On the Limit of Frequency of Electrochemical Oscillators and Its Relationship to Kinetic Parameters

The class of electrochemical oscillators characterized by a partially hidden negative differential resistance in an N-shaped current potential curve encompasses a myriad of experimental examples. We present a comprehensive methodological analysis of the oscillation frequency of this class of systems and discuss its dependence on electrical and kinetic parameters. The analysis is developed from a skeleton ordinary differential equation model, and an equation for the oscillation frequency is obtained. Simulations are carried out for a model system, namely, the nickel electrodissolution, and the numerical results are confirmed by experimental data on this system. In addition, the treatment is further applied to the electro-oxidation of ethylene glycol where unusually large oscillation frequencies have been reported. Despite the distinct chemistry underlying the oscillatory dynamics of these systems, a very good agreement between experiments and theoretical predictions is observed. The application of the developed theory is suggested as an important step for primary kinetic characterization.

Entanglement entropy in long-range harmonic oscillators

We study the Von Neumann and Renyi entanglement entropy of long-range harmonic oscillators (LRHO) by both theoretical and numerical means. We show that the entanglement entropy in massless harmonic oscillators increases logarithmically with the sub-system size as S - c(eff)/3 log l. Although the entanglement entropy of LRHO's shares some similarities with the entanglement entropy at conformal critical points we show that the Renyi entanglement entropy presents some deviations from the expected conformal behaviour. In the massive case we demonstrate that the behaviour of the entanglement entropy with respect to the correlation length is also logarithmic as the short-range case. Copyright (c) EPLA, 2012

Stochastische Modelle für nichtlineare Antwortfunktionen in ungeordneten Systemen

In dieser Arbeit werden nichtlineare Experimente zur Untersuchung der Dynamik in amorphen Festkörpern im Rahmen von Modellrechnungen diskutiert. Die Experimente beschäftigen sich mit der Frage nach dynamischen Heterogenitäten, worunter man das Vorliegen dynamischer Prozesse auf unterschiedlichen Zeitskalen versteht. Ist es möglich, gezielt 'langsame' oder 'schnelle' Dynamik in der Probe nachzuweisen, so ist die Existenz von dynamischen Heterogenitäten gezeigt. Ziel der Experimente sind deshalb sogenannte frequenzselektive Anregungen des Systems. In den beiden diskutierten Experimenten, zum einen nichtresonantes Lochbrennen, zum anderen ein ähnliches Experiment, das auf dem dynamischen Kerreffekt beruht, werden nichtlineare Antwortfunktionen gemessen. Um eine Probe in frequenzselektiver Weise anzuregen, werden zunächst einer oder mehrere Zyklen eines oszillierenden elektrischen Feldes an die Probe angelegt. Die Experimente werden zunächst im Terahertz-Bereich untersucht. Auf dieser Zeitskala findet man phonon-ähnliche kollektive Schwingungen in Gläsern. Diese Schwingungen werden durch (anharmonische) Brownsche Oszillatoren beschrieben. Der zentrale Befund der Modellrechnungen ist, daß eine frequenzselektive Anregung im Terahertz-Bereich möglich ist. Ein Nachweis dynamischer Heterogenitäten im Terahertz-Bereich ist somit durch beide Experimente möglich. Anschliessend wird das vorgestellte Kerreffekt-Experiment im Bereich wesentlich kleinerer Frequenzen diskutiert. Die langsame Reorientierungsdynamik in unterkühlten Flüssigkeiten wird dabei durch ein Rotationsdiffusionsmodell beschrieben. Es werden zum einen ein heterogenes und zum anderen ein homogenes Szenario zugrundegelegt. Es stellt sich heraus, daß wie beim Lochbrennen eine Unterscheidung durch das Experiment möglich ist. Das Kerreffekt-Experiment wird somit als eine relativ einfache Alternative zur Technik des nichtresonanten Lochbrennens vorgeschlagen.

Prediction of Accurate Anharmonic Experimental Vibrational Frequencies for Water Clusters, (H2O)n, n = 2−5

Accurate anharmonic experimental vibrational frequencies for water clusters consisting of 2−5 water molecules have been predicted on the basis of comparing different methods with MP2/aug-cc-pVTZ calculated and experimental anharmonic frequencies. The combination of using HF/6-31G* scaled frequencies for intramolecular modes and anharmonic frequencies for intermolecular modes gives excellent agreement with experiment for the water dimer and trimer and are as good as the expensive anharmonic MP2 calculations. The water trimer, the cyclic Ci and S4 tetramers, and the cyclic pentamer all have unique peaks in the infrared spectrum between 500 and 800 cm-1 and between 3400 and 3700 cm-1. Under the right experimental conditions these different clusters can be uniquely identified using high-resolution IR spectroscopy.

