Revision of Singlet Quantum Yields in the Catalyzed Decomposition of Cyclic Peroxides

The chemiluminescence of cyclic peroxides activated by oxidizable fluorescent dyes is an example of chemically initiated electron exchange luminescence (CIEEL), which has been used also to explain the efficient bioluminescence of fireflies. Diphenoyl peroxide and dimethyl-1,2-dioxetanone were used as model compounds for the development of this CIEEL mechanism. However, the chemiexcitation efficiency of diphenoyl peroxide was found to be much lower than originally described. In this work, we redetermine the chemiexcitation quantum efficiency of dimethyl-1,2-dioxetanone, a more adequate model for firefly bioluminescence, and found a singlet quantum yield (Phi(s)) of 0.1%, a value at least 2 orders of magnitude lower than previously reported. Furthermore, we synthesized two other 1,2-dioxetanone derivatives and confirm the low chemiexcitation efficiency (Phi(s) < 0.1%) of the intermolecular CIEEL-activated decomposition of this class of cyclic. peroxides. These results are compared with other chemiluminescent reactions, supporting the general trend that intermolecular CIEEL systems are much less efficient in generating singlet excited states than analogous intramolecular processes (Phi(s) approximate to 50%), with the notable exception of the peroxyoxalate reaction (Phi(s) approximate to 60%).

Entropy Production in Nonequilibrium Systems at Stationary States

We present a stochastic approach to nonequilibrium thermodynamics based on the expression of the entropy production rate advanced by Schnakenberg for systems described by a master equation. From the microscopic Schnakenberg expression we get the macroscopic bilinear form for the entropy production rate in terms of fluxes and forces. This is performed by placing the system in contact with two reservoirs with distinct sets of thermodynamic fields and by assuming an appropriate form for the transition rate. The approach is applied to an interacting lattice gas model in contact with two heat and particle reservoirs. On a square lattice, a continuous symmetry breaking phase transition takes place such that at the nonequilibrium ordered phase a heat flow sets in even when the temperatures of the reservoirs are the same. The entropy production rate is found to have a singularity at the critical point of the linear-logarithm type.

Quantum motion in superposition of Aharonov-Bohm with some additional electromagnetic fields

The structure of additional electromagnetic fields to the Aharonov-Bohm field, for which the Schrodinger, Klein-Gordon, and Dirac equations can be solved exactly are described and the corresponding exact solutions are found. It is demonstrated that aside from the known cases (a constant and uniform magnetic field that is parallel to the Aharonov-Bohm solenoid, a static spherically symmetrical electric field, and the field of a magnetic monopole), there are broad classes of additional fields. Among these new additional fields we have physically interesting electric fields acting during a finite time or localized in a restricted region of space. There are additional time-dependent uniform and isotropic electric fields that allow exact solutions of the Schrodinger equation. In the relativistic case there are additional electric fields propagating along the Aharonov-Bohm solenoid with arbitrary electric pulse shape. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4714352]

Characterization and modeling of the barrier properties in nanostructured systems

The object of the present study is the process of gas transport in nano-sized materials, i.e. systems having structural elements of the order of nanometers. The aim of this work is to advance the understanding of the gas transport mechanism in such materials, for which traditional models are not often suitable, by providing a correct interpretation of the relationship between diffusive phenomena and structural features. This result would allow the development new materials with permeation properties tailored on the specific application, especially in packaging systems. The methods used to achieve this goal were a detailed experimental characterization and different simulation methods. The experimental campaign regarded the determination of oxygen permeability and diffusivity in different sets of organic-inorganic hybrid coatings prepared via sol-gel technique. The polymeric samples coated with these hybrid layers experienced a remarkable enhancement of the barrier properties, which was explained by the strong interconnection at the nano-scale between the organic moiety and silica domains. An analogous characterization was performed on microfibrillated cellulose films, which presented remarkable barrier effect toward oxygen when it is dry, while in the presence of water the performance significantly drops. The very low value of water diffusivity at low activities is also an interesting characteristic which deals with its structural properties. Two different approaches of simulation were then considered: the diffusion of oxygen through polymer-layered silicates was modeled on a continuum scale with a CFD software, while the properties of n-alkanthiolate self assembled monolayers on gold were analyzed from a molecular point of view by means of a molecular dynamics algorithm. Modeling transport properties in layered nanocomposites, resulting from the ordered dispersion of impermeable flakes in a 2-D matrix, allowed the calculation of the enhancement of barrier effect in relation with platelets structural parameters leading to derive a new expression. On this basis, randomly distributed systems were simulated and the results were analyzed to evaluate the different contributions to the overall effect. The study of more realistic three-dimensional geometries revealed a prefect correspondence with the 2-D approximation. A completely different approach was applied to simulate the effect of temperature on the oxygen transport through self assembled monolayers; the structural information obtained from equilibrium MD simulations showed that raising the temperature, makes the monolayer less ordered and consequently less crystalline. This disorder produces a decrease in the barrier free energy and it lowers the overall resistance to oxygen diffusion, making the monolayer more permeable to small molecules.

