under the template effects of anions such as sulfate and halides. As reversible reactions metal-ligand exchange and thiol-disulfide exchange were used. Disulfide exchange has previously provided singly- and doubly-linked bis(cyclopeptide) receptors whose anion affinities in 2:1 acetonitrile/water mixtures approached the nanomolar range. Metal-ligand interactions have so far not been used to assemble bis(cyclopeptides) in our group. The cyclopeptide building blocks required for both approaches, namely cyclic hexapeptides containing alternating 6-aminopicolinic acid and either (2S,4S)-4-cyanoproline or (2S,4S)-4-thioproline subunits could be synthesized successfully.
Self-assembly of the bis(cyclopeptide) held together by coordinative interactions has been attempted by treating the cyclopeptide trinitrile with square-planar palladium (II) complexes. The reaction was followed with different NMR spectroscopic techniques. Unfortunately, none of the experiments provides conclusive evidence that the targeted triply-linked cage was indeed formed.
Bis(cyclopeptides) containing three dithiol derived linkers between the cyclopeptide rings could be synthesizes successfully. Two complexes were isolated, albeit in small amounts, one containing linkers derived from 1,2-ethanedithiol and the other one from 1,3-benzenedithiol that contain a sulfate anion incorporated in the cavity between the cyclopeptide rings. Formation of triply-linked bis(cyclopeptides) containing different types of linkers could be achieved by performing the synthesis in the presence of different dithiols. Unfortunately, the two C3 symmetrical bis(cyclopeptides) containing a single linker type could not be isolated in analytically pure form so that only qualitative binding studies could be performed. Investigations in this context indicate extraordinary sulfate affinity for these bis(cyclopeptides). In particular, affinity of the receptor containing the 1,2-ethanedithiol linkers for sulfate anions is so high that is even able to dissolve barium sulfate under appropriate conditions and presumably exceeds the sulfate affinity of the doubly-linked bis(cyclopeptides). The sulfate anion present in the cavity of this bis(cyclopeptide) can be replaced by a large number of other anions, i.e. by selenate, perrhenate, nitrate, tetrafluoroborate, hexafluorophosphate and halides. None of these complexes proved to be as stable as the corresponding sulfate complex. In addition, 1H-NMR spectroscopic investigations provided information about the solution structure of the bis(cyclopeptide) anion complexes. Sulfate release from the cavity of the receptor is a slow process while exchange of other anions is significantly faster. Another interesting feature that has been observed for sulfate and selenate complexes of the 1,2-ethanedithiol-containing bis(cyclopeptide) is the very slow H/D rate with which protons on amide groups located inside the cavity of the cage are replaced by deuterium atoms in protic deuterated solvents. This effect in combination with the observation that the different deuterated bis(cyclopeptide) species exhibit individual amide NH signals in the 1H-NMR spectrum are indicative for well defined complex geometries with strong hydrogen-bonding interactions between the anion and the amide NH groups of the receptor. Following the H/D exchange rate in the presence of various salts indicated that anion exchange proceeds via the dissociated complex and not by direct replacement of one anion by another one.
Tire-soil interaction is important for the performance of off-road vehicles and the soil compaction in the agricultural field. With an analytical model, which is integrated in multibody-simulation software, and a Finite Element model, the forces and moments generated on the tire-soil contact patch were studied to analyze the tire performance. Simulations with these two models for different tire operating conditions were performed to evaluate the mechanical behaviors of an excavator tire. For the FE model validation a single wheel tester connected to an excavator arm was designed. Field tests were carried out to examine the tire vertical stiffness, the contact pressure on the tire – hard ground interface, the longitudinal/vertical force and the compaction of the sandy clay from the test field under specified operating conditions. The simulation and experimental results were compared to evaluate the model quality. The Magic Formula was used to fit the curves of longitudinal and lateral forces. A simplified tire-soil interaction model based on the fitted Magic Formula could be established and further applied to the simulation of vehicle-soil interaction.
Aim of this work was the extension and development of a coupled Computational Fluid Dynamics (CFD) and population balance model (PBM) solver to enable a simulation aided design of stirred liquid-liquid extraction columns. The principle idea is to develop a new design methodology based on a CFD-PBM approach and verify it with existing data and correlations. On this basis, the separation performance in any apparatus geometry should be possible to predict without any experimental input. Reliable “experiments in silico” (computer calculations) should give the engineer a valuable and user-friendly tool for early design studies at minimal costs.
The layout of extraction columns is currently based on experimental investigations from miniplant to pilot plant and a scale-up to the industrial scale. The hydrodynamic properties can be varied by geometrical adjustments of the stirrer diameter, the stirrer height, the free cross sectional area of the stator, the compartment height as well as the positioning and the size of additional baffles. The key parameter for the liquid–liquid extraction is the yield which is mainly determined at the in- and outlets of the column. Local phenomena as the swirl structure are influenced by geometry changes. However, these local phenomena are generally neglected in state-of-the are design methodologies due to the complex required measurement techniques. A geometrical optimization of the column therefore still results in costs for validation experiments as assembly and operation of the column, which can be reduced by numerical investigations. The still mainly in academics used simulation based layout of counter-current extraction columns is based at the beginning of this work on one dimensional simulations of extraction columns and first three dimensional simulations. The one dimensional simulations are based on experimental derived, geometrical dependent correlations for the axial backmixing (axial dispersion), the hold-up, the phase fraction, the droplet sedimentation and the energy dissipation. A combination of these models with droplet population balance modeling resulted in a description of the complex droplet-droplet interactions (droplet size) along the column height. The three dimensional CFD simulations give local information about the flow field (velocity, swirl structure) based on the used numerical mesh corresponding to the real geometry. A coupling of CFD with population balance modeling further provides information about the local droplet size. A backcoupling of the droplet size with the CFD (drag model) results in an enhancement of the local hydrodynamics (e.g. hold-up, dispersed phase velocity). CFD provided local information about the axial dispersion coefficient of simple geometrical design (e.g. Rotating Disc Contactor (RDC) column). First simulations of the RDC column using a two dimensional rotational geometry combined with population balance modeling were performed and gave local information about the droplet size for different boundary conditions (rotational speed, different column sizes).