Advance P. Chem. Problems (I) Populations, Partition Functions, Particle in Box, Harmonic Oscillators, Angular Momentum and Rigid Rotor

This is a set of P. Chem. problems posed at slightly higher than the normal text book level, for students who are continuing in the study of this subject.

Thermodynamical Phase Noise in Oscillators Based on L-C Resonators

Using a new Admittance-based model for electrical noise able to handle Fluctuations and Dissipations of electrical energy, we explain the phase noise of oscillators that use feedback around L-C resonators. We show that Fluctuations produce the Line Broadening of their output spectrum around its mean frequency f0 and that the Pedestal of phase noise far from f0 comes from Dissipations modified by the feedback electronics. The charge noise power 4FkT/R C2/s that disturbs the otherwise periodic fluctuation of charge these oscillators aim to sustain in their L-C-R resonator, is what creates their phase noise proportional to Leeson’s noise figure F and to the charge noise power 4kT/R C2/s of their capacitance C that today’s modelling would consider as the current noise density in A2/Hz of their resistance R. Linked with this (A2/Hz?C2/s) equivalence, R becomes a random series in time of discrete chances to Dissipate energy in Thermal Equilibrium (TE) giving a similar series of discrete Conversions of electrical energy into heat when the resonator is out of TE due to the Signal power it handles. Therefore, phase noise reflects the way oscillators sense thermal exchanges of energy with their environment.

Thermodynamical Phase Noise in Oscillators Based on L-C Resonators (Foundations)

Using a new Admittance-based model for electrical noise able to handle Fluctuations and Dissipations of electrical energy, we explain the phase noise of oscillators that use feedback around L-C resonators. We show that Fluctuations produce the Line Broadening of their output spectrum around its mean frequency f0 and that the Pedestal of phase noise far from f0 comes from Dissipations modified by the feedback electronics. The charge noise power 4FkT/R C2/s that disturbs the otherwise periodic fluctuation of charge these oscillators aim to sustain in their L-C-R resonator, is what creates their phase noise proportional to Leeson’s noise figure F and to the charge noise power 4kT/R C2/s of their capacitance C that today’s modelling would consider as the current noise density in A2/Hz of their resistance R. Linked with this (A2/Hz?C2/s) equivalence, R becomes a random series in time of discrete chances to Dissipate energy in Thermal Equilibrium (TE) giving a similar series of discrete Conversions of electrical energy into heat when the resonator is out of TE due to the Signal power it handles. Therefore, phase noise reflects the way oscillators sense thermal exchanges of energy with their environment

Transpose return relation method for designing low noise oscillators

In this paper, a new linear method for optimizing compact low noise oscillators for RF/MW applications will be presented. The first part of this paper makes an overview of Leeson's model. It is pointed out, and it is demonstrates that the phase noise is always the same inside the oscillator loop. It is presented a general phase noise optimization method for reference plane oscillators. The new method uses Transpose Return Relations (RRT) as true loop gain functions for obtaining the optimum values of the elements of the oscillator, whatever scheme it has. With this method, oscillator topologies that have been designed and optimized using negative resistance, negative conductance or reflection coefficient methods, until now, can be studied like a loop gain method. Subsequently, the main disadvantage of Leeson's model is overcome, and now it is not only valid for loop gain methods, but it is valid for any oscillator topology. The last section of this paper lists the steps to be performed to use this method for proper phase noise optimization during the linear design process and before the final non-linear optimization. The power of the proposed RRT method is shown with its use for optimizing a common oscillator, which is later simulated using Harmonic Balance (HB) and manufactured. Then, the comparison of the linear, HB and measurements of the phase noise are compared.

Non-periodic driving of coupled oscillators:a spherical swing

Nonlinearly coupled, damped oscillators at 1:1 frequency ratio, one oscillator being driven coherently for efficient excitation, are exemplified by a spherical swing with some phase-mismatch between drive and response. For certain damping range, excitation is found to succeed if it lags behind, but to produce a chaotic attractor if it leads the response. Although a period-doubhng sequence, for damping increasing, leads to the attractor, this is actually born as a hard (as regards amplitude) bifurcation at a zero growth-rate parametric line; as damping decreases, an unstable fixed point crosses an invariant plane to enter as saddle-focus a phase-space domain of physical solutions. A second hard bifurcation occurs at the zero mismatch line, the saddle-focus leaving that domain. Times on the attractor diverge when approaching either fine, leading to exactly one-dimensional and noninvertible limit maps, which are analytically determined.