Modeling of complex chemical reactions and macromolecular orientation phenomena in confined geometries

The cooperative motion algorithm was applied on the molecular simulation of complex chemical reactions and macromolecular orientation phenomena in confined geometries. First, we investigated the case of equilibrium step-growth polymerization in lamellae, pores and droplets. In such systems, confinement was quantified as the area/volume ratio. Results showed that, as confinement increases, polymerization becomes slower and the average molecular weight (MW) at equilibrium decreases. This is caused by the sterical hindrance imposed by the walls since chain growth reactions in their close vicinity have less realization possibilities. For reactions inside droplets at surfaces, contact angles usually increased after polymerization to compensate conformation restrictions imposed by confinement upon growing chains. In a second investigation, we considered monodisperse and chemically inert chains and focused on the effect of confinement on chain orientation. Simulations of thin polymer films showed that chains are preferably oriented parallel to the surface. Orientation increases as MW increases or as film thickness d decreases, in qualitative agreement with experiments with low MW polystyrene. It is demonstrated that the orientation of simulated chains results from a size effect, being a function of the ratio between chain end-to-end distance and d. This study was complemented by experiments with thin films of pi-conjugated polymers like MEH-PPV. Anisotropic refractive index measurements were used to analyze chain orientation. With increasing MW, orientation is enhanced. However, for MEH-PPV, orientation does not depend on d even at thicknesses much larger than the chain contour length. This contradiction with simulations was discussed by considering additional causes for orientation, for instance the appearance of nematic-like ordering in polymer films. In another investigation, we simulated droplet evaporation at soluble surfaces and reproduced the formation of wells surrounded by ringlike deposits at the surface, as observed experimentally. In our simulations, swollen substrate particles migrate to the border of the droplet to minimize the contact between solvent and vacuum, which costs the most energy. Deposit formation in the beginning of evaporation results in pinning of the droplet. When polymer chains at the substrate surface have strong uniaxial orientation, the resulting pattern is no longer similar to a ring but to a pair of half-moons. In a final stage, as an extension for the model developed for polymerization in nanoreactors, we studied the effect of geometrical confinement on a hypothetical oscillating reaction following the mechanism of the so called periodically forced Brusselator. It was shown that a reaction which is chaotic in the bulk may be driven to periodicity by confinement and vice-versa, opening new perspectives for chaos control.

