A method to estimate blast-induced damage in rock considering both stress waves and gas expansion phases is presented. The method was developed by assuming a strong correlation between blast-induced damage and stress wave amplitudes, and also by adapting a 2D numerical method to estimate damage in a 3D real case. The numerical method is used to determine stress wave damage and provides an indication of zones prone to suffer greater damage by gas expansion. The specific steps carried out in this study are: i) extensive blast monitoring in hard rock at surface and underground test sites; ii) analysis of seismic waveforms in terms of amplitude and frequency and their azimuthal distribution with respect to borehole axis, iii) measurement of blast-induced damage from single-hole blasts; iv) assessment and implementation of method to utilize 2D numerical model to predict blast damage in 3D situation; v) use of experimental and numerical results to estimate relative contribution of stress waves and gas penetration to damage, and vi) monitoring and modeling of full-scale production blasts to apply developed method to estimate blast-induced damage from stress waves. The main findings in this study are: i) both P and S-waves are generated and show comparable amplitudes by blasting in boreholes; ii) amplitude and frequency of seismic waves are strongly dependent on initiation mode and direction of propagation of explosive reaction in borehole; iii) in-situ measurements indicate strongly non-symmetrical damage dependent on confinement conditions and initiation mode, and existing rock structure, and iv) gas penetration seems to be mainly responsible for damage (significant damage extension 2-4 borehole diameters from stress waves; > 22 from gas expansion). The method has the potential for application in regular production blasts for control of over-breaks and dilution in operating mines. The main areas proposed for future work are: i) verification of seismic velocity changes in rock by blast-induced damage from controlled experiments; ii) incorporation of gas expansion phase into numerical models; iii) use of 3D numerical model and verification of crack distribution prediction; iv) further studies on strain rate dependency of material strength parameters, and v) accurate measurements of in-hole pressure function considering various confinement conditions.

A method to estimate blast-induced damage in rock considering both stress waves and gas expansion phases is presented. The method was developed by assuming a strong correlation between blast-induced damage and stress wave amplitudes, and also by adapting a 2D numerical method to estimate damage in a 3D real case. The numerical method is used to determine stress wave damage and provides an indication of zones prone to suffer greater damage by gas expansion. The specific steps carried out in this study are: i) extensive blast monitoring in hard rock at surface and underground test sites; ii) analysis of seismic waveforms in terms of amplitude and frequency and their azimuthal distribution with respect to borehole axis, iii) measurement of blast-induced damage from single-hole blasts; iv) assessment and implementation of method to utilize 2D numerical model to predict blast damage in 3D situation; v) use of experimental and numerical results to estimate relative contribution of stress waves and gas penetration to damage, and vi) monitoring and modeling of full-scale production blasts to apply developed method to estimate blast-induced damage from stress waves. The main findings in this study are: i) both P and S-waves are generated and show comparable amplitudes by blasting in boreholes; ii) amplitude and frequency of seismic waves are strongly dependent on initiation mode and direction of propagation of explosive reaction in borehole; iii) in-situ measurements indicate strongly non-symmetrical damage dependent on confinement conditions and initiation mode, and existing rock structure, and iv) gas penetration seems to be mainly responsible for damage (significant damage extension 2-4 borehole diameters from stress waves; > 22 from gas expansion). The method has the potential for application in regular production blasts for control of over-breaks and dilution in operating mines. The main areas proposed for future work are: i) verification of seismic velocity changes in rock by blast-induced damage from controlled experiments; ii) incorporation of gas expansion phase into numerical models; iii) use of 3D numerical model and verification of crack distribution prediction; iv) further studies on strain rate dependency of material strength parameters, and v) accurate measurements of in-hole pressure function considering various confinement conditions.

