Space and time characterization of laser-induced plasmas for applications in chemical analysis and thin film deposition

Après des décennies de développement, l'ablation laser est devenue une technique importante pour un grand nombre d'applications telles que le dépôt de couches minces, la synthèse de nanoparticules, le micro-usinage, l’analyse chimique, etc. Des études expérimentales ainsi que théoriques ont été menées pour comprendre les mécanismes physiques fondamentaux mis en jeu pendant l'ablation et pour déterminer l’effet de la longueur d'onde, de la durée d'impulsion, de la nature de gaz ambiant et du matériau de la cible. La présente thèse décrit et examine l'importance relative des mécanismes physiques qui influencent les caractéristiques des plasmas d’aluminium induits par laser. Le cadre général de cette recherche forme une étude approfondie de l'interaction entre la dynamique de la plume-plasma et l’atmosphère gazeuse dans laquelle elle se développe. Ceci a été réalisé par imagerie résolue temporellement et spatialement de la plume du plasma en termes d'intensité spectrale, de densité électronique et de température d'excitation dans différentes atmosphères de gaz inertes tel que l’Ar et l’He et réactifs tel que le N2 et ce à des pressions s’étendant de 10‾7 Torr (vide) jusqu’à 760 Torr (pression atmosphérique). Nos résultats montrent que l'intensité d'émission de plasma dépend généralement de la nature de gaz et qu’elle est fortement affectée par sa pression. En outre, pour un délai temporel donné par rapport à l'impulsion laser, la densité électronique ainsi que la température augmentent avec la pression de gaz, ce qui peut être attribué au confinement inertiel du plasma. De plus, on observe que la densité électronique est maximale à proximité de la surface de la cible où le laser est focalisé et qu’elle diminue en s’éloignant (axialement et radialement) de cette position. Malgré la variation axiale importante de la température le long du plasma, on trouve que sa variation radiale est négligeable. La densité électronique et la température ont été trouvées maximales lorsque le gaz est de l’argon et minimales pour l’hélium, tandis que les valeurs sont intermédiaires dans le cas de l’azote. Ceci tient surtout aux propriétés physiques et chimiques du gaz telles que la masse des espèces, leur énergie d'excitation et d'ionisation, la conductivité thermique et la réactivité chimique. L'expansion de la plume du plasma a été étudiée par imagerie résolue spatio-temporellement. Les résultats montrent que la nature de gaz n’affecte pas la dynamique de la plume pour des pressions inférieures à 20 Torr et pour un délai temporel inférieur à 200 ns. Cependant, pour des pressions supérieures à 20 Torr, l'effet de la nature du gaz devient important et la plume la plus courte est obtenue lorsque la masse des espèces du gaz est élevée et lorsque sa conductivité thermique est relativement faible. Ces résultats sont confirmés par la mesure de temps de vol de l’ion Al+ émettant à 281,6 nm. D’autre part, on trouve que la vitesse de propagation des ions d’aluminium est bien définie juste après l’ablation et près de la surface de la cible. Toutefois, pour un délai temporel important, les ions, en traversant la plume, se thermalisent grâce aux collisions avec les espèces du plasma et du gaz.

Phase effects on synchronization by dynamical relaying in delay-coupled systems

Synchronization in an array of mutually coupled systems with a finite time delay in coupling is studied using the Josephson junction as a model system. The sum of the transverse Lyapunov exponents is evaluated as a function of the parameters by linearizing the equation about the synchronization manifold. The dependence of synchronization on damping parameter, coupling constant, and time delay is studied numerically. The change in the dynamics of the system due to time delay and phase difference between the applied fields is studied. The case where a small frequency detuning between the applied fields is also discussed.

Femtosecond real-time probing of reactions. 13. Multiphoton dynamics of IHgI

Real-time studies of the dynamics were performed on the reaction of HgI_2 in a molecular beam. Excitation was by either one or multi pump photons (311 nm), leading to two separate sets of dynamics, each of which could be investigated by a time-delayed probe laser (622 nm) that ionized the parent molecule and the fragments by REMPI processes. These dynamics were distinguished by combining the information from transients taken at each mass (HgI_2, HgI, I_2, Hg, and I) with the results of pump (and probe) power dependence studies on each mass. A method of plotting the slope of the intensity dependence against the pump-probe time delay proved essential. In the preceding publication, we detailed the dynamics of the reaction initiated by a one photon excitation to the A-continuum. Here, we present studies of higher-energy states. Multiphoton excitation accesses predissociative states of HgI_2, for which there are crossings into the symmetric and asymmetric stretch coordinates. The dynamics of these channels, which lead to atomic (I or Hg) and diatomic (HgI) fragments, are discussed and related to the nature of the intermediates along the reaction pathway.