Coherent excitation of nonlinear oscillators

Coherently driven, dissipative nonlinear oscillators,(driving kept permanently in phase with the oscillators response) are proposed as systems with interesting dynamics. Results for simple, preliminary examples, which do not show chaotic behavior, are briefly discussed.

A swarm intelligence approach based on coupled oscillators: an application in demand side management with photovoltaic distributed generation

Esta Tesis aborda los problemas de eficiencia de las redes eléctrica desde el punto de vista del consumo. En particular, dicha eficiencia es mejorada mediante el suavizado de la curva de consumo agregado. Este objetivo de suavizado de consumo implica dos grandes mejoras en el uso de las redes eléctricas: i) a corto plazo, un mejor uso de la infraestructura existente y ii) a largo plazo, la reducción de la infraestructura necesaria para suplir las mismas necesidades energéticas. Además, esta Tesis se enfrenta a un nuevo paradigma energético, donde la presencia de generación distribuida está muy extendida en las redes eléctricas, en particular, la generación fotovoltaica (FV). Este tipo de fuente energética afecta al funcionamiento de la red, incrementando su variabilidad. Esto implica que altas tasas de penetración de electricidad de origen fotovoltaico es perjudicial para la estabilidad de la red eléctrica. Esta Tesis trata de suavizar la curva de consumo agregado considerando esta fuente energética. Por lo tanto, no sólo se mejora la eficiencia de la red eléctrica, sino que también puede ser aumentada la penetración de electricidad de origen fotovoltaico en la red. Esta propuesta conlleva grandes beneficios en los campos económicos, social y ambiental. Las acciones que influyen en el modo en que los consumidores hacen uso de la electricidad con el objetivo producir un ahorro energético o un aumento de eficiencia son llamadas Gestión de la Demanda Eléctrica (GDE). Esta Tesis propone dos algoritmos de GDE diferentes para cumplir con el objetivo de suavizado de la curva de consumo agregado. La diferencia entre ambos algoritmos de GDE reside en el marco en el cual estos tienen lugar: el marco local y el marco de red. Dependiendo de este marco de GDE, el objetivo energético y la forma en la que se alcanza este objetivo son diferentes. En el marco local, el algoritmo de GDE sólo usa información local. Este no tiene en cuenta a otros consumidores o a la curva de consumo agregado de la red eléctrica. Aunque esta afirmación pueda diferir de la definición general de GDE, esta vuelve a tomar sentido en instalaciones locales equipadas con Recursos Energéticos Distribuidos (REDs). En este caso, la GDE está enfocada en la maximización del uso de la energía local, reduciéndose la dependencia con la red. El algoritmo de GDE propuesto mejora significativamente el auto-consumo del generador FV local. Experimentos simulados y reales muestran que el auto-consumo es una importante estrategia de gestión energética, reduciendo el transporte de electricidad y alentando al usuario a controlar su comportamiento energético. Sin embargo, a pesar de todas las ventajas del aumento de auto-consumo, éstas no contribuyen al suavizado del consumo agregado. Se han estudiado los efectos de las instalaciones locales en la red eléctrica cuando el algoritmo de GDE está enfocado en el aumento del auto-consumo. Este enfoque puede tener efectos no deseados, incrementando la variabilidad en el consumo agregado en vez de reducirlo. Este efecto se produce porque el algoritmo de GDE sólo considera variables locales en el marco local. Los resultados sugieren que se requiere una coordinación entre las instalaciones. A través de esta coordinación, el consumo debe ser modificado teniendo en cuenta otros elementos de la red y buscando el suavizado del consumo agregado. En el marco de la red, el algoritmo de GDE tiene en cuenta tanto información local como de la red eléctrica. En esta Tesis se ha desarrollado un algoritmo autoorganizado para controlar el consumo de la red eléctrica de manera distribuida. El objetivo de este algoritmo es el suavizado del consumo agregado, como en las implementaciones clásicas de GDE. El enfoque distribuido significa que la GDE se realiza desde el lado de los consumidores sin seguir órdenes directas emitidas por una entidad central. Por lo tanto, esta Tesis propone una estructura de gestión paralela en lugar de una jerárquica como en las redes eléctricas clásicas. Esto implica que se requiere un mecanismo de coordinación entre instalaciones. Esta Tesis pretende minimizar la cantidad de información necesaria para esta coordinación. Para lograr este objetivo, se han utilizado dos técnicas de coordinación colectiva: osciladores acoplados e inteligencia de enjambre. La combinación de estas técnicas para llevar a cabo la coordinación de un sistema con las características de la red eléctrica es en sí mismo un enfoque novedoso. Por lo tanto, este objetivo de coordinación no es sólo una contribución en el campo de la gestión energética, sino también en el campo de los sistemas colectivos. Los resultados muestran que el algoritmo de GDE propuesto reduce la diferencia entre máximos y mínimos de la red eléctrica en proporción a la cantidad de energía controlada por el algoritmo. Por lo tanto, conforme mayor es la cantidad de energía controlada por el algoritmo, mayor es la mejora de eficiencia en la red eléctrica. Además de las ventajas resultantes del suavizado del consumo agregado, otras ventajas surgen de la solución distribuida seguida en esta Tesis. Estas ventajas se resumen en las siguientes características del algoritmo de GDE propuesto: • Robustez: en un sistema centralizado, un fallo o rotura del nodo central provoca un mal funcionamiento de todo el sistema. La gestión de una red desde un punto de vista distribuido implica que no existe un nodo de control central. Un fallo en cualquier instalación no afecta el funcionamiento global de la red. • Privacidad de datos: el uso de una topología distribuida causa de que no hay un nodo central con información sensible de todos los consumidores. Esta Tesis va más allá y el algoritmo propuesto de GDE no utiliza información específica acerca de los comportamientos de los consumidores, siendo la coordinación entre las instalaciones completamente anónimos. • Escalabilidad: el algoritmo propuesto de GDE opera con cualquier número de instalaciones. Esto implica que se permite la incorporación de nuevas instalaciones sin afectar a su funcionamiento. • Bajo coste: el algoritmo de GDE propuesto se adapta a las redes actuales sin requisitos