Communication: Transition State Theory for dissipative systems without a dividing surface

Transition state theory is a central cornerstone in reaction dynamics. Its key step is the identification of a dividing surface that is crossed only once by all reactive trajectories. This assumption is often badly violated, especially when the reactive system is coupled to an environment. The calculations made in this way then overestimate the reaction rate and the results depend critically on the choice of the dividing surface. In this Communication, we study the phase space of a stochastically driven system close to an energetic barrier in order to identify the geometric structure unambiguously determining the reactive trajectories, which is then incorporated in a simple rate formula for reactions in condensed phase that is both independent of the dividing surface and exact.

Depth dependent lattice disorder and strain in Mn-implanted and post-annealed InAs thin films

The lattice order degree and the strain in as-grown, Mn-implanted and post-implantedannealedInAsthinfilms were investigated with depth resolution by means of Rutherford backscattering spectrometry in channeling conditions (RBS/C). Three main crystallographic axes were analyzed for both In and As sublattices. The behaviour of the induced defects was evaluated in two regions with different native defects: the interface and the surface. The results show that Mn implantation and post-implantation annealing are anisotropic processes, affecting in a different way the In and As sublattices. The mechanisms influencing the enhancement and deterioration of the crystal quality during the implantation are discussed in relation to the as-grown defects and the segregation of the elements

Contradictio in terminis: dialéctica de la ambigüedad en la arquitectura contemporánea