In this work, two different column types were simulated using an extended OpenSource CFD code. The first was the RDC column, which were mainly used for code development due to its simple geometry. The Kühni DN32 column is equipped with a six-baffled stirring device and flat baffles for disturbing the flow and requires a full three dimensional description. This column type was mainly used for experimental validation of the simulations due to the low required volumetric flow rate. The Kühni DN60 column is similar to the Kühni DN32 column with slight changes to the stirring device (4-baffles) and was used for scale up investigations. For the experimental validation of the hydrodynamics, laser based measurement techniques as Particle Image Velocimetry (PIV) and Laser Induced Fluorescence (LIF) were used. A good agreement between the experimental derived values for velocity, hold-up and energy dissipation, experimentally derived correlations from literature and the simulations with a modified Euler-Euler based OpenSource CFD code could be found. The experimental derived axial dispersion coefficient was further compared to Euler-Lagrange simulations. The experimental derived correlations for the Kühni DN32 in literature fit to the simulated values. Also the axial dispersion coefficient for the dispersed phase satisfied a correlation from literature. However, due to the complexity of the dispersed phase axial dispersion coefficient measurement, the available correlations gave no distinct agreement to each other.
A coupling of the modified Euler-Euler OpenSource CFD code was done with a one group population balance model. The implementation was validated to the analytical solution of the population balance equation for constant breakage and coalescence kernels. A further validation of the population balance transport equation was done by comparing the results of a five compartment section to the results of the commercial CFD code FLUENT using the Quadrature Method of Moments (QMOM).
For the simulation of the droplet-droplet interactions in liquid-liquid extraction columns, several breakage and coalescence models are available in the literature. The models were compared to each other using the one-group population balance model in Matlab which allows the determination of the minimum stable droplet diameter at a certain energy dissipation. Based on this representation, it was possible to determine the parameters for a specific breakage and coalescence model combination which allowed the simulation of a Kühni miniplant column at different rotational speeds. The resulting simulated droplet size was in very good agreement to the experimental derived droplet size from literature. Several column designs of the DN32 were investigated by changing the compartment height and the axial stirrer position. It could be shown that a decrease of the stirrer position increases the phase fraction inside the compartment. At the same time, the droplet size decreases inside the compartment, which allows a higher mass transfer due to a higher available interfacial area. However, the shifting results in an expected earlier flooding of the column due to a compressed flow structure underneath the stirring device. In a next step, the code was further extended by mass transfer equations based on the two-film theory. Mass transfer coefficient models for the dispersed and continuous phase were investigated for the RDC column design.
A first mass transfer simulation of a full miniplant column was done. The change in concentration was accounted by the mixture density, viscosity and interfacial tension in dependence of the concentration, which affects the calculation of the droplet size. The results of the column simulation were compared to own experimental data of the column. It could be shown that the concentration profile along the column height can be predicted by the presented CFD/population balance/mass transfer code. The droplet size decreases corresponding to the interfacial tension along the column height. Compared to the experimental derived droplet size at the outlet, the simulation is in good agreement.
Besides the occurrence of a mono dispersed droplet size, high breakage may lead to the generation of small satellite droplets and coalescence underneath the stator leads to larger droplets inside the column and hence to a change of the hold-up and of the flooding point. A multi-phase code was extended by the Sectional Quadrature Method of Moment (SQMOM) allowing a modeling of the droplet interactions of bimodal droplet interactions or multimodal distributions. The implementations were in good agreement to the analytical solution. In addition, the simulation of an RDC column section showed the different distribution of the smaller droplets and larger droplets. The smaller droplets tend to follow the continuous phase flow structure and show a higher distribution of inside the column. The larger droplets tend to rise directly through the column and show only a low influence to the continuous phase flow.
The current results strengthen the use of CFD for the layout of liquid-liquid extraction columns in future. The coupling of CFD/PBM and mass transfer using an OpenSource CFD code allows the investigation of computational intensive column designs (e.g. pilot plant columns). Furthermore the coupled code enhances the accuracy of the hydrodynamics simulations and leads to a better understanding of counter-current liquid-liquid extraction columns. The gained correlation were finally used as an input for one dimensional mass transfer simulations, where a perfect fit of the concentration profiles at varied boundary conditions could be obtained. By using the multi-scale approach, the computational time for mass transfer simulations could be reduced to minutes. In future, with increasing computational power, a further extend of the multiphase CFD/SQMOM model including mass transfer equation will provide an efficient tool to model multimodal and multivariate systems as bubble column reactors.
Due to tremendous improvements of high-performance computing resources as well
as numerical advances computational simulations became a common tool for modern
engineers. Nowadays, simulation of complex physics is more and more substituting a
large amount of physical experiments. While the vast compute power of large-scale
high-performance systems enabled for simulating more complex numerical equations,
handling the ever increasing amount of data with spatial and temporal resolution
burdens new challenges to scientists. Huge hardware and energy costs desire for
ecient utilization of high-performance systems. However, increasing complexity of
simulations raises the risk of failing simulations resulting in a single simulation to be
restarted multiple times. Computational Steering is a promising approach to interact
with running simulations which could prevent simulation crashes. The large amount
of data expands gaps in the amount of data that can be calculated and the amount of
data that can be processed. Extreme-scale simulations produce more data that can
even be stored. In this thesis, I propose several methods that enhance the process
of steering, exploring, visualizing, and analyzing ongoing numerical simulations.