Quantum dot-dye hybrid systems for energy transfer applications

In this thesis, we focus on the preparation of energy transfer-based quantum dot (QD)-dye hybrid systems. Two kinds of QD-dye hybrid systems have been successfully synthesized: QD-silica-dye and QD-dye hybrid systems.rn rnIn the QD-silica-dye hybrid system, multishell CdSe/CdS/ZnS QDs were adsorbed onto monodisperse Stöber silica particles with an outer silica shell of thickness 2 - 24 nm containing organic dye molecules (Texas Red). The thickness of this dye layer has a strong effect on the total sensitized acceptor emission, which is explained by the increase in the number of dye molecules homogeneously distributed within the silica shell, in combination with an enhanced surface adsorption of QDs with increasing dye amount. Our conclusions were underlined by comparison of the experimental results with Monte-Carlo simulations, and by control experiments confirming attractive interactions between QDs and Texas Red freely dissolved in solution. rnrnNew QD-dye hybrid system consisting of multishell QDs and organic perylene dyes have been synthesized. We developed a versatile approach to assemble extraordinarily stable QD-dye hybrids, which uses dicarboxylate anchors to bind rylene dyes to QD. This system yields a good basis to study the energy transfer between QD and dye because of its simple and compact design: there is no third kind of molecule linking QD and dye; no spacer; and the affinity of the functional group to the QD surface is strong. The FRET signal was measured for these complexes as a function of both dye to QD ratio and center-to-center distance between QD and dye by controlling number of covered ZnS layers. Data showed that fluorescence resonance energy transfer (FRET) was the dominant mechanism of the energy transfer in our QD-dye hybrid system. FRET efficiency can be controlled by not only adjusting the number of dyes on the QD surface or the QD to dye distance, but also properly choosing different dye and QD components. Due to the strong stability, our QD-dye complexes can also be easily transferred into water. Our approach can apply to not only dye molecules but also other organic molecules. As an example, the QDs have been complexed with calixarene molecules and the QD-calixarene complexes also have potential for QD-based energy transfer study. rn

Partial Discharge Phenomena in Converter and Traction Transformers: Identification and Reliability

After the development of power electronics converters, the number of transformers subjected to non-sinusoidal stresses (including DC) has increased in applications such as HVDC links and traction (electric train power cars). The effects of non-sinusoidal voltages on transformer insulation have been investigated by many researchers, but still now, there are some issues that must be understood. Some of those issues are tackled in this Thesis, studying PD phenomena behavior in Kraft paper, pressboard and mineral oil at different voltage conditions like AC, DC, AC+DC, notched AC and square waveforms. From the point of view of converter transformers, it was found that the combined effect of AC and DC voltages produces higher stresses in the pressboard that those that are present under pure DC voltages. The electrical conductivity of the dielectric systems in DC and AC+DC conditions has demonstrated to be a critical parameter, so, its measurement and analysis was also taken into account during all the experiments. Regarding notched voltages, the RMS reduction caused by notches (depending on firing and overlap angles) seems to increase the PDIV. However, the experimental results show that once PD activity has incepted, the notches increase PD repetition rate and magnitude, producing a higher degradation rate of paper. On the other hand, the reduction of mineral oil stocks, their relatively low flash point as well as environmental issues, are factors that are pushing towards the use of esters as transformer insulating fluids. This PhD Thesis also covers the study of two different esters with the scope to validate their use in traction transformers. Mineral oil was used as benchmark. The complete set of dielectric tests performed in the three fluids, show that esters behave better than mineral oil in practically all the investigated conditions, so, their application in traction transformers is possible and encouraged.

Diffusion in heterogeneous systems studied by laser scanning confocal microscopy and fluorescence correlation spectroscopy

Understanding and controlling the mechanism of the diffusion of small molecules, macromolecules and nanoparticles in heterogeneous environments is of paramount fundamental and technological importance. The aim of the thesis is to show, how by studying the tracer diffusion in complex systems, one can obtain information about the tracer itself, and the system where the tracer is diffusing. rnIn the first part of my thesis I will introduce the Fluorescence Correlation Spectroscopy (FCS) which is a powerful tool to investigate the diffusion of fluorescent species in various environments. By using the main advantage of FCS namely the very small probing volume (<1µm3) I was able to track the kinetics of phase separation in polymer blends at late stages by looking on the molecular tracer diffusion in individual domains of the heterogeneous structure of the blend. The phase separation process at intermediate stages was monitored with laser scanning confocal microscopy (LSCM) in real time providing images of droplet coalescence and growth. rnIn a further project described in my thesis I will show that even when the length scale of the heterogeneities becomes smaller than the FCS probing volume one can still obtain important microscopic information by studying small tracer diffusion. To do so, I will introduce a system of star shaped polymer solutions and will demonstrate that the mobility of small molecular tracers on microscopic level is nearly not affected by the transition of the polymer system to a “glassy” macroscopic state. rnIn the last part of the thesis I will introduce and describe a new stimuli responsive system which I have developed, that combines two levels of nanoporosity. The system is based on poly-N-isopropylacrylamide (PNIPAM) and silica inverse opals (iOpals), and allows controlling the diffusion of tracer molecules. rn

