In this work, experimental and theoretical approaches are applied to the study of chemical reaction dynamics. In Chapter 2, two applications of transition state theory are presented: (1) Application of microcanonical transition state theory to determine the rate constant of dissociation of C2F3I after π∗ ← π excitation. It was found that this reaction has a very fast rate constant and thus is a promising system for testing the statistical assumption of molecular reaction dynamics. (2) A general rate constant expression for the reaction of atoms and molecules at surfaces was derived within the statistical framework of flexible transition state theory. In Chapter 4, a computationally efficient TDDFT approach was found to produce useful potential energy surface landscapes for application to non-adiabatic predissociative dynamics of the molecule CS2 after excitation from the ground state to the singlet C-state. In Chapter 5, ultrafast experimental results of excitation of CS2 to the predissociative neutral singlet C-state is presented. The bandwidth of the excitation laser was carefully tuned to span a two-component scattering resonance with each component differently evolving electronically with respect to excited state character during the quasi-bound oscillation. Scalar time-resolved photoelectron spectra (TRPES) and vector time-resolved photoelectron angular distribution (TRPAD) observables were recorded during the predissociation. The TRPES yield of photoelectrons was found to oscillate with a quantum beat pattern for the photoelectrons corresponding to ionization to the vibrationless cation ground state; this beat pattern was obscured for photoelectron energies corresponding to ionization from the vibrationally excited CS2 cation. The TRPAD data was recorded for two general molecular ensemble cases: with and without a pre-excitation alignment laser pulse. It was found that in the case of ensemble alignment (Chapter 6), the “molecular frame” TRPAD (i.e. TRMFPAD) was able to image the purely valence electronic dynamics of the evolving CS2 C-state. The unaligned ensemble TRPAD observable suffers from excessive orientational averaging and was unable to observe the quantum beat. Engineering efforts were also undertaken to eliminate scattered light background signal (Chapter 7, Appendix A) and improve laser stability as a function of ambient pressure (Appendix B) for TRMFPAD experiments. / Thesis (Ph.D, Chemistry) -- Queen's University, 2012-09-11 22:18:20.89

Indiana University-Purdue University Indianapolis (IUPUI) / In recent decades, Petri nets (PNs) have been used to model traffic networks for different purposes, such as signal phase control, routing, and traffic flow estimation, etc. Because of the complex nature of traffic networks where both discrete and continuous dynamics come into play, the Hybrid Petri net (HPN) model becomes an important tool for the modeling and analysis of traffic networks. In Chapter 1 a brief historical summery about traffic systems control and then related work is mentioned followed by the major contributions in this research. Chapter 2 provides a theoretical background on Petri nets. In Chapter 3, we develop a HPN model for a single signalized intersection first, then we extend this model to study a simple traffic network that consists of two successive intersections. Time delays between different points of network are also considered in order to make the model suitable for analysis and simulation. In addition to HPN models, we also consider discrete Petri nets where their modeling simplicity enables the characterization of the occurrences of all events in the system. This discrete PN is particularly useful to give a higher-level representation of the traffic network and study its event occurrences and correlations. In Chapter 4, we build a discrete PN model to represent a traffic network with two successive intersections. However, we find that the model leads to unbounded places which cannot accurately reflect the dynamics of the traffic in terms of event occurrences. Hence, we introduce the Modified Binary Petri nets (MBPN) to overcome the limitation and resolve the confliction problem when we design our controllers. This MBPN model is a powerful tool and can be useful for the modeling and analysis of many other applications in traffic networks. Chapter 5 gives a summary for each chapter, provides conclusion and discusses future work for both discrete and hybrid Petri nets.