There is a growing trend for ever larger wireless sensor networks (WSNs) consisting of thousands or tens of thousands of sensor nodes (e.g., [91, 79]). We believe this trend will continue and thus scalability plays a crucial role in all protocols and mechanisms for WSNs. Another trend in many modern WSN applications is the time sensitivity to information from sensors to sinks. In particular, WSNs are a central part of the vision of cyber-physical systems and as these are basically closed-loop systems many WSN applications will have to operate under stringent timing requirements. Hence, it is crucial to develop algorithms that minimize the worst-case delay in WSNs. In addition, almost all WSNs consist of battery-powered nodes, and thus energy-efficiency clearly remains another premier goal in order to keep network lifetime high. This dissertation presents and evaluates designs for WSNs using multiple sinks to achieve high lifetime and low delay. Firstly, we investigate random and deterministic node placement strategies for large-scale and time-sensitive WSNs. In particular, we focus on tiling-based deterministic node placement strategies and analyze their effects on coverage, lifetime, and delay performance under both exact placement and stochastically disturbed placement. Next, we present sink placement strategies, which constitutes the main contributions of this dissertation. Static sinks will be placed and mobile sinks will be given a trajectory. A proper sink placement strategy can improve the performance of a WSN significantly. In general, the optimal sink placement with lifetime maximization is an NP-hard problem. The problem is even harder if delay is taken into account. In order to achieve both lifetime and delay goals, we focus on the problem of placing multiple (static) sinks such that the maximum worst-case delay is minimized while keeping the energy consumption as low as possible. Different target networks may need a corresponding sink placement strategy under differing levels of apriori assumptions. Therefore, we first develop an algorithm based on the Genetic Algorithm (GA) paradigm for known sensor nodes' locations. For a network where global information is not feasible we introduce a self-organized sink placement (SOSP) strategy. While GA-based sink placement achieves a near-optimal solution, SOSP provides a good sink placement strategy with a lower communication overhead. How to plan the trajectories of many mobile sinks in very large WSNs in order to simultaneously achieve lifetime and delay goals had not been treated so far in the literature. Therefore, we delve into this difficult problem and propose a heuristic framework using multiple orbits for the sinks' trajectories. The framework is designed based on geometric arguments to achieve both, high lifetime and low delay. In simulations, we compare two different instances of our framework, one conceived based on a load-balancing argument and one based on a distance minimization argument, with a set of different competitors spanning from statically placed sinks to battery-state aware strategies. We find our heuristics outperform the competitors in both, lifetime and delay. Furthermore, and probably even more important, the heuristic, while keeping its good delay and lifetime performance, scales well with an increasing number of sinks. In brief, the goal of this dissertation is to show that placing nodes and sinks in conventional WSNs as well as planning trajectories in mobility enabled WSNs carefully really pays off for large-scale and time-sensitive WSNs.
Constructing accurate earth models from seismic data is a challenging task. Traditional methods rely on ray based approximations of the wave equation and reach their limit in geologically complex areas. Full waveform inversion (FWI) on the other side seeks to minimize the misfit between modeled and observed data without such approximation.
While superior in accuracy, FWI uses a gradient based iterative scheme that makes it also very computationally expensive. In this thesis we analyse and test an Alternating Direction Implicit (ADI) scheme in order to reduce the costs of the two dimensional time domain algorithm for solving the acoustic wave equation. The ADI scheme can be seen as an intermediate between explicit and implicit finite difference modeling schemes. Compared to full implicit schemes the ADI scheme only requires the solution of much smaller matrices and is thus less computationally demanding. Using ADI we can handle coarser discretization compared to an explicit method. Although order of convergence and CFL conditions for the examined explicit method and ADI scheme are comparable, we observe that the ADI scheme is less prone to dispersion. Furhter, our algorithm is efficiently parallelized with vectorization and threading techniques. In a numerical comparison, we can demonstrate a runtime advantage of the ADI scheme over an explicit method of the same accuracy.
With the modeling in place, we test and compare several inverse schemes in the second part of the thesis. With the goal of avoiding local minima and improving speed of convergence, we use different minimization functions and hierarchical approaches. In several tests, we demonstrate superior results of the L1 norm compared to the L2 norm – especially in the presence of noise. Furthermore we show positive effects for applying three different multiscale approaches to the inverse problem. These methods focus on low frequency, early recording, or far offset during early iterations of the minimization and then proceed iteratively towards the full problem. We achieve best results with the frequency based multiscale scheme, for which we also provide a heuristical method of choosing iteratively increasing frequency bands.
Finally, we demonstrate the effectiveness of the different methods first on the Marmousi model and then on an extract of the 2004 BP model, where we are able to recover both high contrast top salt structures and lower contrast inclusions accurately.
Recent progresses and advances in the field of consumer electronics, driven by display
technologies and also the sector of mobile, hand-held devices, enable new ways in
presenting information to users, as well as new ways of user interaction, therefore
providing a basis for user-centered applications and work environments.
My thesis focuses on how arbitrary display environments can be utilized to improve
both the user experience, regarding perception of information, and also to provide
intuitive interaction possibilities. On the one hand advances in display technologies
provide the basis for new ways of visualizing content and collaborative work, on the
other hand forward-pressing developments in the consumer market, especially the
market of smart phones, offer potential to enhance usability in terms of interaction
and therefore can provide additional benefit for users.