Femtosecond time-resolved molecular multiphoton ionization and fragmentation of Na_2

We present a comparison between experimental and theoretical results for pump/probe multiphoton ionizing transitions of the sodium dimer, initiated by femtosecond laser pulses. It is shown that the motion of vibrational wavepackets in two electronic states is probed simultaneously and their dynamics is reflected in the total Na^+_2 ion signal which is recorded as a function of the time delay between pump and probe pulse. The time dependent quantum calculations demonstrate that two ionization pathways leading to the same final states of the molecularion exist: one gives an oscillating contribution to the ion signal, the other yields a constant background. From additional measurements of the Na^+ -transient photofragmentation spectrum it is deduced that another ionization process leading to different final ionic states exists. The process includes the excitation of a doubly excitedbound Rydberg state. This conclusion is supported by the theoretical simulation.

Including a time-of-year effect in the analysis of a matched case-control study

Motivated by a matched case-control study to investigate potential risk factors for meningococcal disease amongst adolescents, we consider the analysis of matched case-control studies where disease incidence, and possibly other risk factors, vary with time of year. For the cases, the time of infection may be recorded. For controls, however, the recorded time is simply the time of data collection, which is shortly after the time of infection for the matched case, and so depends on the latter. We show that the effect of risk factors and interactions may be adjusted for the time of year effect in a standard conditional logistic regression analysis without introducing any bias. We also show that, if the time delay between data collection for cases and controls is constant, provided this delay is not very short, estimates of the time of year effect are approximately unbiased. In the case that the length of the delay varies over time, the estimate of the time of year effect is biased. We obtain an approximate expression for the degree of bias in this case. Copyright © 2004 John Wiley & Sons, Ltd.

Financial time series analysis : Chaos and neurodynamics approach

This work aims at combining the Chaos theory postulates and Artificial Neural Networks classification and predictive capability, in the field of financial time series prediction. Chaos theory, provides valuable qualitative and quantitative tools to decide on the predictability of a chaotic system. Quantitative measurements based on Chaos theory, are used, to decide a-priori whether a time series, or a portion of a time series is predictable, while Chaos theory based qualitative tools are used to provide further observations and analysis on the predictability, in cases where measurements provide negative answers. Phase space reconstruction is achieved by time delay embedding resulting in multiple embedded vectors. The cognitive approach suggested, is inspired by the capability of some chartists to predict the direction of an index by looking at the price time series. Thus, in this work, the calculation of the embedding dimension and the separation, in Takens‘ embedding theorem for phase space reconstruction, is not limited to False Nearest Neighbor, Differential Entropy or other specific method, rather, this work is interested in all embedding dimensions and separations that are regarded as different ways of looking at a time series by different chartists, based on their expectations. Prior to the prediction, the embedded vectors of the phase space are classified with Fuzzy-ART, then, for each class a back propagation Neural Network is trained to predict the last element of each vector, whereas all previous elements of a vector are used as features.

Pareto Frontier for the time-energy cost vector to an Earth-Moon transfer orbit using the patched-conic approximation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Explosive synchronization enhanced by time-delayed coupling

This paper deals with the emergence of explosive synchronization in scale-free networks by considering the Kuramoto model of coupled phase oscillators. The natural frequencies of oscillators are assumed to be correlated with their degrees, and a time delay is included in the system. This assumption allows enhancing the explosive transition to reach a synchronous state. We provide an analytical treatment developed in a star graph, which reproduces results obtained in scale-free networks. Our findings have important implications in understanding the synchronization of complex networks since the time delay is present in most real-world complex systems due to the finite speed of the signal transmission over a distance.

Closed-loop stable model predictive control of integrating systems with dead time

Model predictive control (MPC) applications in the process industry usually deal with process systems that show time delays (dead times) between the system inputs and outputs. Also, in many industrial applications of MPC, integrating outputs resulting from liquid level control or recycle streams need to be considered as controlled outputs. Conventional MPC packages can be applied to time-delay systems but stability of the closed loop system will depend on the tuning parameters of the controller and cannot be guaranteed even in the nominal case. In this work, a state space model based on the analytical step response model is extended to the case of integrating time systems with time delays. This model is applied to the development of two versions of a nominally stable MPC, which is designed to the practical scenario in which one has targets for some of the inputs and/or outputs that may be unreachable and zone control (or interval tracking) for the remaining outputs. The controller is tested through simulation of a multivariable industrial reactor system. (C) 2012 Elsevier Ltd. All rights reserved.

