Microscopic theory of cooperative spin crossover: Interaction of molecular modes with phonons

In this article, we present a new microscopic theoretical approach to the description of spin crossover in molecular crystals. The spin crossover crystals under consideration are composed of molecular fragments formed by the spin-crossover metal ion and its nearest ligand surrounding and exhibiting well defined localized (molecular) vibrations. As distinguished from the previous models of this phenomenon, the developed approach takes into account the interaction of spin-crossover ions not only with the phonons but also a strong coupling of the electronic shells with molecular modes. This leads to an effective coupling of the local modes with phonons which is shown to be responsible for the cooperative spin transition accompanied by the structural reorganization. The transition is characterized by the two order parameters representing the mean values of the products of electronic diagonal matrices and the coordinates of the local modes for the high- and low-spin states of the spin crossover complex. Finally, we demonstrate that the approach provides a reasonable explanation of the observed spin transition in the [Fe(ptz)6](BF4)2 crystal. The theory well reproduces the observed abrupt low-spin → high-spin transition and the temperature dependence of the high-spin fraction in a wide temperature range as well as the pronounced hysteresis loop. At the same time within the limiting approximations adopted in the developed model, the evaluated high-spin fraction vs. T shows that the cooperative spin-lattice transition proves to be incomplete in the sense that the high-spin fraction does not reach its maximum value at high temperature.

Experimental and Calculated Spectra of π-Stacked Mild Charge-Transfer Complexes: Jet-Cooled Perylene·(Tetrachloroethene) n , n = 1,2

The S0 ↔ S1 spectra of the mild charge-transfer (CT) complexes perylene·tetrachloroethene (P·4ClE) and perylene·(tetrachloroethene)2 (P·(4ClE)2) are investigated by two-color resonant two-photon ionization (2C-R2PI) and dispersed fluorescence spectroscopy in supersonic jets. The S0 → S1 vibrationless transitions of P·4ClE and P·(4ClE)2 are shifted by δν = −451 and −858 cm–1 relative to perylene, translating to excited-state dissociation energy increases of 5.4 and 10.3 kJ/mol, respectively. The red shift is ∼30% larger than that of perylene·trans-1,2-dichloroethene; therefore, the increase in chlorination increases the excited-state stabilization and CT character of the interaction, but the electronic excitation remains largely confined to the perylene moiety. The 2C-R2PI and fluorescence spectra of P·4ClE exhibit strong progressions in the perylene intramolecular twist (1au) vibration (42 cm–1 in S0 and 55 cm–1 in S1), signaling that perylene deforms along its twist coordinate upon electronic excitation. The intermolecular stretching (Tz) and internal rotation (Rc) vibrations are weak; therefore, the P·4ClE intermolecular potential energy surface (IPES) changes little during the S0 ↔ S1 transition. The minimum-energy structures and inter- and intramolecular vibrational frequencies of P·4ClE and P·(4ClE)2 are calculated with the dispersion-corrected density functional theory (DFT) methods B97-D3, ωB97X-D, M06, and M06-2X and the spin-consistent-scaled (SCS) variant of the approximate second-order coupled-cluster method, SCS-CC2. All methods predict the global minima to be π-stacked centered coplanar structures with the long axis of tetrachloroethene rotated by τ ≈ 60° relative to the perylene long axis. The calculated binding energies are in the range of −D0 = 28–35 kJ/mol. A second minimum is predicted with τ ≈ 25°, with ∼1 kJ/mol smaller binding energy. Although both monomers are achiral, both the P·4ClE and P·(4ClE)2 complexes are chiral. The best agreement for adiabatic excitation energies and vibrational frequencies is observed for the ωB97X-D and M06-2X DFT methods.