Tiled display setups, combining both large screen real estate and high resolution,
provide new possibilities and chances to visualize large datasets and to facilitate col-
laboration in front of a large screen area. Furthermore these display setups present
several advantages over the traditional single-user-workspace environments: con-
trary to single-user-workspaces, multiple users are able to explore a dataset displayed
on a tiled display system, at the same time, thus allowing new forms of collabora-
tive work. Based on that, face-to-face discussions are enabled, an additional value
is added. Large displays also allow the utilization of the user’s spatial memory, al-
lowing physical navigation without the need of switching between different windows
to explore information.
With Tiled++ I contributed a versatile approach to address the bezel problem. The
bezel problem is one of the Top Ten research challenges in the research field of LCD-
based tiled wall setups. By applying the Tiled++ approach a large high resolution
Focus & Context screen is created, combining high resolution focus areas with low
resolution context information, projected onto the bezel area.
Additionally the field of user interaction poses an important challenge, especially
regarding the utilization of large tiled displays, since traditional keyboard & mouse
interaction devices reached their limits. My focus in this thesis is on Mobile HCI.Devices like mobile phones are utilized to interact with large displays, since they
feature various interaction modalities and preserve user mobility.
Large public displays, as a modernized form of traditional bulletin boards, also en-
able new ways of handling information, displaying content, and user interaction.
Utilized in hot spots, Digital Interactive Public Pinboards can provide an adequate
answer to questions like how to approach pressing issues like disaster and crisis man-
agement for both responders as well as citizens and also new ways of how to handle
information flow (contribution & distribution & accession). My contribution to the
research field of public display environments was the conception and implementa-
tion of an easy-to-use and easy-to-set-up architecture to overcome shortcomings of
current approaches and to cover the needs of aid personnel.
Although being a niche, Virtual Reality (VR) environments can provide additional
value for visualizing specific content. Disciplines like earth sciences & geology, me-
chanical engineering, design, and architecture can benefit from VR environments. In
order to consider the variety of users, I introduce a more intuitive and user friendly
interaction metaphor, the ARC metaphor.
Visualization challenges base on being able to cope with more and more complex
datasets and to bridge the gap between comprehensibility and loss of information.
Furthermore the visualization approach has to be reasonable, which is a crucial
factor when working in interdisciplinary teams, where the standard of knowledge
is diverse. Users have to be able to conceive the visualized content in a fast and
reliable way. My contribution are visualization approaches in the field of supportive
visualization.
Finally, my work illuminates how the synthesis of visualization, interaction and dis-
play technologies enhance the user experience. I promote a holistic view. The user
is brought back into the focus of attention, provided with a tool-set to support him,
without overextending the abilities of, for example, non-expert users, a crucial factor
in the more and more interdisciplinary field of computer science.
The use of trading stops is a common practice in financial markets for a variety of reasons: it provides a simple way to control losses on a given trade, while also ensuring that profit-taking is not deferred indefinitely; and it allows opportunities to consider reallocating resources to other investments. In this thesis, it is explained why the use of stops may be desirable in certain cases.
This is done by proposing a simple objective to be optimized. Some simple and commonly-used rules for the placing and use of stops are investigated; consisting of fixed or moving barriers, with fixed transaction costs. It is shown how to identify optimal levels at which to set stops, and the performances of different rules and strategies are compared. Thereby, uncertainty and altering of the drift parameter of the investment are incorporated.
Cyanobacteria are the only prokaryotes with the ability to conduct oxygenic photosynthesis,
therefore having major influence on the evolution of life on earth. Their diverse morphology
was traditionally the basis for taxonomy and classification. For example, the genus
Chroococcidiopsis has been classified within the order Pleurocapsales, based on a unique
reproduction modus by baeocytes. Recent phylogenetic results suggested a closer
relationship of this genus to the order Nostocales. However, these studies were based
mostly on the highly conserved 16S rRNA and a small selection of Chroococcidiopsis
strains. One aim of this present thesis was to investigate the evolutionary relationships of
the genus Chroococcidiopsis, the Pleurocapsales and remaining cyanobacteria using
16S rRNA, rpoC1 and gyrB gene. Including the single gene, as the multigene analyses of
97 strains clearly showed a separation of the genus Chroococcidiopsis from the
Pleurocapsales. Furthermore, a sister relationship between the genus Chroococcidiopsis
and the order Nostocales was confirmed. Consequently, the monogeneric family
Chroococcidiopsidaceae Geitler ex. Büdel, Donner & Kauff familia nova is justified. The
phylogenetic analyses also revealed the polyphyly of the remaining Pleurocapsales, due to
the fact that the strain Pleurocapsa PCC 7327 was always separated from other strains.
This is supported by differences in their metabolism, ecology and physiology.
A second aim of this study was to investigate the thylakoid arrangement of
Chroococcidiopsis and a selection of cyanobacterial strains. The investigation of 13 strains
with Low Temperature Scanning Electron Microscopy revealed two unknown thylakoidal
arrangements within Chroococcidiopsis (parietal and stacked). This result revised the
knowledge of the thylakoid arrangement in this genus. Previously, only a coiled
arrangement was known for three strains. Based on the data of 66 strains, the feature
thylakoid arrangement was tested as a potential feature for morphological identification of
cyanobacteria. The results showed a strong relationship between the group assignment of
cyanobacteria and their thylakoid arrangements. Hence, it is in general possible to
conclude from this certain phenotypic character the affiliation to a particular family, order
or genus.
The third aim of this study was to investigate biogeographical patterns of the worldwide
distributed genus Chroococcidiopsis. The phylogenetic analysis suggested that the genus do not have biogeographical patterns, which is in contrast with a recent study on hypolithic
living Chroococcidiopsis strains and the majority of phylogeographic analysis of
microorganisms. Further analysis showed no separation of different life-strategies within
the genus. These results could be related to the genetic markers utilized, which may not
contain biogeographical information. Hence the present study can neither exclude nor
prove the possibility of biogeographic and life-strategy patterns in the genus
Chroococcidiopsis.