Evolutionary demography of long-lived monocarpic perennials: a time-lagged integral projection model

1. The evolution of flowering strategies (when and at what size to flower) in monocarpic perennials is determined by balancing current reproduction with expected future reproduction, and these are largely determined by size-specific patterns of growth and survival. However, because of the difficulty in following long-lived individuals throughout their lives, this theory has largely been tested using short-lived species (< 5 years). 2. Here, we tested this theory using the long-lived monocarpic perennial Campanula thyrsoides which can live up to 16 years. We used a novel approach that combined permanent plot and herb chronology data from a 3-year field study to parameterize and validate integral projection models (IPMs). 3. Similar to other monocarpic species, the rosette leaves of C. thyrsoides wither over winter and so size cannot be measured in the year of flowering. We therefore extended the existing IPM framework to incorporate an additional time delay that arises because flowering demography must be predicted from rosette size in the year before flowering. 4. We found that all main demographic functions (growth, survival probability, flowering probability and fecundity) were strongly size-dependent and there was a pronounced threshold size of flowering. There was good agreement between the predicted distribution of flowering ages obtained from the IPMs and that estimated in the field. Mostly, there was good agreement between the IPM predictions and the direct quantitative field measurements regarding the demographic parameters lambda, R-0 and T. We therefore conclude that the model captures the main demographic features of the field populations. 5. Elasticity analysis indicated that changes in the survival and growth function had the largest effect (c. 80%) on lambda and this was considerably larger than in short-lived monocarps. We found only weak selection pressure operating on the observed flowering strategy which was close to the predicted evolutionary stable strategy. 6. Synthesis. The extended IPM accurately described the demography of a long-lived monocarpic perennial using data collected over a relatively short period. We could show that the evolution of flowering strategies in short- and long-lived monocarps seem to follow the same general rules but with a longevity-related emphasis on survival over fecundity.

Eye movements discriminate fatigue due to chronotypical factors and time spent on task--a double dissociation

Systematic differences in circadian rhythmicity are thought to be a substantial factor determining inter-individual differences in fatigue and cognitive performance. The synchronicity effect (when time of testing coincides with the respective circadian peak period) seems to play an important role. Eye movements have been shown to be a reliable indicator of fatigue due to sleep deprivation or time spent on cognitive tasks. However, eye movements have not been used so far to investigate the circadian synchronicity effect and the resulting differences in fatigue. The aim of the present study was to assess how different oculomotor parameters in a free visual exploration task are influenced by: a) fatigue due to chronotypical factors (being a 'morning type' or an 'evening type'); b) fatigue due to the time spent on task. Eighteen healthy participants performed a free visual exploration task of naturalistic pictures while their eye movements were recorded. The task was performed twice, once at their optimal and once at their non-optimal time of the day. Moreover, participants rated their subjective fatigue. The non-optimal time of the day triggered a significant and stable increase in the mean visual fixation duration during the free visual exploration task for both chronotypes. The increase in the mean visual fixation duration correlated with the difference in subjectively perceived fatigue at optimal and non-optimal times of the day. Conversely, the mean saccadic speed significantly and progressively decreased throughout the duration of the task, but was not influenced by the optimal or non-optimal time of the day for both chronotypes. The results suggest that different oculomotor parameters are discriminative for fatigue due to different sources. A decrease in saccadic speed seems to reflect fatigue due to time spent on task, whereas an increase in mean fixation duration a lack of synchronicity between chronotype and time of the day.