Excitonic splittings in molecular dimers: why static ab initio calculations cannot match them

After decades of research on molecular excitons, only few molecular dimers are available on which exciton and vibronic coupling theories can be rigorously tested. In centrosymmetric H-bonded dimers consisting of identical (hetero)aromatic chromophores, the monomer electronic transition dipole moment vectors subtract or add, yielding S0 → S1 and S0 → S2 transitions that are symmetry-forbidden or -allowed, respectively. Symmetry breaking by 12C/13C or H/D isotopic substitution renders the forbidden transition weakly allowed. The excitonic coupling (Davydov splitting) can then be measured between the S0 → S1 and S0 → S2 vibrationless bands. We discuss the mass-specific excitonic spectra of five H-bonded dimers that are supersonically cooled to a few K and investigated using two-color resonant two-photon ionization spectroscopy. The excitonic splittings Δcalc predicted by ab initio methods are 5–25 times larger than the experimental excitonic splittings Δexp. The purely electronic ab initio splittings need to be reduced (“quenched”), reflecting the coupling of the electronic transition to the optically active vibrations of the monomers. The so-called quenching factors Γ < 1 can be determined from experiment (Γexp) and/or calculation (Γcalc). The vibronically quenched splittings Γ·Δcalc are found to nicely reproduce the experimental exciton splittings.

Molecular Machanics of Water Monomer-Maple Code

This is the Maple code to support the molecular dynamics of a water monomer molecule, allowing investigation of the classical vibrations of this molecule.

Geochemical parameters of bottom sediments from the Stromboli Canyon

In recent sediments of the Stromboli Canyon sides features of mineral and grain size compositions, redox conditions, behavior of Fe, Mn, organic carbon, Mo, and W in an environment of active input of pyroclastic material are considered. Differences in conditions of sedimentation and early diagenesis in the east and west sides of the canyon depending on position of the prevailing direction of drift and steepness of the slopes, as well as types of differentiation of detrital material in sediments under conditions of permanent vibrations are specified.

Aplicación de Métodos Meshless al Análisis de Problemas de Autovalores

La presente Tesis Doctoral aborda la aplicación de métodos meshless, o métodos sin malla, a problemas de autovalores, fundamentalmente vibraciones libres y pandeo. En particular, el estudio se centra en aspectos tales como los procedimientos para la resolución numérica del problema de autovalores con estos métodos, el coste computacional y la viabilidad de la utilización de matrices de masa o matrices de rigidez geométrica no consistentes. Además, se acomete en detalle el análisis del error, con el objetivo de determinar sus principales fuentes y obtener claves que permitan la aceleración de la convergencia. Aunque en la actualidad existe una amplia variedad de métodos meshless en apariencia independientes entre sí, se han analizado las diferentes relaciones entre ellos, deduciéndose que el método Element-Free Galerkin Method [Método Galerkin Sin Elementos] (EFGM) es representativo de un amplio grupo de los mismos. Por ello se ha empleado como referencia en este análisis. Muchas de las fuentes de error de un método sin malla provienen de su algoritmo de interpolación o aproximación. En el caso del EFGM ese algoritmo es conocido como Moving Least Squares [Mínimos Cuadrados Móviles] (MLS), caso particular del Generalized Moving Least Squares [Mínimos Cuadrados Móviles Generalizados] (GMLS). La formulación de estos algoritmos indica que la precisión de los mismos se basa en los siguientes factores: orden de la base polinómica p(x), características de la función de peso w(x) y forma y tamaño del soporte de definición de esa función. Se ha analizado la contribución individual de cada factor mediante su reducción a un único parámetro cuantificable, así como las interacciones entre ellos tanto en distribuciones regulares de nodos como en irregulares. El estudio se extiende a una serie de problemas estructurales uni y bidimensionales de referencia, y tiene en cuenta el error no sólo en el cálculo de autovalores (frecuencias propias o carga de pandeo, según el caso), sino también en términos de autovectores. This Doctoral Thesis deals with the application of meshless methods to eigenvalue problems, particularly free vibrations and buckling. The analysis is focused on aspects such as the numerical solving of the problem, computational cost and the feasibility of the use of non-consistent mass or geometric stiffness matrices. Furthermore, the analysis of the error is also considered, with the aim of identifying its main sources and obtaining the key factors that enable a faster convergence of a given problem. Although currently a wide variety of apparently independent meshless methods can be found in the literature, the relationships among them have been analyzed. The outcome of this assessment is that all those methods can be grouped in only a limited amount of categories, and that the Element-Free Galerkin Method (EFGM) is representative of the most important one. Therefore, the EFGM has been selected as a reference for the numerical analyses. Many of the error sources of a meshless method are contributed by its interpolation/approximation algorithm. In the EFGM, such algorithm is known as Moving Least Squares (MLS), a particular case of the Generalized Moving Least Squares (GMLS). The accuracy of the MLS is based on the following factors: order of the polynomial basis p(x), features of the weight function w(x), and shape and size of the support domain of this weight function. The individual contribution of each of these factors, along with the interactions among them, has been studied in both regular and irregular arrangement of nodes, by means of a reduction of each contribution to a one single quantifiable parameter. This assessment is applied to a range of both one- and two-dimensional benchmarking cases, and includes not only the error in terms of eigenvalues (natural frequencies or buckling load), but also of eigenvectors