This thesis deals with the so-called Basis Set Superposition Error (BSSE) from both a methodological and a practical point of view. The purpose of the present thesis is twofold: (a) to contribute step ahead in the correct characterization of weakly bound complexes and, (b) to shed light the understanding of the actual implications of the basis set extension effects in the ab intio calculations and contribute to the BSSE debate. The existing BSSE-correction procedures are deeply analyzed, compared, validated and, if necessary, improved. A new interpretation of the counterpoise (CP) method is used in order to define counterpoise-corrected descriptions of the molecular complexes. This novel point of view allows for a study of the BSSE-effects not only in the interaction energy but also on the potential energy surface and, in general, in any property derived from the molecular energy and its derivativesA program has been developed for the calculation of CP-corrected geometry optimizations and vibrational frequencies, also using several counterpoise schemes for the case of molecular clusters. The method has also been implemented in Gaussian98 revA10 package. The Chemical Hamiltonian Approach (CHA) methodology has been also implemented at the RHF and UHF levels of theory for an arbitrary number interacting systems using an algorithm based on block-diagonal matrices. Along with the methodological development, the effects of the BSSE on the properties of molecular complexes have been discussed in detail. The CP and CHA methodologies are used for the determination of BSSE-corrected molecular complexes properties related to the Potential Energy Surfaces and molecular wavefunction, respectively.First, the behaviour of both BSSE-correction schemes are systematically compared at different levels of theory and basis sets for a number of hydrogen-bonded complexes. The Complete Basis Set (CBS) limit of both uncorrected and CP-corrected molecular properties like stabilization energies and intermolecular distances has also been determined, showing the capital importance of the BSSE correction. Several controversial topics of the BSSE correction are addressed as well. The application of the counterpoise method is applied to internal rotational barriers. The importance of the nuclear relaxation term is also pointed out. The viability of the CP method for dealing with charged complexes and the BSSE effects on the double-well PES blue-shifted hydrogen bonds is also studied in detail. In the case of the molecular clusters the effect of high-order BSSE effects introduced with the hierarchical counterpoise scheme is also determined.The effect of the BSSE on the electron density-related properties is also addressed. The first-order electron density obtained with the CHA/F and CHA/DFT methodologies was used to assess, both graphically and numerically, the redistribution of the charge density upon BSSE-correction. Several tools like the Atoms in Molecules topologycal analysis, density difference maps, Quantum Molecular Similarity, and Chemical Energy Component Analysis were used to deeply analyze, for the first time, the BSSE effects on the electron density of several hydrogen bonded complexes of increasing size. The indirect effect of the BSSE on intermolecular perturbation theory results is also pointed out It is shown that for a BSSE-free SAPT study of hydrogen fluoride clusters, the use of a counterpoise-corrected PES is essential in order to determine the proper molecular geometry to perform the SAPT analysis.

La tesis tracta diferents aspectes relacionats amb el càlcul de la semblança quàntica, així com la seva aplicació en la racionalització i predicció de l'activitat de fàrmacs. Es poden destacar dos progressos importants en el desenvolupament de noves metodologies que faciliten el càlcul de les mesures de semblança quàntica. En primer lloc, la descripció de les molècules mitjançant les funciones densitat aproximades PASA (Promolecular Atomic Shell Approximation) ha permès descriure amb suficient precisió la densitat electrònica dels sistemes moleculars analitzats, reduint substancialment el temps de càlcul de les mesures de semblança. En segon lloc, el desenvolupament de tècniques de superposició molecular específiques de les mesures de semblança quàntica ha permès resoldre el problema de l'alineament en l'espai dels compostos comparats. El perfeccionament d'aquests nous procediments i algoritmes matemàtics associats a les mesures de semblança molecular quàntica, ha estat essencial per poder progressar en diferents disciplines de la química computacional, sobretot les relacionades amb les anàlisis quantitatives entre les estructures moleculars i les seves activitats biològiques, conegudes amb les sigles angleses QSAR (Quantitative Structure-Activity Relationships). Precisament en l'àrea de les relacions estructura-activitat