[ES] Desde hace aproximadamente dos décadas, las ayudas tecnológicas a la conducciónn han ido creciendo a un ritmo vertiginoso con la intención de hacer estos sistemas más eficientes y seguros. Estas ayudas a la conducción han ido cubriendo fallos que los investigadores denominan "conducción errática" ó "comportamientos inseguros al volante" y que son decisiones arbitrarias tomadas por un conductor humano, que ponen en peligro a todos los usuarios de la carretera. Estas malas decisiones, sumadas al creciente número de viajes en coche en una ciudad hoy en día (post pandemia), muestran la necesidad de seguir haciendo propuestas tecnológicas, enfocadas a donde se producen interacciones más complejas entre vehículos; por ejemplo, una intersección en hora punta. Los desarrollos en ayudas a la conducción se han orientado en dos temas: el primero sobre la automatización de la conducción (Sistemas Avanzados de Asistencia al Conductor - ADAS y Vehículos Automatizados - AV) y el segundo sobre la gestión del tráfico vial (algoritmos centralizados o distribuidos para el control del tráfico). Aunque en la actualidad hay varias empresas automotrices y centros de investigación trabajando en los dos temas, y en especial en algunos casos eliminando de la ecuación el comportamiento humano, todavía hay carencias en las configuraciones, para que un vehículo autónomo sea capaz de tomar decisiones óptimas, frente a todas las posibles condiciones disponibles en un tráfico vial. Ahora bien, y teniendo en cuenta los dos temas antes mencionados sobre los desarrollos en ayudas a la conducción, los investigadores prevén a grandes rasgos, que para alcanzar mayores niveles de conducción autónoma en la próxima década, es necesario estudiar cómo hacer más eficientes las interacciones autónomas entre vehículos. Por ello, las intersecciones viales son un ejemplo clave, donde es posible analizar casos de interacciones de alta complejidad entre vehículos, ya que se trata de una parte de la infraestructura vial, donde los vehículos comparten carriles, vías, cruces o cambios de carril a voluntad, y que podría generar colisiones en puntos de conflicto y retrasos en los desplazamientos si no existe una cooperación adecuada. De esta forma, en esta tesis se propone una serie de algoritmos distribuidos para el control del tráfico en intersecciones, basados en el intercambio de comunicaciones entre vehículos autónomos (interacciones locales) cercano a las intersecciones y donde se muestran comportamientos emergentes en el tráfico, resultando en cruces de forma cooperativa, segura y eficiente, desde bajas a altas densidades de tráfico vehicular en las intersecciones. Esta investigación se desarrolla utilizando simuladores de tráfico vial, con calles estilo Manhattan; primero implementando escenarios menos complejos con calles urbanas de un carril, y luego incrementando la complejidad con múltiples carriles. / [CA] Des de fa aproximadament dues dècades, les ajudes tecnològiques a la conducció han anat creixent a un ritme vertiginós amb la intenció de fer aquests sistemes més eficients i segurs. Aquestes ajudes a la conducció han anat cobrint fallades que els investigadors denominen "conducció erràtica" o "comportaments insegurs al volant" i que són decisions arbitràries preses per un conductor humà, que posen en perill a tots els usuaris de la carretera. Aquestes males decisions, sumades al creixent nombre de viatges en cotxe en una ciutat avui dia (post pandèmia), mostren la necessitat de seguir fent propostes tecnològiques, enfocades a on es produeixen interaccions més complexes entre vehicles; per exemple, una intersecció en hora punta. Els desenvolupaments en ajudes a la conducció s'han orientat en dos temes: el primer sobre l'automatització de la conducció (Sistemes Avançats d'Assistència al Conductor - ADAS i Vehicles Automatitzats - AV) i el segon sobre la gestió del trànsit vial (algoritmes centralitzats o distribuïts per al control del trànsit). Encara que actualment hi ha diverses empreses automobilístiques i centres de recerca treballant en els dos temes, i en especial en alguns casos eliminant de l'equació el comportament humà, encara hi ha mancances en les configuracions, perquè un vehicle autònom siga capaç de prendre decisions òptimes, davant totes les possibles condicions disponibles en un trànsit vial. Ara bé, i tenint en compte els dos temes abans esmentats sobre els desenvolupaments en ajudes a la conducció, els investigadors preveuen a grans trets, que per assolir majors nivells de conducció autònoma en la propera dècada, és necessari estudiar com fer més eficients les interaccions autònomes entre vehicles. Per això, les interseccions vials són un exemple clau, on és possible analitzar casos d'interaccions d'alta complexitat entre vehicles, ja que es tracta d'una part de la infraestructura vial, on els vehicles comparteixen carrils, vies, creus o canvis de carril a voluntat, i que podria generar col·lisions en punts de conflicte i retards en els desplaçaments si no existeix una cooperació adequada. D'aquesta manera, en aquesta tesi es proposa una sèrie d'algoritmes distribuïts per al control del trànsit en interseccions, basats en l'intercanvi de comunicacions entre vehicles autònoms (interaccions locals) properes a les interseccions i on es mostren comportaments emergents en el trànsit, resultant en creus de forma cooperativa, segura i eficient, des de baixes a altes densitats de trànsit vehicular en les interseccions. Aquesta investigació es desenvolupa utilitzant simuladors de trànsit vial, amb carrers estil Manhattan; primer implementant escenaris menys complexos amb carrers urbans d'un carril, i després incrementant la complexitat amb múltiples