Eigenstructure Assignment Based Controllers Applied to Flexible Spacecraft

The objective of this paper is to evaluate the behaviour of a controller designed using a parametric Eigenstructure Assignment method and to evaluate its suitability for use in flexible spacecraft. The challenge of this objective lies in obtaining a suitable controller that is specifically designated to alleviate the deflections and vibrations suffered by external appendages in flexible spacecraft while performing attitude manoeuvres. One of the main problems in these vehicles is the mechanical cross-coupling that exists between the rigid and flexible parts of the spacecraft. Spacecraft with fine attitude pointing requirements need precise control of the mechanical coupling to avoid undesired attitude misalignment. In designing an attitude controller, it is necessary to consider the possible vibration of the solar panels and how it may influence the performance of the rest of the vehicle. The nonlinear mathematical model of a flexible spacecraft is considered a close approximation to the real system. During the process of controller evaluation, the design process has also been taken into account as a factor in assessing the robustness of the system.

Comparison of vibration and rolling noise emission of resilient and solid monobloc railway wheels in underground lines

Flat or worn wheels rolling on rough or corrugated tracks can provoke airborne noise and ground-borne vibration, which can be a serious concern for nearby neighbours of urban rail transit lines. Among the various treatments used to reduce vibration and noise, resilient wheels play an important role. In conventional resilient wheels, a slightly prestressed V­shaped rubber ring is mounted between the steel wheel centre and tyre. The elastic layer enhances rolling noise and vibration suppression, as well as impact reduction on the track. In this paper the effectiveness of resilient wheels in underground lines, in comparison to monobloc ones, is assessed. The analysed resilient wheel is able to carry greater loads than standard resilient wheels used for light vehicles. It also presents a greater radial resiliency and a higher axial stiffness than conventional V­wheels. The finite element method was used in this study. A quarter car model was defined, in which the wheelset was modelled as an elastic body. Several simulations were performed in order to assess the vibrational behaviour of elastic wheels, including modal, harmonic and random vibration analysis, the latter allowing the introduction of realistic vertical track irregularities, as well as the influence of the running speed. Due to numerical problems some simplifications were needed. Parametric variations were also performed, in which the sensitivity of the whole system to variations of rubber prestress and Poisson’s ratio of the elastic material was assessed.Results are presented in the frequency domain, showing a better performance of the resilient wheels for frequencies over 200 Hz. This result reveals the ability of the analyzed design to mitigate rolling noise, but not structural vibrations, which are primarily found in the lower frequency range.