s'han presentat dues aproximacions fonamentades en la semblança molecular quàntica que s'originen a partir de dues representacions diferents de les molècules. La primera descripció considera la densitat electrònica global de les molècules i és important, entre altres, la disposició dels objectes comparats en l'espai i la seva conformació tridimensional. El resultat és una matriu de semblança amb les mesures de semblança de tots els parells de compostos que formen el conjunt estudiat. La segona descripció es fonamenta en la partició de la densitat global de les molècules en fragments. S'utilitzen mesures d'autosemblança per analitzar els requeriments bàsics d'una determinada activitat des del punt de vista de la semblança quàntica. El procés permet la detecció de les regions moleculars que són responsables d'una alta resposta biològica. Això permet obtenir un patró amb les regions actives que és d'evident interès per als propòsits del disseny de fàrmacs. En definitiva, s'ha comprovat que mitjançant la simulació i manipulació informàtica de les molècules en tres dimensions es pot obtenir una informació essencial en l'estudi de la interacció entre els fàrmacs i els seus receptors macromoleculars. / There is probably no other concept that contributed to the development of chemistry so remarkably as the ill-defined, qualitative concept of similarity. From the intuitively understood meaning of similarity arises also one of the most powerful chemical principles - the principle of analogy - which in early days of chemistry served as the basis for the classification and systematization of molecules and reactions. The same principle underlies also the widely used idea that similar structures have similar properties which, in turn, is the basis for the existence of various empirical relations between the structure and activity known as QSAR relationships. Because of the fundamental role which similarity plays in so many different situations it is not surprising that its systematic investigation has become the focus of intense scientific interest. Main attention in this respect was devoted to the design of new quantitative measures of molecular similarity. The philosophy underlying the development of quantitative, similarity measures based on quantum theory, arises from the idea that properties of molecules, whether chemical, physical or biological are predetermined by the molecular structure. The rationalization of empirical structure-activity relationships is to considerable extent connected with the recent efforts in the design of new molecular descriptors based on quantum theory. The simplest of such quantities is the electron density function and most of the theoretical molecular descriptors are derived just from this quantity. Among them, a privileged place belongs to the so-called Molecular Quantum Similarity Measures (MQSM). These measures are generally based on the pairwise comparison of electron density functions of the corresponding molecules.This contribution pretends to present an up-to-date revision of Quantum Similarity concepts and their application to QSAR. The general form of MQSM is introduced, and the concrete definitions for practical implementations are specified. Two important topics related to the application of MQSM are discussed: first the Promolecular Atomic Shell Approximation (PASA), a method for fitting first-order molecular density functions for a fast and efficient calculation of the MQSM. Afterwards, a possible solution to the problem of molecular alignment, a determinant procedure in all 3D QSAR methodologies. Finally, the application of Quantum Similarity to QSAR is discussed in detail. Two kind of descriptors derived from molecular quantum similarity theory were used to construct QSAR models: molecular quantum similarity matrices and fragment quantum self-similarity measures. The practical implementation of those ideas has led to the publication of several papers, and finally, to the present work.

Als Teilprojekt des Themenkreises III "Transitionskontrolle" des Schwerpunkt-Forschungsprogramms "Transition" der Deutschen Forschungsgemeinschaft, konzentriert sich diese Arbeit auf experimentelle Grundlagenuntersuchungen zum laminar-turbulenten Grenzsichtumschlag. Die Experimente wurden in der Grenzschicht einer ebenen, parallel angeblasenen, hydraulisch glatten Platte durchgeführt. Einen besonderen Schwerpunkt bildet die Abhängigkeit der Entwicklung der Instabilitäten, der sogenannten Tollmien-Schlichting Wellen, von deren Schräglaufwinkel zur Plattenvorderkante. Weiterhin wird der Einfluss zahlreicher Parameter wie z.B. des Schalldruckpegels und der Anregungsfrequenz diskutiert. Die Anregung der Tollmien-Schlichting Wellen erfolgte über periodisches Ausblasen / Ansaugen von Luft durch oberflächenbündige Schlitze quer zur Strömungsrichtung. Mit einem zeitlich hochauflösenden, restlichverstärkendem