Time domain passivity control for delayed teleoperation

La telepesencia combina diferentes modalidades sensoriales, incluyendo, entre otras, la visual y la del tacto, para producir una sensación de presencia remota en el operador. Un elemento clave en la implementación de sistemas de telepresencia para permitir una telemanipulación del entorno remoto es el retorno de fuerza. Durante una telemanipulación, la energía mecánica es transferida entre el operador humano y el entorno remoto. En general, la energía es una propiedad de los objetos físicos, fundamental en su mutual interacción. En esta interacción, la energía se puede transmitir entre los objetos, puede cambiar de forma pero no puede crearse ni destruirse. En esta tesis, se aplica este principio fundamental para derivar un nuevo método de control bilateral que permite el diseño de sistemas de teleoperación estables para cualquier arquitectura concebible. El razonamiento parte del hecho de que la energía mecánica insertada por el operador humano en el sistema debe transferirse hacia el entorno remoto y viceversa. Tal como se verá, el uso de la energía como variable de control permite un tratamiento más general del sistema que el control convencional basado en variables específicas del sistema. Mediante el concepto de Red de Potencia de Retardo Temporal (RPRT), el problema de definir los flujos de energía en un sistema de teleoperación es solucionado con independencia de la arquitectura de comunicación. Como se verá, los retardos temporales son la principal causa de generación de energía virtual. Este hecho se observa con retardos a partir de 1 milisegundo. Esta energía virtual es añadida al sistema de forma intrínseca y representa la causa principal de inestabilidad. Se demuestra que las RPRTs son transportadoras de la energía deseada intercambiada entre maestro y esclavo pero a la vez generadoras de energía virtual debido al retardo temporal. Una vez estas redes son identificadas, el método de Control de Pasividad en el Dominio Temporal para RPRTs se propone como mecanismo de control para asegurar la pasividad del sistema, y as__ la estabilidad. El método se basa en el simple hecho de que esta energía virtual debido al retardo debe transformarse en disipación. As__ el sistema se aproxima al sistema deseado, donde solo la energía insertada desde un extremo es transferida hacia el otro. El sistema resultante presenta dos cualidades: por un lado la estabilidad del sistema queda garantizada con independencia de la arquitectura del sistema y del canal de comunicación; por el otro, el rendimiento es maximizado en términos de fidelidad de transmisión energética. Los métodos propuestos se sustentan con sistemas experimentales con diferentes arquitecturas de control y retardos entre 2 y 900 ms. La tesis concluye con un experimento que incluye una comunicación espacial basada en el satélite geoestacionario ASTRA. ABSTRACT Telepresence combines different sensorial modalities, including vision and touch, to produce a feeling of being present in a remote location. The key element to successfully implement a telepresence system and thus to allow telemanipulation of a remote environment is force feedback. In a telemanipulation, mechanical energy must convey from the human operator to the manipulated object found in the remote environment. In general, energy is a property of all physical objects, fundamental to their mutual interactions in which the energy can be transferred among the objects and can change form but cannot be created or destroyed. In this thesis, we exploit this fundamental principle to derive a novel bilateral control mechanism that allows designing stable teleoperation systems with any conceivable communication architecture. The rationale starts from the fact that the mechanical energy injected by a human operator into the system must be conveyed to the remote environment and Vice Versa. As will be seen, setting energy as the control variable allows a more general treatment of the controlled system in contrast to the more conventional control of specific systems variables. Through the Time Delay Power Network (TDPN) concept, the issue of defining the energy flows involved in a teleoperation system is solved with independence of the communication architecture. In particular, communication time delays are found to be a source of virtual energy. This fact is observed with delays starting from 1 millisecond. Since this energy is added, the resulting teleoperation system can be non-passive and thus become unstable. The Time Delay Power Networks are found to be carriers of the desired exchanged energy but also generators of virtual energy due to the time delay. Once these networks are identified, the Time Domain Passivity Control approach for TDPNs is proposed as a control mechanism to ensure system passivity and therefore, system stability. The proposed method is based on the simple fact that this intrinsically added energy due to the communication must be transformed into dissipation. Then the system becomes closer to the ambitioned one, where only the energy injected from one end of the system is conveyed to the other one. The resulting system presents two benefits: On one hand, system stability is guaranteed through passivity independently from the chosen control architecture and communication channel; on the other, performance is maximized in terms of energy transfer faithfulness. The proposed methods are sustained with a set of experimental implementations using different control architectures and communication delays ranging from 2 to 900 milliseconds. An experiment that includes a communication Space link based on the geostationary satellite ASTRA concludes this thesis.

Diseño de algoritmos de guerra electrónica y radar para su implementación en sistemas de tiempo real