Spectral-analysis-surface-waves-method in ground characterization

The prediction of train induced vibration levels in structures close to railway tracks before track construction starts is important in order to avoid having to implement costly mitigation measures afterwards. The used models require an accurate characterization of the propagation medium i.e. the soil layers. To this end the spectral analysis of surface waves (SASW) method has been chosen among the active surface waves techniques available. As dynamic source a modal sledge hammer has been used. The generated vibrations have been measured at known offsets by means of several accelerometers. There are many parameters involved in estimating the experimental dispersion curve and, later on, thickness and propagation velocities of the different layers. Tests have been carried out at the Segovia railway station. Its main building covers some of the railway tracks and vibration problems in the building should be avoided. In the paper these tests as well as the influence of several parameters on the estimated soil profile will be detailed.

Robustness Analysis of Eigenstructure Assignment Controllers on Rigid-Flexible Satellites

Flexible spacecraft with attached solar panels may exhibit undesired vibrations and structural deformations. These types of vehicles show an intrinsic coupling of the elements of the structure. The attitude maneuvers performed by flexible spacecraft may cause non-desired deflections of attached flexible elements. Any attitude and orbit control system generally solves these problems using filters that are designed to attenuate the relative deflections of flexible appendages. In this paper, we propose a method for designing attitude static controllers using an eigenstructure assignment (EA) method. A set of requirements were specified from our understanding of the system modes in an open loop. Exhaustive theoretical and numerical simulations were performed on special cases to verify the controller design procedure. In the design of the controller, we considered all of the aspects that relate to the eigenstructure assignment. The primary objective of this paper is to demonstrate the feasibility of obtaining a high degree of decoupling for some selected modes via the application of an EA method. Finally a robustness analysis is perform to the system together with the designed controller by means of a mu-analysis

Problemas de interacción suelo estructura en cimentaciones y muros de contención. Influencia de los fenómenos de despegue y deslizamiento

Los terremotos constituyen una de las más importantes fuentes productoras de cargas dinámicas que actúan sobre las estructuras y sus cimentaciones. Cuando se produce un terremoto la energía liberada genera movimientos del terreno en forma de ondas sísmicas que pueden provocar asientos en las cimentaciones de los edificios, empujes sobre los muros de contención, vuelco de las estructuras y el suelo puede licuar perdiendo su capacidad de soporte. Los efectos de los terremotos en estructuras constituyen unos de los aspectos que involucran por su condición de interacción sueloestructura, disciplinas diversas como el Análisis Estructural, la Mecánica de Suelo y la Ingeniería Sísmica. Uno de los aspectos que han sido poco estudiados en el cálculo de estructuras sometidas a la acciones de los terremotos son los efectos del comportamiento no lineal del suelo y de los movimientos que pueden producirse bajo la acción de cargas sísmicas, tales como posibles despegues y deslizamientos. En esta Tesis se estudian primero los empujes sísmicos y posibles deslizamientos de muros de contención y se comparan las predicciones de distintos tipos de cálculos: métodos pseudo-estáticos como el de Mononobe-Okabe (1929) con la contribución de Whitman-Liao (1985), y formulaciones analíticas como la desarrollada por Veletsos y Younan (1994). En segundo lugar se estudia el efecto del comportamiento no lineal del terreno en las rigideces de una losa de cimentación superficial y circular, como la correspondiente a la chimenea de una Central Térmica o al edificio del reactor de una Central Nuclear, considerando su variación con frecuencia y con el nivel de cargas. Finalmente se estudian los posibles deslizamientos y separación de las losas de estas dos estructuras bajo la acción de terremotos, siguiendo la formulación propuesta por Wolf (1988). Para estos estudios se han desarrollado una serie de programas específicos (MUROSIS, VELETSOS, INTESES y SEPARSE) cuyos listados y detalles se incluyen en los Apéndices. En el capítulo 6 se incluyen las conclusiones resultantes de estos estudios y recomendaciones para futuras investigaciones. ABSTRACT Earthquakes constitute one of the most important sources of dynamic loads that acting on structures and foundations. When an earthquake occurs the liberated energy generates seismic waves that can give rise to structural vibrations, settlements of the foundations of buildings, pressures on retaining walls, and possible sliding, uplifting or even overturning of structures. The soil can also liquefy losing its capacity of support The study of the effects of earthquakes on structures involve the use of diverse disciplines such as Structural Analysis, Soil Mechanics and Earthquake Engineering. Some aspects that have been the subject of limited research in relation to the behavior of structures subjected to earthquakes are the effects of nonlinear soil behavior and geometric nonlinearities such as sliding and uplifting of foundations. This Thesis starts with the study of the seismic pressures and potential displacements of retaining walls comparing the predictions of two types of formulations and assessing their range of applicability and limitations: pseudo-static methods as proposed by Mononobe-Okabe (1929), with the contribution of Whitman-Liao (1985), and analytical formulations as the one developed by Veletsos and Younan (1994) for rigid walls. The Thesis deals next with the effects of nonlinear soil behavior on the dynamic stiffness of circular mat foundations like the chimney of a Thermal Power Station or the reactor building of a Nuclear Power Plant, as a function of frequency and level of forces. Finally the seismic response of these two structures accounting for the potential sliding and uplifting of the foundation under a given earthquake are studied, following an approach suggested by Wolf (1988). In order to carry out these studies a number of special purposes computer programs were developed (MUROSIS, VELETSOS, INTESES and SEPARSE). The listing and details of these programs are included in the appendices. The conclusions derived from these studies and recommendations for future work are presented in Chapter 6.