Kamerasystem konnten Aufnahmen der Strömungsvisualisierung erzielt werden, die unter anderem die zeitliche Entwicklung von Wirbelstrukturen (Lambda- Wirbel) zeigen. Zur Analyse der experimentell gewonnen Daten werden vergleichend Berechnungen nach der "Linearen Stabilitätstheorie" diskutiert. Einen weiteren Schwerpunkt bilden Untersuchungen zur aktiven Transitionskontrolle. Dabei wird der künstlich angeregten Tollmien Schlichting Welle eine gegenphasige Störwelle stromab überlagert. Es konnte nachgewiesen werden, das mit diesem Verfahren entsprechend des Superpositionsprinzips, die anfängliche Störamplitude der Tollmien Schlichting Welle deutlich reduziert wird. Es kommt zu einer fast vollständigen Störauslöschung. Untersuchungen im Nahfeld der Störeinkopplung, sowohl im Bereich der Anregnung als auch der gegenphasigen Dämpfungseinkopplung, zeigen deren Auswirkung auf die Entwicklung der Grenzschicht. / A sub-project of the working group III, "Transition Control" of the German Research Community's project "Transition", this paper is focused on experimental fundamental investigations in the field of laminar-turbulent transition. The experiments were carried out in the boundary layer of a flat plat with tangential blowing. The main topic is the development of instabilities, or so-called Tollmien-Schlichting Waves (TSWs), based on the oblique angle between the TSWs and the leading edge. In addition the influence of other parameters, including the sound-pressure level and the frequency of the TSWs are discussed. The instabilities are initialised by suction and blowing through flush, oblique slots in the surface of a flat plate. Pictures of the flow visualisation, recorded with a high-speed camera system, show the time-resolved development of structures (Lamda-Vortices) within the boundary layer. In order to analyse the experimental data, a comparison is made between it and numerical calculations corresponding to the Linear Instability Theory. Another main topic is the investigation of the active transition control. According to the Super Position Principle a second wave with opposite phase is superimposed on the TSW. It can be demonstrated that this technique works with oblique waves too. The initialised instabilities can almost completely be cancelled out. Investigations very close to the initialising slots of the TSW with a high special resolution show their influence on the development of the boundary layer.

L'utilisation des matériaux cellulaires à base de polymères type mousse gagne de plus en plus de terrain, notamment pour l'absorption acoustique. L'objectif de ce travail est de présenter de nouvelles approches pour la caractérisation de ces matériaux.<br /> Diverses méthodes ont été développées afin de caractériser ces matériaux, en particulier leur domaine linéaire, zone privilégiée pour l'absorption acoustique et la détermination des paramètres mécaniques courants. Cependant ces caractérisations restent souvent limitées à une faible plage fréquentielle. Une première étude présente ici le comportement linéaire sur une large gamme de fréquences grâce à l'application du principe de Superposition Temps-Température (TTS). L'utilisation du TTS sur une famille de mousses obtenues avec le même polymère, de même densité, mais dont la taille des pores est différente, met en évidence deux aspects importants: seulement 3 % du squelette solide participe à la transmission de la contrainte, et le module élastique à fréquence nulle décroît avec la taille des pores.<br /> Les mousses de polymères sont certes souvent utilisées dans leur domaine linéaire, mais leur comportement mécanique diffère à de plus forts niveaux de déformation. Les courbes en contrainte-déformation présentent un comportement en hystérésis, avec trois zones de comportement distinctes (linéaire, flambement et densification). Il existe d'autres phénomènes en hystérésis qui ont été plus simplement modélisés, par exemple à l'aide de la théorie de Preisach-Krasnoselskii-Mayergoyz (PKM) issue du magnétisme. Une seconde partie de ce travail présente une nouvelle extension de cette théorie PKM aux mousses de polymères réticulés à cellules ouvertes, soumises à de grandes déformations: nous pouvons ainsi modéliser l'hystérésis observée expérimentalement, à partir d'une distribution d'hysterons microscopiques contenus dans un espace de Preisach-Mayergoyz.<br /> Dans une troisième partie, l'influence de l'histoire passée des contraintes sur la mesure des paramètres mécaniques d'une mousse est étudiée, et plus particulièrement la rhéologie de ces mousses dans le cadre de la relaxation de compression, en distinguant deux mécanismes, l'un en zone linéaire de chargement et l'autre en dehors. Liée à l'histoire des contraintes passées, ce second mécanisme de relaxation permet la réduction des contraintes par réarrangement topologique des poutres de la mousse.