The twentieth century brought a new sensibility characterized by the discredit of cartesian rationality and the weakening of universal truths, related with aesthetic values as order, proportion and harmony. In the middle of the century, theorists such as Theodor Adorno, Rudolf Arnheim and Anton Ehrenzweig warned about the transformation developed by the artistic field. Contemporary aesthetics seemed to have a new goal: to deny the idea of art as an organized, finished and coherent structure. The order had lost its privileged position. Disorder, probability, arbitrariness, accidentality, randomness, chaos, fragmentation, indeterminacy... Gradually new terms were coined by aesthetic criticism to explain what had been happening since the beginning of the century. The first essays on the matter sought to provide new interpretative models based on, among other arguments, the phenomenology of perception, the recent discoveries of quantum mechanics, the deeper layers of the psyche or the information theories. Overall, were worthy attempts to give theoretical content to a situation as obvious as devoid of founding charter. Finally, in 1962, Umberto Eco brought together all this efforts by proposing a single theoretical frame in his book Opera Aperta. According to his point of view, all of the aesthetic production of twentieth century had a characteristic in common: its capacity to express multiplicity. For this reason, he considered that the nature of contemporary art was, above all, ambiguous. The aim of this research is to clarify the consequences of the incorporation of ambiguity in architectural theoretical discourse. We should start making an accurate analysis of this concept. However, this task is quite difficult because ambiguity does not allow itself to be clearly defined. This concept has the disadvantage that its signifier is as imprecise as its signified. In addition, the negative connotations that ambiguity still has outside the aesthetic field, stigmatizes this term and makes its use problematic. Another problem of ambiguity is that the contemporary subject is able to locate it in all situations. This means that in addition to distinguish ambiguity in contemporary productions, so does in works belonging to remote ages and styles. For that reason, it could be said that everything is ambiguous. And that’s correct, because somehow ambiguity is present in any creation of the imperfect human being. However, as Eco, Arnheim and Ehrenzweig pointed out, there are two major differences between current and past contexts. One affects the subject and the other the object. First, it’s the contemporary subject, and no other, who has acquired the ability to value and assimilate ambiguity. Secondly, ambiguity was an unexpected aesthetic result in former periods, while in contemporary object it has been codified and is deliberately present. In any case, as Eco did, we consider appropriate the use of the term ambiguity to refer to the contemporary aesthetic field. Any other term with more specific meaning would only show partial and limited aspects of a situation quite complex and difficult to diagnose. Opposed to what normally might be expected, in this case ambiguity is the term that fits better due to its particular lack of specificity. In fact, this lack of specificity is what allows to assign a dynamic condition to the idea of ambiguity that in other terms would hardly be operative. Thus, instead of trying to define the idea of ambiguity, we will analyze how it has evolved and its consequences in architectural discipline. Instead of trying to define what it is, we will examine what its presence has supposed in each moment. We will deal with ambiguity as a constant presence that has always been latent in architectural production but whose nature has been modified over time. Eco, in the mid-twentieth century, discerned between classical ambiguity and contemporary ambiguity. Currently, half a century later, the challenge is to discern whether the idea of ambiguity has remained unchanged or have suffered a new transformation. What this research will demonstrate is that it’s possible to detect a new transformation that has much to do with the cultural and aesthetic context of last decades: the transition from modernism to postmodernism. This assumption leads us to establish two different levels of contemporary ambiguity: each one related to one these periods. The first level of ambiguity is widely well-known since many years. Its main characteristics are a codified multiplicity, an interpretative freedom and an active subject who gives conclusion to an object that is incomplete or indefinite. This level of ambiguity is related to the idea of indeterminacy, concept successfully introduced into contemporary aesthetic language. The second level of ambiguity has been almost unnoticed for architectural criticism, although it has been identified and studied in other theoretical disciplines. Much of the work of Fredric Jameson and François Lyotard shows reasonable evidences that the aesthetic production of postmodernism has transcended modern ambiguity to reach a new level in which, despite of the existence of multiplicity, the interpretative freedom and the active subject have been questioned, and at last denied. In this period ambiguity seems to have reached a new level in which it’s no longer possible to obtain a conclusive and complete interpretation of the object because it has became an unreadable device. The postmodern production offers a kind of inaccessible multiplicity and its nature is deeply contradictory. This hypothetical transformation of the idea of ambiguity has an outstanding analogy with that shown in the poetic analysis made by William Empson, published in 1936 in his Seven Types of Ambiguity. Empson established