Estudio de vibraciones de las voladuras de producción en la cantera de Buruntza y su afección sobre el tramo de la red ferroviaria Andoain – Urnieta (País Vasco)

El estudio de vibraciones tiene por objetivo fijar una banda de seguridad para proteger la nueva línea ferroviaria de alta velocidad Madrid – Vitoria – San Sebastián (tramo Andoain – Urnieta).Las tomas de datos han permitido el cálculo de unas leyes de amortiguación de la propagación de las ondas de vibración que permiten predecir cuál será la magnitud de vibración generada a una cierta distancia de la explotación cuando se detona una carga de explosivo determinada. Así mismo, se lleva a cabo un análisis de las concentraciones de energía (vibraciones) que podrían producirse durante una voladura tipo de producción atendiendo a diferentes secuencias de disparo. Con este método, basado en el disparo de un “barreno semilla” de similares condiciones de carga y arranque que un barreno típico de producción, se pretende resaltar la importancia que tiene el rango de las frecuencias en el proceso de generación y transmisión de vibraciones en el terreno, y consecuentemente en los criterios de protección de estructuras frente a tales vibraciones. ABSTRACT The aim of the vibration study is to set a security band to protect the Spanish high speed train (AVE) which goes Madrid-Vitoria-San Sebastian (section Andoain- Urnieta). The data gathered has made possible the calculation of absorption laws of propagation of vibrating waves, that allow the prediction of the magnitude created at a certain distance of the detonation of a known explosive. In addition, an analysis of the energy concentrations that could appear during a blasting in different sequences is made. With this method based on the firing of a seed drill with similar load and boot conditions of a common production drill, is intended to highlight the importance of the frequency range in the process of vibrations transmission and generation in the field, and consequently the importance in the structures protection criteria against these vibrations.

Amplificador de señal analógico basado en conceptos biomiméticos. Desarrollo de modelos computacionales y validación experimental