Flow and transport phenomena in the subsurface often span a wide range of length (nanometers to kilometers) and time (nanoseconds to years) scales, and frequently arise in applications of CO₂ sequestration, pollutant transport, and near-well acid stimulation. Reliable field-scale predictions depend on our predictive capacity at each individual scale as well as our ability to accurately propagate information across scales. Pore-scale modeling (coupled with experiments) has assumed an important role in improving our fundamental understanding at the small scale, and is frequently used to inform/guide modeling efforts at larger scales. Among the various methods, there often exists a trade-off between computational efficiency/simplicity and accuracy. While high-resolution methods are very accurate, they are computationally limited to relatively small domains. Since macroscopic properties of a porous medium are statistically representative only when sample sizes are sufficiently large, simple and efficient pore-scale methods are more attractive. In this work, two Eulerian pore-network models for simulating single-phase flow and solute transport are developed. The models focus on capturing two key pore-level mechanisms: a) partial mixing within pores (large void volumes), and b) shear dispersion within throats (narrow constrictions connecting the pores), which are shown to have a substantial impact on transverse and longitudinal dispersion coefficients at the macro scale. The models are verified with high-resolution pore-scale methods and validated against micromodel experiments as well as experimental data from the literature. Studies regarding the significance of different pore-level mixing assumptions (perfect mixing vs. partial mixing) in disordered media, as well as the predictive capacity of network modeling as a whole for ordered media are conducted. A mortar domain decomposition framework is additionally developed, under which efficient and accurate simulations on even larger and highly heterogeneous pore-scale domains are feasible. The mortar methods are verified and parallel scalability is demonstrated. It is shown that they can be used as “hybrid” methods for coupling localized pore-scale inclusions to a surrounding continuum (when insufficient scale separation exists). The framework further permits multi-model simulations within the same computational domain. An application of the methods studying “emergent” behavior during calcite precipitation in the context of geologic CO₂ sequestration is provided. / text

This thesis examines a multivariate point process in time with focus on a mu- tual relations of its marginal point processes. The first chapter acquaints the re- ader with the theoretical background of multivariate point processes and their properties, especially the higher-order cumulant-correlation measures. Later on, several models of multivariate point processes with different dependence structu- res are characterized, such as the random superposition model, a Poisson depen- dent superposition point process, a jitter Poisson dependent superposition point process orrenewal processes models. Simulations of each of them are provided. Furthermore, two statistical methods for higher-order correlations are presented; the cumulant based inference of higher-order correlations, and the extended til- ling coefficient. Finally, the introduced methods are applied not only on the data from simulations, but also on the real, simultaneously recorded nerve cells spike train data. The results are discussed. 1

As características arquitetônicas e o desempenho estrutural de pontes suspensas, estaiadas ou pênseis, têm determinado a sua crescente utilização em obras de arte destinadas a vencer grandes vãos. Essa utilização crescente que ocorreu no mundo nas últimas décadas se repete agora nos últimos anos no país. Várias dessas obras estão em execução e em projeto. Um dos aspectos relevantes na análise estrutural das pontes suspensas é o de seu comportamento quando submetidas à ação do vento. Apresenta-se o sistema computacional ANA-PSp desenvolvido especialmente para o estudo do movimento de tabuleiros de pontes suspensas sujeitas a esforços aeroelásticos e aerodinâmicos. Esse sistema computacional formado por um conjunto de subsistemas, é elaborado para a análise aeroelástica de pontes suspensas sob a ação de vento e permite análises paramétricas extensas dos fenômenos de drapejamento (flutter) e de martelamento (buffeting). A discretização da estrutura é efetuada pelo método dos elementos finitos e a redução dos graus de liberdade é realizada por superposição modal com modos selecionados que melhor descrevem os movimentos do tabuleiro. Utiliza-se modelo matemático reduzido para a análise multimodal no domínio do tempo e da freqüência. A velocidade crítica ou velocidade de drapejamento é determinada por procedimento de autovalores complexos com a obtenção de freqüências e taxas de amortecimentos modais para várias velocidades