different levels of ambiguity and classified them according to their poetic effect. This layout had an ascendant logic towards incoherence. In seventh level, where ambiguity is higher, he located the contradiction between irreconcilable opposites. It could be said that contradiction, once it undermines the coherence of the object, was the better way that contemporary aesthetics found to confirm the Hegelian judgment, according to which art would ultimately reject its capacity to express truth. Much of the transformation of architecture throughout last century is related to the active involvement of ambiguity in its theoretical discourse. In modern architecture ambiguity is present afterwards, in its critical review made by theoreticians like Colin Rowe, Manfredo Tafuri and Bruno Zevi. The publication of several studies about Mannerism in the forties and fifties rescued certain virtues of an historical style that had been undervalued due to its deviation from Renacentist canon. Rowe, Tafuri and Zevi, among others, pointed out the similarities between Mannerism and certain qualities of modern architecture, both devoted to break previous dogmas. The recovery of Mannerism allowed joining ambiguity and modernity for first time in the same sentence. In postmodernism, on the other hand, ambiguity is present ex-professo, developing a prominent role in the theoretical discourse of this period. The distance between its analytical identification and its operational use quickly disappeared because of structuralism, an analytical methodology with the aspiration of becoming a modus operandi. Under its influence, architecture began to be identified and studied as a language. Thus, postmodern theoretical project discerned between the components of architectural language and developed them separately. Consequently, there is not only one, but three projects related to postmodern contradiction: semantic project, syntactic project and pragmatic project. Leading these projects are those prominent architects whose work manifested an especial interest in exploring and developing the potential of the use of contradiction in architecture. Thus, Robert Venturi, Peter Eisenman and Rem Koolhaas were who established the main features through which architecture developed the dialectics of ambiguity, in its last and extreme level, as a theoretical project in each component of architectural language. Robert Venturi developed a new interpretation of architecture based on its semantic component, Peter Eisenman did the same with its syntactic component, and also did Rem Koolhaas with its pragmatic component. With this approach this research aims to establish a new reflection on the architectural transformation from modernity to postmodernity. Also, it can serve to light certain aspects still unaware that have shaped the architectural heritage of past decades, consequence of a fruitful relationship between architecture and ambiguity and its provocative consummation in a contradictio in terminis. Esta investigación centra su atención fundamentalmente sobre las repercusiones de la incorporación de la ambigüedad en forma de contradicción en el discurso arquitectónico postmoderno, a través de cada uno de sus tres proyectos teóricos. Está estructurada, por tanto, en torno a un capítulo principal titulado Dialéctica de la ambigüedad como proyecto teórico postmoderno, que se desglosa en tres, de títulos: Proyecto semántico. Robert Venturi; Proyecto sintáctico. Peter Eisenman; y Proyecto pragmático. Rem Koolhaas. El capítulo central se complementa con otros dos situados al inicio. El primero, titulado Dialéctica de la ambigüedad contemporánea. Una aproximación realiza un análisis cronológico de la evolución que ha experimentado la idea de la ambigüedad en la teoría estética del siglo XX, sin entrar aún en cuestiones arquitectónicas. El segundo, titulado Dialéctica de la ambigüedad como crítica del proyecto moderno se ocupa de examinar la paulatina incorporación de la ambigüedad en la revisión crítica de la modernidad, que sería de vital importancia para posibilitar su posterior introducción operativa en la postmodernidad. Un último capítulo, situado al final del texto, propone una serie de Proyecciones que, a tenor de lo analizado en los capítulos anteriores, tratan de establecer una relectura del contexto arquitectónico actual y su evolución posible, considerando, en todo momento, que la reflexión en torno a la ambigüedad todavía hoy permite vislumbrar nuevos horizontes discursivos. Cada doble página de la Tesis sintetiza la estructura tripartita del capítulo central y, a grandes rasgos, la principal herramienta metodológica utilizada en la investigación. De este modo, la triple vertiente semántica, sintáctica y pragmática con que se ha identificado al proyecto teórico postmoderno se reproduce aquí en una distribución específica de imágenes, notas a pie de página y cuerpo principal del texto. En la columna de la izquierda están colocadas las imágenes que acompañan al texto principal. Su distribución atiende a criterios estéticos y compositivos, cualificando, en la medida de lo posible, su condición semántica. A continuación, a su derecha, están colocadas las notas a pie de página. Su disposición es en columna y cada nota está colocada a la misma altura que su correspondiente llamada en el texto principal. Su distribución reglada, su valor como notación y su posible equiparación con una estructura profunda aluden a su condición sintáctica. Finalmente, el cuerpo principal del texto ocupa por completo la mitad derecha de cada doble página. Concebido como un relato continuo, sin apenas interrupciones, su papel como responsable de satisfacer las demandas discursivas que plantea una investigación doctoral está en correspondencia con su condición pragmática.