La presente tesis doctoral estudia las características de un transductor acústico bioinspirado en la estructura del maxilar inferior de un Zifio de Couvier (Ziphius cavirostris). El mecanismo de funcionamiento del sensor se basa en las características de un sistema acoplado formado por los distintos componentes acústicos identificados en el maxilar. Para analizar las características del sensor se propone un modelo simplificado 2D que consta de una cavidad cerrada con forma de bocina acoplada a una lengüeta. Una parte de la lengüeta se encuentra dentro de la cavidad y otra en el exterior. Dicha lengüeta detecta los cambios de presión acústica y las vibraciones generadas por el sonido y las transmite con ondas de flexión al interior de la cavidad. La excitación prolongada sobre la placa puede provocar la activación de los modos propios del sistema acoplado. Dichos modos se caracterizan porque presentan un máximo de presión en el cono de la bocina la cual a su vez actúa como un amplificador acústico. Mediante el Método de los elementos Finitos se analizan las características acústicas del sensor y se construye un prototipo experimental para validar los resultados evaluados en el modelo numérico. Se propone una metodología numérica que permite desarrollar y validar un elemento tetraédrico para caracterizar el comportamiento isotrópico de los medios porosos. La metodología permite construir elementos de línea y bidimensionales. A partir de esta metodología se desarrolla un elemento plano ortotrópico. Se realiza un modelo de la cavidad en el que una de las paredes de la bocina está constituida por material poroso y se une la parte exterior de la lengüeta a dicho material para que constituya una viga sobre un apoyo elástico. Se calcula la respuesta modal y se discuten los efectos del material poroso en la eficiencia del transductor y las posibles mejoras a introducir en el mismo. SUMMARY This Thesis studies the characteristics of an acoustic transducer bioinspired by the structure of the lower maxilla of an odontoceto. In this case a Cuvier’s beaked whale (Ziphius cavirostris). The transducer working mechanism is based in a coupled system, with components identified in the maxilla. To analyze the transducer a simplified 2D model composed by a horn shaped closed cavity is modeled. The cavity is coupled with a flat belt. The belt has one part inside the cavity and the other part outside of it. The belt traverses the cavity wall and it is in charge to pick the vibrations from outside and introduce it inside the cavity. The transmission is obtained through the belt bending. A sustained external load with the right frequency contents will allow the system to reach a stationary pressure intensity distribution inside the cavity. Frequencies with modal shapes that show an important intensity increase at the horn tip are of special interest because of the signal amplification. A finite element model is constructed to study the transducer coupled modes and a prototype is constructed to validate the numerical results. A numerical methodology to construct and validate a tetrahedral finite element for isotropic porous materials is presented. The methodology allows constructing linear and 2D elements. It is extended to model orthotropic porous materials behavior. At the end, one of the horn walls is made of an orthotropic material and the external belt is glued to it in order to configure a belt over an elastic foundation. Modal response is evaluated and the porous material effects in the transducer efficiency and further improvements are discussed.

Estudio de vibraciones en una cantera de caliza con empleo de detonadores electrónicos

El proyecto refleja el estudio de vibraciones entre dos voladuras, una iniciada con detonadores no eléctricos y otra iniciada con detonadores electrónicos, con aproximadamente la misma cantidad de explosivos y situadas en el mismo punto, en una explotación ubicada al sureste de la Comunidad de Madrid en el término municipal de Morata de Tajuña. Es una explotación en la que se extrae caliza mediante arranque por voladura utilizando como carga base una emulsión y como carga columna anfo. En la cantera suelen realizarse dos voladuras cada mes. El estudio de vibraciones se realizó debido a las quejas de los vecinos ante la onda aérea que producían las voladuras y las posibles grietas en estructuras cercanas a la explotación. ABSTRACT The project reflects the study of vibrations between two blasts, one started with nonelectric detonators and other with electronic detonators, with approximately the same amount of explosives placed in the same spot, on a quarry located at southeast of the Community of Madrid the town of Morata de Tajuña. It is a quarry where limestone is extracted by blasting using as base charge an emulsion, and ANFO as column charge. The quarry do two blast per month. The study of vibrations it´s did to the complains of the neighbors to the aerial wave that it´s produce by the blasts and possible cracks in the structures near at the quarry.

Abutments influence in the dynamic response of bridges

A simplified analytical model of a short span bridge is proposed. The inertial interaction effects of pier foundations and abutments has been included in order to evaluate the response sensitivities to different soil-structure interaction variables. The modification of natural frequency and damping properties is shown for typical short span bridges of the integral deck-abutment type for longitudinal vibrations or general bridges for the transverse ones.