High-mass Drell-Yan cross-section and search for new phenomena in multi-electron/positron final states with the ATLAS detector

The Standard Model of particle physics is a very successful theory which describes nearly all known processes of particle physics very precisely. Nevertheless, there are several observations which cannot be explained within the existing theory. In this thesis, two analyses with high energy electrons and positrons using data of the ATLAS detector are presented. One, probing the Standard Model of particle physics and another searching for phenomena beyond the Standard Model.rnThe production of an electron-positron pair via the Drell-Yan process leads to a very clean signature in the detector with low background contributions. This allows for a very precise measurement of the cross-section and can be used as a precision test of perturbative quantum chromodynamics (pQCD) where this process has been calculated at next-to-next-to-leading order (NNLO). The invariant mass spectrum mee is sensitive to parton distribution functions (PFDs), in particular to the poorly known distribution of antiquarks at large momentum fraction (Bjoerken x). The measurementrnof the high-mass Drell-Yan cross-section in proton-proton collisions at a center-of-mass energy of sqrt(s) = 7 TeV is performed on a dataset collected with the ATLAS detector, corresponding to an integrated luminosity of 4.7 fb-1. The differential cross-section of pp -> Z/gamma + X -> e+e- + X is measured as a function of the invariant mass in the range 116 GeV < mee < 1500 GeV. The background is estimated using a data driven method and Monte Carlo simulations. The final cross-section is corrected for detector effects and different levels of final state radiation corrections. A comparison isrnmade to various event generators and to predictions of pQCD calculations at NNLO. A good agreement within the uncertainties between measured cross-sections and Standard Model predictions is observed.rnExamples of observed phenomena which can not be explained by the Standard Model are the amount of dark matter in the universe and neutrino oscillations. To explain these phenomena several extensions of the Standard Model are proposed, some of them leading to new processes with a high multiplicity of electrons and/or positrons in the final state. A model independent search in multi-object final states, with objects defined as electrons and positrons, is performed to search for these phenomenas. Therndataset collected at a center-of-mass energy of sqrt(s) = 8 TeV, corresponding to an integrated luminosity of 20.3 fb-1 is used. The events are separated in different categories using the object multiplicity. The data-driven background method, already used for the cross-section measurement was developed further for up to five objects to get an estimation of the number of events including fake contributions. Within the uncertainties the comparison between data and Standard Model predictions shows no significant deviations.

Ultracold Quantum Gases and Lattice Systems: Quantum Simulation of Lattice Gauge Theories

Abelian and non-Abelian gauge theories are of central importance in many areas of physics. In condensed matter physics, AbelianU(1) lattice gauge theories arise in the description of certain quantum spin liquids. In quantum information theory, Kitaev’s toric code is a Z(2) lattice gauge theory. In particle physics, Quantum Chromodynamics (QCD), the non-Abelian SU(3) gauge theory of the strong interactions between quarks and gluons, is nonperturbatively regularized on a lattice. Quantum link models extend the concept of lattice gauge theories beyond the Wilson formulation, and are well suited for both digital and analog quantum simulation using ultracold atomic gases in optical lattices. Since quantum simulators do not suffer from the notorious sign problem, they open the door to studies of the real-time evolution of strongly coupled quantum systems, which are impossible with classical simulation methods. A plethora of interesting lattice gauge theories suggests itself for quantum simulation, which should allow us to address very challenging problems, ranging from confinement and deconfinement, or chiral symmetry breaking and its restoration at finite baryon density, to color superconductivity and the real-time evolution of heavy-ion collisions, first in simpler model gauge theories and ultimately in QCD.

Search for new phenomena in photon+jet events collected in proton–proton collisions at √s = 8 TeV with the ATLAS detector

This Letter describes a model-independent search for the production of new resonances in photon + jet events using 20 inverse fb of proton--proton LHC data recorded with the ATLAS detector at a centre-of-mass energy of s√ = 8 TeV. The photon + jet mass distribution is compared to a background model fit from data; no significant deviation from the background-only hypothesis is found. Limits are set at 95% credibility level on generic Gaussian-shaped signals and two benchmark phenomena beyond the Standard Model: non-thermal quantum black holes and excited quarks. Non-thermal quantum black holes are excluded below masses of 4.6 TeV and excited quarks are excluded below masses of 3.5 TeV.