Future research should be focused on finding appropriate genetic markers investigate of
evolutionary relationships and biogeographical patterns within Chroococcidiopsis.
This thesis deals with generalized inverses, multivariate polynomial interpolation and approximation of scattered data. Moreover, it covers the lifting scheme, which basically links the aforementioned topics. For instance, determining filters for the lifting scheme is connected to multivariate polynomial interpolation. More precisely, sets of interpolation sites are required that can be interpolated by a unique polynomial of a certain degree. In this thesis a new class of such sets is introduced and elements from this class are used to construct new and computationally more efficient filters for the lifting scheme.
Furthermore, a method to approximate multidimensional scattered data is introduced which is based on the lifting scheme. A major task in this method is to solve an ordinary linear least squares problem which possesses a special structure. Exploiting this structure yields better approximations and therefore this particular least squares problem is analyzed in detail. This leads to a characterization of special generalized inverses with partially prescribed image spaces.
The application behind the subject of this thesis are multiscale simulations on highly heterogeneous particle-reinforced composites with large jumps in their material coefficients. Such simulations are used, e.g., for the prediction of elastic properties. As the underlying microstructures have very complex geometries, a discretization by means of finite elements typically involves very fine resolved meshes. The latter results in discretized linear systems of more than \(10^8\) unknowns which need to be solved efficiently. However, the variation of the material coefficients even on very small scales reveals the failure of most available methods when solving the arising linear systems. While for scalar elliptic problems of multiscale character, robust domain decomposition methods are developed, their extension and application to 3D elasticity problems needs to be further established.
The focus of the thesis lies in the development and analysis of robust overlapping domain decomposition methods for multiscale problems in linear elasticity. The method combines corrections on local subdomains with a global correction on a coarser grid. As the robustness of the overall method is mainly determined by how well small scale features of the solution can be captured on the coarser grid levels, robust multiscale coarsening strategies need to be developed which properly transfer information between fine and coarse grids.
We carry out a detailed and novel analysis of two-level overlapping domain decomposition methods for the elasticity problems. The study also provides a concept for the construction of multiscale coarsening strategies to robustly solve the discretized linear systems, i.e. with iteration numbers independent of variations in the Young's modulus and the Poisson ratio of the underlying composite. The theory also captures anisotropic elasticity problems and allows applications to multi-phase elastic materials with non-isotropic constituents in two and three spatial dimensions.
Moreover, we develop and construct new multiscale coarsening strategies and show why they should be preferred over standard ones on several model problems. In a parallel implementation (MPI) of the developed methods, we present applications to real composites and robustly solve discretized systems of more than \(200\) million unknowns.
Factorization of multivariate polynomials is a cornerstone of many applications in computer algebra. To compute it, one uses an algorithm by Zassenhaus who used it in 1969 to factorize univariate polynomials over \(\mathbb{Z}\). Later Musser generalized it to the multivariate case. Subsequently, the algorithm was refined and improved.
In this work every step of the algorithm is described as well as the problems that arise in these steps.
In doing so, we restrict to the coefficient domains \(\mathbb{F}_{q}\), \(\mathbb{Z}\), and \(\mathbb{Q}(\alpha)\) while focussing on a fast implementation. The author has implemented almost all algorithms mentioned in this work in the C++ library factory which is part of the computer algebra system Singular.
Besides, a new bound on the coefficients of a factor of a multivariate polynomial over \(\mathbb{Q}(\alpha)\) is proven which does not require \(\alpha\) to be an algebraic integer. This bound is used to compute Hensel lifting and recombination of factors in a modular fashion. Furthermore, several sub-steps are improved.
Finally, an overview on the capability of the implementation is given which includes benchmark examples as well as random generated input which is supposed to give an impression of the average performance.
This thesis reports on investigations on the structure and reactivity of dipeptide-alkali metal complexes, a series of ruthenium bearing catalysts, dysprosium based single molecule magnets and organometallic di-cobalt complexes. A variety of experimental and theoretical methods was used dependent on the problem: collision induced dissociation, hydrogen/deuterium exchange reactions, gas phase reactions with \(D_2\), infrared multiple-photon dissociation and the determination of minimum energy structures, IR absorption spectra, transition states and electronic transitions based on density functional theory.
A case study was carried out to explore the influence of alkali metal ions on the gas phase structure of the dipeptide Carnosine. CID experiments on protonated Carnosine and its alkali metal complexes in an ion trap resulted in different fragment pathways dependent on the size of the alkali metal. The complexation of small ions (\(Li^+\) and \(Na^+\)) promoted the cleavage of bonds in the molecules backbone under CID, while \(Rb^+\)- and \(Cs^+\)-Carnosine complexes underwent the exclusive loss of the alkali metal. CID breakdown curves reflected the different binding behavior of the alkali ions to Carnosine. Gas phase H/D exchange reactions with \(D_2O\) resulted in the exchange of several protons of the protonated dipeptide, while its alkali metal complexes underwent no exchange reactions. DFT derived energetical minimum isomers exhibited only charge solvated tridentate structures, whereas salt bridge as well as charge solvated binding motives are reported in literature on complexes of alkali metal ions and oligopeptides. This study was published in a similar version as a paper in Zeitschrift für Physikalische Chemie.