Esta tesis se centra en el estudio y desarrollo de algoritmos de guerra electrónica {electronic warfare, EW) y radar para su implementación en sistemas de tiempo real. La llegada de los sistemas de radio, radar y navegación al terreno militar llevó al desarrollo de tecnologías para combatirlos. Así, el objetivo de los sistemas de guerra electrónica es el control del espectro electomagnético. Una de la funciones de la guerra electrónica es la inteligencia de señales {signals intelligence, SIGINT), cuya labor es detectar, almacenar, analizar, clasificar y localizar la procedencia de todo tipo de señales presentes en el espectro. El subsistema de inteligencia de señales dedicado a las señales radar es la inteligencia electrónica {electronic intelligence, ELINT). Un sistema de tiempo real es aquel cuyo factor de mérito depende tanto del resultado proporcionado como del tiempo en que se da dicho resultado. Los sistemas radar y de guerra electrónica tienen que proporcionar información lo más rápido posible y de forma continua, por lo que pueden encuadrarse dentro de los sistemas de tiempo real. La introducción de restricciones de tiempo real implica un proceso de realimentación entre el diseño del algoritmo y su implementación en plataformas “hardware”. Las restricciones de tiempo real son dos: latencia y área de la implementación. En esta tesis, todos los algoritmos presentados se han implementado en plataformas del tipo field programmable gate array (FPGA), ya que presentan un buen compromiso entre velocidad, coste total, consumo y reconfigurabilidad. La primera parte de la tesis está centrada en el estudio de diferentes subsistemas de un equipo ELINT: detección de señales mediante un detector canalizado, extracción de los parámetros de pulsos radar, clasificación de modulaciones y localization pasiva. La transformada discreta de Fourier {discrete Fourier transform, DFT) es un detector y estimador de frecuencia quasi-óptimo para señales de banda estrecha en presencia de ruido blanco. El desarrollo de algoritmos eficientes para el cálculo de la DFT, conocidos como fast Fourier transform (FFT), han situado a la FFT como el algoritmo más utilizado para la detección de señales de banda estrecha con requisitos de tiempo real. Así, se ha diseñado e implementado un algoritmo de detección y análisis espectral para su implementación en tiempo real. Los parámetros más característicos de un pulso radar son su tiempo de llegada y anchura de pulso. Se ha diseñado e implementado un algoritmo capaz de extraer dichos parámetros. Este algoritmo se puede utilizar con varios propósitos: realizar un reconocimiento genérico del radar que transmite dicha señal, localizar la posición de dicho radar o bien puede utilizarse como la parte de preprocesado de un clasificador automático de modulaciones. La clasificación automática de modulaciones es extremadamente complicada en entornos no cooperativos. Un clasificador automático de modulaciones se divide en dos partes: preprocesado y el algoritmo de clasificación. Los algoritmos de clasificación basados en parámetros representativos calculan diferentes estadísticos de la señal de entrada y la clasifican procesando dichos estadísticos. Los algoritmos de localization pueden dividirse en dos tipos: triangulación y sistemas cuadráticos. En los algoritmos basados en triangulación, la posición se estima mediante la intersección de las rectas proporcionadas por la dirección de llegada de la señal. En cambio, en los sistemas cuadráticos, la posición se estima mediante la intersección de superficies con igual diferencia en el tiempo de llegada (time difference of arrival, TDOA) o diferencia en la frecuencia de llegada (frequency difference of arrival, FDOA). Aunque sólo se ha implementado la estimación del TDOA y FDOA mediante la diferencia de tiempos de llegada y diferencia de frecuencias, se presentan estudios exhaustivos sobre los diferentes algoritmos para la estimación del TDOA, FDOA y localización pasiva mediante TDOA-FDOA. La segunda parte de la tesis está dedicada al diseño e implementación filtros discretos de respuesta finita (finite impulse response, FIR) para dos aplicaciones radar: phased array de banda ancha mediante filtros retardadores (true-time delay, TTD) y la mejora del alcance de un radar sin modificar el “hardware” existente para que la solución sea de bajo coste. La operación de un phased array de banda ancha mediante desfasadores no es factible ya que el retardo temporal no puede aproximarse mediante un desfase. La solución adoptada e implementada consiste en sustituir los desfasadores por filtros digitales con retardo programable. El máximo alcance de un radar depende de la relación señal a ruido promedio en el receptor. La relación señal a ruido depende a su vez de la energía de señal transmitida, potencia multiplicado por la anchura de pulso. Cualquier cambio hardware que se realice conlleva un alto coste. La solución que se propone es utilizar una técnica de compresión de pulsos, consistente en introducir una modulación interna a la señal, desacoplando alcance y resolución. ABSTRACT This thesis is focused on the study and development of electronic warfare (EW) and radar algorithms for real-time implementation. The arrival of radar, radio and navigation systems to the military sphere led to the development of technologies to fight them. Therefore, the objective of EW systems is the control of the electromagnetic spectrum. Signals Intelligence (SIGINT) is one of the EW functions, whose mission is to detect, collect, analyze, classify and locate all kind of electromagnetic emissions. Electronic intelligence (ELINT) is the SIGINT subsystem that is devoted to radar signals. A real-time system is the one whose correctness depends not only on the provided result but also on the time in which this result is obtained. Radar and EW systems must provide information as fast as possible on a continuous basis and they can be defined as real-time systems. The introduction of real-time constraints implies a feedback process between the design of the algorithms and their hardware implementation. Moreover, a real-time constraint consists of two parameters: Latency and area of the implementation. All the algorithms in this thesis have been implemented on field programmable gate array (FPGAs) platforms, presenting a trade-off among performance, cost, power consumption and reconfigurability. The first part of the thesis is related to the study of different key subsystems of an ELINT equipment: Signal detection with channelized receivers, pulse parameter extraction, modulation classification for radar signals and passive location algorithms. The discrete Fourier transform (DFT) is a nearly optimal detector and frequency estimator for narrow-band signals buried in white noise. The introduction of fast algorithms to calculate the DFT, known as FFT, reduces the complexity and the processing time of the DFT computation. These properties have placed the FFT as one the most conventional methods for narrow-band signal detection for real-time applications. An algorithm for real-time spectral analysis for user-defined bandwidth, instantaneous dynamic range and resolution is presented. The most characteristic parameters of a pulsed signal are its time of arrival (TOA) and the pulse width (PW). The estimation of these basic parameters is a fundamental task in an ELINT equipment. A basic pulse parameter extractor (PPE) that is able to estimate all these parameters is designed and implemented. The PPE may be useful to perform a generic radar recognition process, perform an emitter location technique and can be used as the preprocessing part of an automatic modulation classifier (AMC). Modulation classification is a difficult task in a non-cooperative environment. An AMC consists of two parts: Signal preprocessing and the classification algorithm itself. Featurebased algorithms obtain different characteristics or features of the input signals. Once these features are extracted, the classification is carried out by processing these features. A feature based-AMC for pulsed radar signals with real-time requirements is studied, designed and implemented. Emitter passive location techniques can be divided into two classes: Triangulation systems, in which the emitter location is estimated with the intersection of the different lines of bearing created from the estimated directions of arrival, and quadratic position-fixing systems, in which the position is estimated through the intersection of iso-time difference of arrival (TDOA) or iso-frequency difference of arrival (FDOA) quadratic surfaces. Although TDOA and FDOA are only implemented with time of arrival and frequency differences, different algorithms for TDOA, FDOA and position estimation are studied and analyzed. The second part is dedicated to FIR filter design and implementation for two different radar applications: Wideband phased arrays with true-time delay (TTD) filters and the range improvement of an operative radar with no hardware changes to minimize costs. Wideband operation of phased arrays is unfeasible because time delays cannot be approximated by phase shifts. The presented solution is based on the substitution of the phase shifters by FIR discrete delay filters. The maximum range of a radar depends on the averaged signal to noise ratio (SNR) at the receiver. Among other factors, the SNR depends on the transmitted signal energy that is power times pulse width. Any possible hardware change implies high costs. The proposed solution lies in the use of a signal processing technique known as pulse compression, which consists of introducing an internal modulation within the pulse width, decoupling range and resolution.