Laminar-turbulent transition induced by a discrete roughness element in a supersonic boundary layer

The linear instability and breakdown to turbulence induced by an isolated roughness element in a boundary layer at Mach 2:5, over an isothermal flat plate with laminar adiabatic wall temperature, have been analysed by means of direct numerical simulations, aided by spatial BiGlobal and three-dimensional parabolized (PSE-3D) stability analyses. It is important to understand transition in this flow regime since the process can be slower than in incompressible flow and is crucial to prediction of local heat loads on next-generation flight vehicles. The results show that the roughness element, with a height of the order of the boundary layer displacement thickness, generates a highly unstable wake, which is composed of a low-velocity streak surrounded by a three-dimensional high-shear layer and is able to sustain the rapid growth of a number of instability modes. The most unstable of these modes are associated with varicose or sinuous deformations of the low-velocity streak; they are a consequence of the instability developing in the three-dimensional shear layer as a whole (the varicose mode) or in the lateral shear layers (the sinuous mode). The most unstable wake mode is of the varicose type and grows on average 17% faster tan the most unstable sinuous mode and 30 times faster than the most unstable boundary layer mode occurring in the absence of a roughness element. Due to the high growthrates registered in the presence of the roughness element, an amplification factor of N D 9 is reached within 50 roughness heights from the roughness trailing edge. The independently performed Navier–Stokes, spatial BiGlobal and PSE-3D stability results are in excellent agreement with each other, validating the use of simplified theories for roughness-induced transition involving wake instabilities. Following the linear stages of the laminar–turbulent transition process, the roll-up of the three-dimensional shear layer leads to the formation of a wedge of turbulence, which spreads laterally at a rate similar to that observed in the case of compressible turbulent spots for the same Mach number.