A combination of the four dipeptides Carnosine, Anserine, GlyHis and HisGly with alkali metal ions was investigated with the help of CID, IR-MPD spectroscopy and H/D exchange reactions with \(ND_3\). The aim of the survey was to elucidate the influence of the methyl-group at the histidine ring, of the peptide sequence and chain length on the binding motives of the alkali ions. The experimental results were compared to DFT derived minimum energetical isomers. A moderate accordance was found for DFT predicted IR absorptions to IR-MPD spectra. A systematic nomenclature was developed reflecting all binding motives of the four dipeptides to alkali ions. Carnosine complexes all alkali metal ions in an uniform motive. DFT derived energetical minimum isomers of the three other dipeptides showed strong conformational changes with increasing size of the alkali ion. The most favored binding motive of all peptides was the tridentate complexation of the alkali ion by a carboxylic and an amidic oxygen atom, while the electron donating nitrogen atom either belongs to the Histidine ring or the amine group. The ability to form hydrogen bonds in a certain binding motive is essential for the preference of the Histidine or amine nitrogen atom as an electron donor. The charge solvated binding motive is the most common within all found isomers. Several structures exhibited hydrogen bonded protons. Those can be interpretated as intermediates between the charge solvated and the salt bridge binding motive. CID breakdown curves of the cationic complexes of the dipeptides with \(K^+\), \(Rb^+\) and \(Cs^+\) resulted in a fair agreement of \(E^{50\%}_{com}\) values with DFT derived Gibbs free binding energies. CID led to multiple fragments of the \(Li^+\) and \(Na^+\) dipeptide complexes and to an insufficient correlation between the \(E^{50\%}_{com}\) values and metal-dipeptide free binding enthalpies. Gas phase H/D exchange reactions of the protonated dipeptides with \(ND_3\) resulted in the exchange of all labile protons with comparable relative partial rate constants. The assumption of coexisting single and double exchange reactions per single collision led to an enhancement in quality of the pseudo first order kinetic fits of the experimental derived data. The \(Li^+\), \(Na^+\) and \(K^+\) complexes of the dipeptides exhibited a reduction in the number of exchanged protons, significantly lower rate constants for H/D exchange and only single exchange reactions.
The complexation of the doubly charged cationic transition metal \(Zn^{2+}\) by deprotonated Carnosine led to crucial conformational changes with respect to the alkali metal complexes. Former DFT calculations on the gas phase structure of \([Carn-H,Zn^{II}]^+\) were now compared to IR-MPD spectra. IR-MPD spectra exhibited several of the DFT predicted IR absorptions while the overall agreement in the position of bands is only partially satisfactory. The complex \([Carn-H,Zn^{II}]^+\) was furthermore used in order to study the band dependent enhancement of fragmentation efficiency by application of a resonant 2-color IR-MPD pump/probe scheme. In literature, it is assumed that the slopes of linear fits to the log-log scale of experimental data (fragmentation efficiency vs. laser pulse energy) correlate to the number of photons needed for fragmentation. No reasonable number of photons for the fragmentation of the molecule was derived with this approach. However, it could be shown that the number of photons of the pump laser needed for fragmentation is reduced by the use of a second IR color. The change of the delay between the pump and probe laser pulse had an influence on the shape of the absorption bands. Irradiation with the probe laser pulse before the pump laser caused a heating of the molecule which resulted in a broadening of bands. No broadening was observed when the probe laser was applied simultaneously or after the pump laser. CID and IR-MPD fragmentation channels differed in their relative abundance. Furthermore, relative abundancies of fragments were specific to the excited vibrational motions. This study provides essential approaches for the further study of the mechanism of resonant 2-color IR-MPD spectroscopy.
Several ruthenium catalysts for transfer hydrogenation reactions were synthesized by L. Ghoochany (research group W. Thiel, TU Kaiserlautern). CID measurements on isotopic labeled species led to the following conclusion about the activation process of the catalyst: a nitrogen-ruthenium bond is broken, the pyrimidine ring of the substituted 2-R-4-(2-pyridinyl)pyrimidine ligand rotates about 160° and a carbon-ruthenium bond is formed under subsequent loss of a HCl (or DCl) molecule. The mass spectrometers CID amplitude was calibrated with a set of “thermometer ions”. CID breakdown curves were used for determination of \(E^{50\%}_{com}\) values of three differently substituted catalysts. Finally, activation energies were estimated by means of the calibration. The resulting activation energies showed a qualitative correlation to DFT derived activation energies. These results are part of a manuscript which was submitted to Chemistry – A European Journal and is currently in the review process. Further studies on this series of transition metal complexes included CID on ligand exchanged species, 1- and 2-color IR-MPD spectroscopy, gas phase reactions with \(D_2\) and DFT based modeling of the reaction coordinate of the \(D_2\) insertion. The exchange of the anionic chlorido ligand in solution led to three complexes with different fragmentation thresholds. CID derived activation amplitudes correspond well to the order predicted by the hard/soft acids/bases (HSAB) concept. 1-color IR-MPD experiments on two complexes showed only a few bands. Resonant 2-color IR-MPD increased the overall fragmentation efficiency and uncovered several dark bands. DFT derived IR absorption spectra correlate well to IR-MPD spectra while some bands are still not observable. Gas phase reactions with \(D_2\) showed an increase of the mass of the activated complex of +4 m/z. This was interpreted in terms of an incorporation of a \(D_2\) molecule under heterolytical cleavage of the \(D_2\) molecule and can be compared to a back reaction of the activation. The reaction coordinate of the \(D_2\) incorporation was modeled with DFT at the B3LYP/cc-pVTZ level of theory and different activation energies were derived dependent on the substituent. Reactions of three differently substituted complexes with \(D_2\) resulted in different relative partial rate constants. The comparison to rate constants derived from transition state theory showed a qualitative but not quantitative correlation to the experimental results. This study contributes to our ongoing work on the assignment and isolation of reaction intermediates in the gas phase.