topológicos. Además, todas las instalaciones calculan su propia gestión con un bajo requerimiento computacional. Por lo tanto, no se requiere un nodo central con un alto poder de cómputo. • Rápido despliegue: las características de escalabilidad y bajo coste de los algoritmos de GDE propuestos permiten una implementación rápida. No se requiere una planificación compleja para el despliegue de este sistema. ABSTRACT This Thesis addresses the efficiency problems of the electrical grids from the consumption point of view. In particular, such efficiency is improved by means of the aggregated consumption smoothing. This objective of consumption smoothing entails two major improvements in the use of electrical grids: i) in the short term, a better use of the existing infrastructure and ii) in long term, the reduction of the required infrastructure to supply the same energy needs. In addition, this Thesis faces a new energy paradigm, where the presence of distributed generation is widespread over the electrical grids, in particular, the Photovoltaic (PV) generation. This kind of energy source affects to the operation of the grid by increasing its variability. This implies that a high penetration rate of photovoltaic electricity is pernicious for the electrical grid stability. This Thesis seeks to smooth the aggregated consumption considering this energy source. Therefore, not only the efficiency of the electrical grid is improved, but also the penetration of photovoltaic electricity into the grid can be increased. This proposal brings great benefits in the economic, social and environmental fields. The actions that influence the way that consumers use electricity in order to achieve energy savings or higher efficiency in energy use are called Demand-Side Management (DSM). This Thesis proposes two different DSM algorithms to meet the aggregated consumption smoothing objective. The difference between both DSM algorithms lie in the framework in which they take place: the local framework and the grid framework. Depending on the DSM framework, the energy goal and the procedure to reach this goal are different. In the local framework, the DSM algorithm only uses local information. It does not take into account other consumers or the aggregated consumption of the electrical grid. Although this statement may differ from the general definition of DSM, it makes sense in local facilities equipped with Distributed Energy Resources (DERs). In this case, the DSM is focused on the maximization of the local energy use, reducing the grid dependence. The proposed DSM algorithm significantly improves the self-consumption of the local PV generator. Simulated and real experiments show that self-consumption serves as an important energy management strategy, reducing the electricity transport and encouraging the user to control his energy behavior. However, despite all the advantages of the self-consumption increase, they do not contribute to the smooth of the aggregated consumption. The effects of the local facilities on the electrical grid are studied when the DSM algorithm is focused on self-consumption maximization. This approach may have undesirable effects, increasing the variability in the aggregated consumption instead of reducing it. This effect occurs because the algorithm only considers local variables in the local framework. The results suggest that coordination between these facilities is required. Through this coordination, the consumption should be modified by taking into account other elements of the grid and seeking for an aggregated consumption smoothing. In the grid framework, the DSM algorithm takes into account both local and grid information. This Thesis develops a self-organized algorithm to manage the consumption of an electrical grid in a distributed way. The goal of this algorithm is the aggregated consumption smoothing, as the classical DSM implementations. The distributed approach means that the DSM is performed from the consumers side without following direct commands issued by a central entity. Therefore, this Thesis proposes a parallel management structure rather than a hierarchical one as in the classical electrical grids. This implies that a coordination mechanism between facilities is required. This Thesis seeks for minimizing the amount of information necessary for this coordination. To achieve this objective, two collective coordination techniques have been used: coupled oscillators and swarm intelligence. The combination of these techniques to perform the coordination of a system with the characteristics of the electric grid is itself a novel approach. Therefore, this coordination objective is not only a contribution in the energy management field, but in the collective systems too. Results show that the proposed DSM algorithm reduces the difference between the maximums and minimums of the electrical grid proportionally to the amount of energy controlled by the system. Thus, the greater the amount of energy controlled by the algorithm, the greater the improvement of the efficiency of the electrical grid. In addition to the advantages resulting from the smoothing of the aggregated consumption, other advantages arise from the distributed approach followed in this Thesis. These advantages are summarized in the following features of the proposed DSM algorithm: • Robustness: in a centralized system, a failure or breakage of the central node causes a malfunction of the whole system. The management of a grid from a distributed point of view implies that there is not a central control node. A failure in any facility does not affect the overall operation of the grid. • Data privacy: the use of a distributed topology causes that there is not a central node with sensitive information of all consumers. This Thesis goes a step further and the proposed DSM algorithm does not use specific information about the consumer behaviors, being the coordination between facilities completely anonymous. • Scalability: the proposed DSM algorithm operates with any number of facilities. This implies that it allows the incorporation of new facilities without affecting its operation. • Low cost: the proposed DSM algorithm adapts to the current grids without any topological requirements. In addition, every facility calculates its own management with low computational requirements. Thus, a central computational node with a high computational power is not required. • Quick deployment: the scalability and low cost features of the proposed DSM algorithms allow a quick deployment. A complex schedule of the deployment of this system is not required.