carrils. / [EN] Since a couple of decades, the technological driving aids have gone growing at a dizzying pace with the intention of making these systems more efficient and safe. These driving aids have been covering failures that the researchers name "erratic driving" or "unsafe driving behaviors" and are arbitrary decisions taken by a human driver which endanger all road users. These bad decisions in addition to the increasing number of driving commutes in a city nowadays (post pandemic), show the need to continue doing technological proposals focused on where there are more complex interactions between vehicles when density increases; for instance, an intersection in rush hour. The developments in driving aids have been orientated in two topics: the first driving automation (Advanced Driver Assistance Systems - ADAS and Automated Vehicles - AV) and the second road traffic management (centralized or distributed algorithms to traffic control). Although there are currently several automotive companies and research centers working in the two topics, and in special in some cases removing the equation the human behavior, there are still lacks in the configurations for an vehicle autonomous be able to make optimal decisions front to all possible conditions available in a road traffic. Now, and take into account the two topics aforementioned about driving aids developments, researchers broadly envisage that in order to reach autonomous driving levels higher (first topic) in the next decade, is necessary to study how to do autonomous vehicle interactions (second topic) more efficient. Therefore, road intersections are an instance where it is possible to analyse cases of highly complexity interactions between vehicles, because it is a part of road infrastructure where the vehicles sharing lanes, paths, crossings or lane changes at will and it could generate collisions on conflict points and time delay in the commutes if there is not an appropriate cooperation. Hence, this thesis proposes a series of distributed algorithms to traffic control on intersections, based on interchange of communications between autonomous vehicles (local interactions) near to the intersections that show emergent behaviors to crossing cooperative, safe way and efficiency with high densities the traffic system on intersections. This research is developed using simulators with Manhattan-style streets; first implementing scenarios less complex with one-lane city streets and then increase the complexity with multiple-lanes. / González Pinzón, CL. (2024). Distributed Intersection Management Algorithms for Autonomous Vehicles [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/204406

Cette thèse est consacrée à l'étude de la géométrie des variétés de Fano complexes en utilisant les propriétés des sous-faisceaux du fibré tangent et la géométrie du diviseur fondamental. Les résultats principaux compris dans ce texte sont : (i) Une généralisation de la conjecture de Hartshorne: une variété lisse projective est isomorphe à un espace projectif si et seulement si son fibré tangent contient un sous-faisceau ample.(ii) Stabilité du fibré tangent des variétés de Fano lisses de nombre de Picard un : à l'aide de théorèmes d'annulation sur les espaces hermitiens symétriques irréductibles de type compact M, nous montrons que pour presque toute intersection complète générale dans M, le fibré tangent est stable. La même méthode nous permet de donner une réponse sur la stabilité de la restriction du fibré tangent de l'intersection complète à une hypersurface générale.(iii) Non-annulation effective pour des variétés de Fano et ses applications : nous étudions la positivité de la seconde classe de Chern des variétés de Fano lisses de nombre de Picard un. Ceci nous permet de montrer un théorème de non-annulation pour les variétés de Fano lisses de dimension n et d'indice n-3. Comme application, nous étudions la géométrie anticanonique des variétés de Fano et nous calculons les constantes de Seshadri des diviseurs anticanoniques des variétés de Fano d'indice grand.(iv) Diviseurs fondamentaux des variétés de Moishezon lisses de dimension trois et de nombre de Picard un : nous montrons l'existence d'un diviseur lisse dans le système fondamental dans certain cas particulier. / This thesis is devoted to the study of complex Fano varieties via the properties of subsheaves of the tangent bundle and the geometry of the fundamental divisor. The main results contained in this text are:(i) A generalization of Hartshorne's conjecture: a projective manifold is isomorphic to a projective space if and only if its tangent bundle contains an ample subsheaf.(ii) Stability of tangent bundles of Fano manifolds with Picard number one: by proving vanishing theorems on the irreducible Hermitian symmetric spaces of compact type M, we establish that the tangent bundles of almost all general complete intersections in M are stable. Moreover, the same method also gives an answer to the problem of stability of the restriction of the tangent bundle of a complete intersection on a general hypersurface.(iii) Effective non-vanishing for Fano varieties and its applications: we study the positivity of the second Chern class of Fano manifolds with Picard number one, this permits us to prove a non-vanishing result for n-dimensional Fano manifolds with index n-3. As an application, we study the anticanonical geometry of Fano varieties and calculate the Seshadri constants of anticanonical divisors of Fano manifolds with large index.(iv) Fundamental divisors of smooth Moishezon threefolds with Picard number one: we prove the existence of a smooth divisor in the fundamental linear system in some special cases.