A series of dysprosium based complexes was synthesized by A. Bhunia (research group P. W. Roesky, KIT) and studied within the collaborative research center SFB/TRR 88 “3MET”. We contributed to this work with ESI-MS, CID and experiments on H/D exchange reactions with \(ND_3\) in the gas phase. Those complexes consist of a central triple-charged dysprosium cation and two identical salen-type ligands which allow for a complexation of up to two transition metals. The monometallic dysprosium complex shows single molecule magnet (SMM) behavior in SQUID measurements, while the incorporation of two double-charged manganese cations leads to ferromagnetic behavior. The interaction of terminal amine groups with the manganese ions caused a hinderance of the exchange H/D exchange reaction with \(ND_3\) in the gas phase. Alternatively, the terminal amine groups of the monometallic dysprosium complex allow for the bond of two \(Ni^{2+}(tren)\) complexes. ESI-MS studies showed anionic as well as cationic complexes due to deprotonation or protonation in solution. CID studies led to fragmentation schemes which correlate quite well to the predicted structures of the complexes. These results are part of two publications in Inorganic Chemistry and Dalton Transactions. Further studies on this series of mono-, di- and trimetallic complexes are reported in this thesis. H/D exchange reactions with \(D_2O\) in solution yielded in an exchange of all labile protons for the cationic complexes. Anionic complexes underwent a partial or a complete exchange of labile protons. A comparison of 1- and 2-color IR-MPD spectra of anionic and cationic complexes as well as H/D exchanged species allowed for the assignment of vibrational bands. Furthermore, preferred protonation sites were derived by comparing the results of IR-MPD experiments and H/D exchange reactions in solution and in the gas phase. This study contributes to our ongoing work on the determination of magnetic properties of isolated ions in the gas phase at the Helmholtz-Zentrum Berlin.
The complex \([(^4CpCo)_2(\mu-C_2Ph_2)]\) (\(^4Cp\) = tetraisopropyl-cyclopentadiene) was synthesized by J. Becker (research group H. Sitzmann, TU Kaiserslautern). The cationic complex and several reaction products were characterized by ESI-MS. Some of the experimental data contributed to the diploma thesis of J. Becker. The cationic reaction products and the complex itself were subject of IR spectroscopic characterization. IR-MPD efficiency changed crucially with modification of the complex, yielding \([(^4CpCo)_2(\mu-C_2Ph_2)X]^+ (X=H, (H+CH_3CN), Cl, O)\). The contribution of various fragmentation channels to the overall fragmentation efficiency was studied in detail. An increase of photon flux resulted in a saturation of preferred \(C_2Ph_2\) loss, additional alkyl fragments out of the \(^4Cp\) rings arising. Several absorption bands were found in the mid- and near-IR region. A model system from literature was used to identify seemingly levels of DFT theory by reference to X-ray crystal structure data. The B3LYP and the B97D functional with cc-pVDZ and Stuttgart 1997 ECP basis sets were identified for calculations of the complex \([(^4CpCo)_2(\mu-C_2Ph_2)]^+\) and of its reaction products. An elongation of the Co-Co bond distance was observed for the cationic reaction products with \(Cl^-\) and \(O^{2-}\). Calculations with B3LYP and B97D resulted in different electronic ground states. We did not obtain a good agreement of calculated vibrational modes and recorded IR-MPD spectra. DFT predicted more absorption bands than observed, especially those corresponding to aliphatic symmetric \(CH_n (n=2, 3)\) and aromatic CH stretch motions. Future 2-color IR-MPD experiments might resolve currently prevailing discrepancies. TD-DFT calculations yielded several electronic transitions that do not correspond to the IR-MPD spectra. The chosen levels of theory for DFT and TD-DFT calculations does not seem to be appropriate. IR-MPD spectra have to be remeasured in order to normalize the spectra to photon flux. Furthermore, a different strategy has to be developed for ab initio calculations on the complexes under study.
A combination of various methods applied to isolated ions in the gas phase and in solution allowed for the study of their structure, binding energies and reactivity. 1- and 2-color IR-MPD spectroscopy combined with DFT predicted absorption spectra of different isomers enabled an assignment of vibrational bands and binding motives of the molecules. The derived results are important for further studies on the binding behavior of peptides and the reaction behavior of metal complexes.
This work shall provide a foundation for the cross-design of wireless networked control systems with limited resources. A cross-design methodology is devised, which includes principles for the modeling, analysis, design, and realization of low cost but high performance and intelligent wireless networked control systems. To this end, a framework is developed in which control algorithms and communication protocols are jointly designed, implemented, and optimized taking into consideration the limited communication, computing, memory, and energy resources of the low performance, low power, and low cost wireless nodes used. A special focus of the proposed methodology is on the prediction and minimization of the total energy consumption of the wireless network (i.e. maximization of the lifetime of wireless nodes) under control performance constraints (e.g. stability and robustness) in dynamic environments with uncertainty in resource availability, through the joint (offline/online) adaptation of communication protocol parameters and control algorithm parameters according to the traffic and channel conditions. Appropriate optimization approaches that exploit the structure of the optimization problems to be solved (e.g. linearity, affinity, convexity) and which are based on Linear Matrix Inequalities (LMIs), Dynamic Programming (DP), and Genetic Algorithms (GAs) are investigated. The proposed cross-design approach is evaluated on a testbed consisting of a real lab plant equipped with wireless nodes. Obtained results show the advantages of the proposed cross-design approach compared to standard approaches which are less flexible.