Analysis of the problems associated with dynamic interaction between train, track and structure at transition zones

El gran desarrollo experimentado por la alta velocidad en los principales países de la Unión Europea, en los últimos 30 años, hace que este campo haya sido y aún sea uno de los principales referentes en lo que a investigación se refiere. Por otra parte, la aparición del concepto super − alta velocidad hace que la investigación en el campo de la ingeniería ferroviaria siga adquiriendo importancia en los principales centros de investigación de los países en los que se desea implantar este modo de transporte, o en los que habiendo sido ya implantado, se pretenda mejorar. Las premisas de eficacia, eficiencia, seguridad y confort, que este medio de transporte tiene como razón de ser pueden verse comprometidas por diversos factores. Las zonas de transición, definidas en la ingeniería ferroviaria como aquellas secciones en las que se produce un cambio en las condiciones de soporte de la vía, pueden afectar al normal comportamiento para el que fue diseñada la infraestructura, comprometiendo seriamente los estándares de eficiencia en el tiempo de viaje, confort de los pasajeros y aumentando considerablemente los costes de mantenimiento de la vía, si no se toman las medidas oportunas. En esta tesis se realiza un estudio detallado de la zonas de transición, concretamente de aquellas en las que existe una cambio en la rigidez vertical de la vía debido a la presencia de un marco hidráulico. Para realizar dicho estudio se lleva a cabo un análisis numérico de interacción entre el vehículo y la estructura, con un modelo bidimensional de elemento finitos, calibrado experimentalmente, en estado de tensión plana. En este análisis se tiene en cuenta el efecto de las irregularidades de la vía y el comportamiento mecánico de la interfaz suelo-estructura, con el objetivo de reproducir de la forma más real posible el efecto de interacción entre el vehículo, la vía y la estructura. Otros efectos como la influencia de la velocidad del tren y los asientos diferenciales, debidos a deformaciones por consolidación de los terraplenes a ambos lados el marco hidráulico, son también analizados en este trabajo. En esta tesis, los cálculos de interacción se han llevado a cabo en dos fases diferentes. En la primera, se ha considerado una interacción sencilla debida al paso de un bogie de un tren Eurostar. Los cálculos derivados de esta fase se han denominado cálculos a corto plazo. En la segunda, se ha realizado un análisis considerando múltiples pasos de bogie del tren Eurostar, conformando un análisis de degradación en el que se tiene en cuenta, en cada ciclo, la deformación de la capa de balasto. Los cálculos derivados de esta fase, son denominados en el texto como cálculos a largo plazo. Los resultados analizados muestran que la utilización de los denominados elementos de contacto es fundamental cuando se desea estudiar la influencia de asientos diferenciales, especialmente en transiciones terraplén-estructura en las que la cuña de cimentación no llega hasta la base de cimentación de la estructura. Por otra parte, tener en cuenta los asientos del terraplén, es sumamente importante, cuando se desea realizar un análisis de degradación de la vía ya que su influencia en la interacción entre el vehículo y la vía es muy elevada, especialmente para valores altos de velocidad del tren. En cuanto a la influencia de las irregularidades de la vía, en los cálculos efectuados, se revela que su importancia es muy notable, siendo su influencia muy destacada cuanto mayor sea la velocidad del tren. En este punto cabe destacar la diferencia de resultados derivada de la consideración de perfiles de irregularidades de distinta naturaleza. Los resultados provenientes de considerar perfiles artificiales son en general muy elevados, siendo estos más apropiados para realizar estudios de otra índole, como por ejemplo de seguridad al descarrilamiento. Los resultados provenientes de perfiles reales, dados por diferentes Administradores ferroviarios, presentan resultados menos elevados y más propios del problema analizar. Su influencia en la interacción dinámica entre el vehículo y la vía es muy importante, especialmente para velocidades elevadas del tren. Además el fenómeno de degradación conocido como danza de traviesas, asociado a zonas de transición, es muy susceptible a la consideración de irregularidades de la vía, tal y como se desprende de los cálculos efectuados a largo plazo. The major development experienced by high speed in the main countries of the European Union, in the last 30 years, makes railway research one of the main references in the research field. It should also be mentioned that the emergence of the concept superhigh − speed makes research in the field of Railway Engineering continues to gain importance in major research centers in the countries in which this mode of transportation is already implemented or planned to be implemented. The characteristics that this transport has as rationale such as: effectiveness, efficiency, safety and comfort, may be compromised by several factors. The transition zones are defined in railway engineering as a region in which there is an abrupt change of track stiffness. This stiffness variation can affect the normal behavior for which the infrastructure has been designed, seriously compromising efficiency standards in the travel time, passenger comfort and significantly increasing the costs of track maintenance, if appropriate measures are not taken. In this thesis a detailed study of the transition zones has been performed, particularly of those in which there is a change in vertical stiffness of the track due to the presence of a reinforced concrete culvert. To perform such a study a numerical interaction analysis between the vehicle, the track and the structure has been developed. With this purpose a two-dimensional finite element model, experimentally calibrated, in a state of plane stress, has been used. The implemented numerical models have considered the effects of track irregularities and mechanical behavior of soil-structure interface, with the objective of reproducing as accurately as possible the dynamic interaction between the vehicle the track and the structure. Other effects such as the influence of train speed and differential settlement, due to secondary consolidation of the embankments on both sides of culvert, have also been analyzed. In this work, the interaction analysis has been carried out in two different phases. In the first part a simple interaction due to the passage of a bogie of a Eurostar train has been considered. Calculations derived from this phase have been named short-term analysis. In the second part, a multi-load assessment considering an Eurostar train bogie moving along the transition zone, has been performed. The objective here is to simulate a degradation process in which vertical deformation of the ballast layer was considered. Calculations derived from this phase have been named long-term analysis. The analyzed results show that the use of so-called contact elements is essential when one wants to analyze the influence of differential settlements, especially in embankment-structure transitions in which the wedge-shaped backfill does not reach the foundation base of the structure. Moreover, considering embankment settlement is extremely important when it is desired to perform an analysis of track degradation. In these cases the influence on the interaction behaviour between the vehicle and the track is very high, especially for higher values of speed train. Regarding the influence of the track irregularities, this study has proven that the track’s dynamic response is heavily influenced by the irregularity profile and that this influence is more important for higher train velocities. It should also be noted that the difference in results derived from consideration of irregularities profiles of different nature. The results coming from artificial profiles are generally very high, these might be more appropriate in order to study other effects, such as derailment safety. Results from real profiles, given by the monitoring works of different rail Managers, are softer and they fit better to the context of this thesis. The influence of irregularity profiles on the dynamic interaction between the train and the track is very important, especially for high-speeds of the train. Furthermore, the degradation phenomenon known as hanging sleepers, associated with transition zones, is very susceptible to the consideration of track irregularities, as it can be concluded from the long-term analysis.

Analysis of SnS2 hyperdoped with V proposed as efficient absorber material

Intermediate-band materials can improve the photovoltaic efficiency of solar cells through the absorption of two subband-gap photons that allow extra electron-hole pair formations. Previous theoretical and experimental findings support the proposal that the layered SnS2 compound, with a band-gap of around 2 eV, is a candidate for an intermediate-band material when it is doped with a specific transition-metal. In this work we characterize vanadium doped SnS2 using density functional theory at the dilution level experimentally found and including a dispersion correction combined with the site-occupancy-disorder method. In order to analyze the electronic characteristics that depend on geometry, two SnS2 polytypes partially substituted with vanadium in symmetry-adapted non-equivalent configurations were studied. In addition the magnetic configurations of vanadium in a SnS2 2H-polytype and its comparison with a 4H-polytype were also characterized. We demonstrate that a narrow intermediate-band is formed, when these dopant atoms are located in different layers. Our theoretical predictions confirm the recent experimental findings in which a paramagnetic intermediate-band material in a SnS2 2H-polytype with 10% vanadium concentration is obtained.