A Modified Positive Velocity and Position Feedback scheme with delay compensation for improved nanopositioning performance

Acknowledgments This paper was sponsored by the Spanish FPU12/00984 Program (Ministerio de Educacion, Cultura y Deporte). It was also sponsored by the Spanish Government Research Program with the Project DPI2012-37062-CO2-01 (Ministerio de Economia y Competitividad) and by the European Social Fund.

Bathorhodopsin structure in the room-temperature rhodopsin photosequence: picosecond time-resolved coherent anti-Stokes Raman scattering.

Structural changes in the retinal chromophore during the formation of the bathorhodopsin intermediate (bathoRT) in the room-temperature rhodopsin (RhRT) photosequence (i.e., vision) are examined using picosecond time-resolved coherent anti-Stokes Raman scattering. Specifically, the retinal structure assignable to bathoRT following 8-ps excitation of RhRT is measured via vibrational Raman spectroscopy at a 200-ps time delay where the only intermediate present is bathoRT. Significant differences are observed between the C=C stretching frequencies of the retinal chromophore at low temperature where bathorhodopsin is stabilized and at room temperature where bathorhodopsin is a transient species in the RhRT photosequence. These vibrational data are discussed in terms of the formation of bathoRT, an important step in the energy storage/transduction mechanism of RhRT.