This thesis combined gas phase mass spectrometric investigations of ionic transition metal clusters that are either homogeneous \((Nb_n^{+/-}, Co_n^{+/-})\) or heterogeneous \(([Co_nPt_m]^{+/-})\), of their organo metallic reaction products, and of organic molecules (aspartame and Asp-Phe) and their alkali metal ion adducts.At the Paris FEL facility CLIO a newly installed FT-ICR mass spectrometer has been modified by inclusion of an ion bender that allows for the usage of additional ion sources beyond the installed ESI source. The installation of an LVAP metal cluster source served to produce metal cluster adsorbate complex ions of the type \([Nb_n(C_6H_6)]^{+/-}\). IR-MPD of the complexes \([Nb_n(C_6H_6)]^{+/-} (n = 18, 19)\) resulted in \([Nb_n(C_6)]^{+/-} (n = 18, 19)\) fragments. Spectra are broad, possibly because of vibronic / electronic transitions. In Kaiserslautern the capabilities of the LVAP source were extended by adding a gas pick up unit. Complex gases containing C-H bonds otherwise break within the cluster forming plasma. More stable gases like CO seem to attach at least partially intact. Metal cluster production with argon tagged onto the cluster failed when introducing argon through the pick up source, but succeeded when using argon as expansion gas. A new mass spectrometer concept of an additional multipole collision cell for metal cluster adsorbate formation is currently under construction. Subsequent cooling shall achieve high resolution IR-MPD spectra of transition metal cluster adsorbate complexes.Prior work on reaction of transition metal clusters with benzene was extended by investigating the reaction with benzene and benzene-d6 of size selected cationic cobalt clusters \(Co_n^+\) and of anionic cobalt clusters \(Co_n^-\) in the size range \(n = 3 - 28\) and of bimetallic cobalt platinum clusters \([Co_nPt_m]^{+/-}\) in the size range \(n + m \le 8\). Dehydrogenation by cationic cobalt clusters \(Co_n^+\) is sparse, it is effective in small bimetallic clusters \([Co_nPt_m]^+ (n + m \le 3)\). Thus single platinum atoms promote benzene dehydrogenation while further cobalt atoms quench it. Dehydrogenation is ubiquitous in reactions of anionic cobalt clusters. Mixed triatomic clusters \([Co_2Pt_1]^-\) and \([Co_1Pt_2]^-\) are special in causing effective reactions and single dehydrogenation through some kind of cooperativity while \([Co_nPt_{1,2}]^- (n \ge 3)\) do not react at all. Kinetic isotope effects KIE(n) in total reaction rates are inverse and - in part - large, dehydrogenation isotope effects DIE(n) are normal. A multistep model of adsorption and stepwise dehydrogenation from the precursor adsorbate proves suitable to rationalize the found KIEs and DIEs in principle. Particular insights into the effects of charge and of cluster size are largely beyond this model. Some DFT calculations - though preliminary - lend strong support to the otherwise assumed structures and enthalpies. More insights into the cause of the found effects of charge, size and composition of both pure and mixed clusters shall arise from ongoing high level ab initio modeling (of especially the \(n + m = 3\) case for mixed clusters).The influence of the methylester group in the molecules aspartame (Asp-PheOMe) and Asp-Phe has been explored. Therefore, their protonated and deprotonated species and their complexes with alkali metal ions attached were investigated with different techniques utilizing mass spectrometry.Gas phase H-/D-exchange with \(ND_3\) has proven that in both molecules all acidic NH and OH binding motifs do exchange their hydrogen atom and that simultaneous multi exchange is present. Kinetic studies revealed that with alkali metal ions attached the speed of the first exchange step decreases with increasing ion size. The additional OH of the carboxylic COOHPhe group in Asp-Phe increases the exchange speed by a constant value. CID experiments yielded water and the protonated Asp-Phe anhydride as main fragments out of the protonated molecules, neutral Asp anhydride and \([Phe M]^+ / [PheOMe M]^+\) for \(Li^+\) and \(Na^+\) attached, and neutral aspartame / Asp-Phe and ionic \(M^+\) for \(K^+\), \(Rb^+\) and \(Cs^+\) attached. The threshold energy \(E_{CID}\), indicating ion stability, decreases with increasing ion size. For aspartame fragmentation occurs at lower \(E_{CID}\) values for complexes with \(H^+\), \(Li^+\) and \(Na^+\) than for the Asp-Phe analoga. Complexes with \(K^+\), \(Rb^+\) and \(Cs^+\) give the same \(E_{CID}\) value for aspartame and Asp-Phe. IR-MPD investigations lead to the same fragments as the CID experiments. In combination with quantum mechanical calculations a change in the preferred structure from charge-solvated, tridentate type for complexes with small alkali metal ions (\(Li^+\)) to salt-bridge type structure for large alkali metal ions (\(Cs^+\)) could be confirmed. Calculations thereby reveal nearly no structural differences between aspartame and Asp-Phe for cationized species. The deprotonation of the additional COOHPhe group in Asp-Phe is preferred against other acidic positions. A better experimental distinction between possible (calculated) structure types would arise from additional FEL IR-MPD measurements in the energy range of 600 to 1800 \(cm^{-1}\). The comparison of the \(E_{CID}\) values with calculated fragmentation energy values proves that not only for alkali metal complexes with \(K^+\), \(Rb^+\) and \(Cs^+\), but also for \(Li^+\) and \(Na^+\) the bond breaking of all metal atom bonds is part of the transition state. The lower \(E_{CID}\) values for aspartame with small cations may be explained in terms of internal energy. Aspartame is a larger molecule, possesses more internal energy and can be recognized as the larger heat bath. Less energy is needed for fragmentation, if the Phe part with the additional methylester group is involved in the fragmentation process.