Hydrated myoglobin's anharmonic fluctuations are not primarily due to dihedral transitions.

To characterize the functionally important anharmonic motions of proteins, simulations of carboxymyoglobin (MbCO) dynamics have been performed during which dihedral transitions were prohibited. Comparison of torsionally restrained and unrestrained protein dynamics simulated at three levels of hydration and at temperatures ranging from 100 to 400 K suggests that hydration "catalyzes" protein mobility by facilitating collective anharmonic motions that do not require dihedral transitions. When dihedral transitions were prohibited, dehydrated MbCO, to a good approximation, exhibited only harmonic fluctuations, whereas hydrated MbCO exhibited both harmonic and anharmonic motions. The fluctuation of helix centers of mass also remained highly anharmonic in the torsionally restrained hydrated system. Atomic mean-square fluctuation at 300 K was reduced upon prohibition of dihedral transitions by only 28% and 10% for MbCO hydrated by 350 and 3830 water molecules, respectively.

Two distinct oscillators in the rat suprachiasmatic nucleus in vitro.

In the rat suprachiasmatic nucleus slice culture, circadian rhythms in the release of arginine vasopressin and vasoactive intestinal polypeptide were measured simultaneously and longitudinally. The phase relationship between the two peptide rhythms was relatively constant in the culture without a treatment of antimitotic drugs but became diverse by an introduction of antimitotics, which is generally used to reduce the number of glial cells. By monitoring the two rhythms continuously for 6 days, different periods were detected in culture with the antimitotic treatment. Furthermore, N-methyl-D-aspartate shifted the phase of the two peptide rhythms in the same culture differently. These results indicate that the arginine vasopressin and vasoactive intestinal polypeptide release are under control of different circadian oscillators.

Accurate integration of forced and damped oscillators

The new methods accurately integrate forced and damped oscillators. A family of analytical functions is introduced known as T-functions which are dependent on three parameters. The solution is expressed as a series of T-functions calculating their coefficients by means of recurrences which involve the perturbation function. In the T-functions series method the perturbation parameter is the factor in the local truncation error. Furthermore, this method is zero-stable and convergent. An application of this method is exposed to resolve a physic IVP, modeled by means of forced and damped oscillators. The good behavior and precision of the methods, is evidenced by contrasting the results with other-reputed algorithms implemented in MAPLE.

The energy transport properties of one dimensional anharmonic lattices.

Vita.