do vento. Adicionalmente, o fenômeno do drapejamento é estudado por séries temporais de respostas de coordenadas generalizadas e de deslocamentos selecionados e por análise espectral dessas séries temporais, que permitem a verificação das características de vibração do tabuleiro da ponte no domínio da freqüência. O estudo do fenômeno de martelamento considera esforços aeroelásticos determinísticos e esforços aerodinâmicos estocásticos e apresentam-se resultados em espectros de potência de deslocamentos e em desvios padrão de deslocamentos ao longo do tabuleiro. Para validar o sistema ANA-PSp, apresentam-se estudos de caso para a ponte estaiada da Normandia, para a ponte pênsil colapsada de Tacoma Narrows e para a ponte estaiada projetada, mas não executada, sobre o Rio Tietê e localizada na extremidade do complexo viário Jacu-Pêssego. / The architectonic characteristics and the structural performance of suspension bridges and cable-stayed bridges have determined their growing use on large span bridges. This growing usage, which has occurred world-wide during the last decades, is now being repeated in Brazil during the last few years. Several such bridges are presently either undergoing construction or being designed. One of the outstanding aspects in the structural analysis of suspension bridges is their behavior under wind action. This paper presents the computer system ANA-PSp, specially developed for studying the movement of suspended bridge decks under aeroelastic and aerodynamic forces. This computer system is formed by a group of subsystems and is created for aeroelastic analysis of suspended bridges under wind action. It allows extended parametric analyses of the flutter and the buffeting phenomena. Structural discretization is done by the finite element method and the reduction of degrees of freedom is obtained by modal superposition of the selected modes which best describe the deck movements. A reduced mathematical model is used for the multimodal analysis in the time and frequency domains. Critical velocity or flutter velocity is determined by a procedure of complex eigenvalues which obtains frequencies and damping ratios for different wind speeds. Additionally, the flutter phenomenon is studied by temporal series of answers to generalized coordinate responses and of selected displacements by spectral analysis of such temporal series, which allow us to verify the characteristics of the vibrations of the bridge deck in the frequency domain. The study of the buffeting phenomenon considers deterministic aeroelastic and stochastic aerodynamic forces. The paper presents results in displacement power spectra and in the standard deviation of displacements along the deck. In order to validate system ANA-PSp, case studies are presented for the cable-stayed Ponte de Normandie in Le Havre (France), for the collapsed suspension bridge on Tacoma Narrows and for the cable-stayed bridge, already designed but not built, on Tietê River, located at one end of the highway complex Jacu-Pêssego (São Paulo, SP, Brazil).

The formation and patterns of a monolayer are determined by the interplay of two fundamental interactions, adsorbate-substrate and intermolecular interactions. The binding strength between adsorbate and substrate affects the mobility of the adsorbate at the surface and the stability of the complex. The intermolecular interaction plays a significant role in the monolayer patterns on the epitaxial layer of the substrate. A monolayer can be formed either by a spontaneous self-assembly, or by fabrication via atomic-layer deposition (ALD). The physical and chemical properties of the resulting monolayer have a broad array of applications in fabricating functional materials for hydrophobic or hydrophilic surfaces, biological sensors, alternating the properties of the substrate, catalysis and forming ordered layered structures. In this dissertation, the investigation focuses primarily on the influence of the surface topology on the binding behaviour of adsorbate-surface complexes. The state of the art DFT-TS method is used to simulate the sulfur-containing amino acids at complex gold surfaces and examine the relationship between the binding strengths and the binding sites with various nearest neighbouring environments. The same method is also used to determine if a chemical reaction will take place for various catalytic silicon precursors at a silicon oxide surface. Simulating surface chemistry using the DFT-TS method requires intensive com- puting resources, including CPU use and computing time. Another focus of this dissertation is to increase the data generating speed by reducing the size of the sim- ulated systems without altering the outcome. A relatively small gold cluster is used to study the binding behaviours of small organic molecules on the cluster. The same strategy is also used to simulate the chemical reactions between various self-catalying silicon precursors and a water molecule. / Graduate / 2021-10-21