ATLAS search for new phenomena in dijet mass and angular distributions using pp collisions at sqrts=7 TeV

Mass and angular distributions of dijets produced in LHC proton-proton collisions at a centre-of-mass energy root s = 7TeV have been studied with the ATLAS detector using the full 2011 data set with an integrated luminosity of 4.8 fb(-1). Dijet masses up to similar to 4.0TeV have been probed. No resonance-like features have been observed in the dijet mass spectrum, and all angular distributions are consistent with the predictions of QCD. Exclusion limits on six hypotheses of new phenomena have been set at 95% CL in terms of mass or energy scale, as appropriate. These hypotheses include excited quarks below 2.83 TeV, colour octet scalars below 1.86TeV, heavy W bosons below 1.68 TeV, string resonances below 3.61 TeV, quantum black holes with six extra space-time dimensions for quantum gravity scales below 4.11 TeV, and quark contact interactions below a compositeness scale of 7.6 TeV in a destructive interference scenario.

Quantum communications in optical networks

La posibilidad de utilizar sistemas cuánticos para procesar y transmitir información ha impulsado la aparición de tecnologías de información cuántica, p. ej., distribución cuántica de claves. Aunque prometedoras, su uso fuera del laboratorio es actualmente demasiado costoso y complicado. En este trabajo mostramos como utilizarlas en redes ópticas de telecomunicaciones. Al utilizar una infraestructura existente y pervasiva, y compartirla con otras señales, tanto clásicas como cuánticas, el coste se reduce drásticamente y llega a un mayor público. Comenzamos integrando señales cuánticas en los tipos más utilizados de redes ópticas pasivas, por su simplicidad y alcance a usuarios finales. Luego ampliamos este estudio, proponiendo un diseño de red óptica metropolitana basado en la división en longitud de onda para multiplexar y direccionar las señales. Verificamos su funcionamiento con un prototipo. Posteriormente, estudiamos la distribución de pares de fotones entrelazados entre los usuarios de dicha red con el objetivo de abarcar más tecnologías. Para ampliar la capacidad de usuarios, rediseñamos la red troncal, cambiando tanto la topología como la tecnología utilizada en los nodos. El resultado es una red metropolitana cuántica que escala a cualquier cantidad de usuarios, a costa de una mayor complejidad y coste. Finalmente, tratamos el problema de la limitación en distancia. La solución propuesta está basada en codificación de red y permite, mediante el uso de varios caminos y nodos, modular la cantidad de información que tiene cada nodo, y así, la confianza depositada en él. ABSTRACT The potential use of quantum systems to process and transmit information has impulsed the emergence of quantum information technologies such as quantum key distribution. Despite looking promising, their use out of the laboratory is limited since they are a very delicate technology due to the need of working at the single quantum level. In this work we show how to use them in optical telecommunication networks. Using an existing infrastructure and sharing it with other signals, both quantum and conventional, reduces dramatically the cost and allows to reach a large group of users. In this work, we will first integrate quantum signals in the most common passive optical networks, for their simplicity and reach to final users. Then, we extend this study by proposing a quantum metropolitan optical network based on wavelength-division multiplexing and wavelengthaddressing, verifying its operation mode in a testbed. Later, we study the distribution of entangled photon-pairs between the users of the network with the objective of covering as much different technologies as possible. We further explore other network architectures, changing the topology and the technology used at the nodes. The resulting network scales better at the cost of a more complex and expensive infrastructure. Finally, we tackle the distance limitation problem of quantum communications. The solution offered is based on networkcoding and allows, using multiple paths and nodes, to modulate the information leaked to each node, and thus, the degree of trust placed in them.

Human Factor in Resilience Systems

This paper shows the importance of a holistic comprehension of the Earth as a living planet, where man inhabits and is exposed to environmental incidences of different nature. The aim of the paper here summarized is a reflection on all these concepts and scientific considerations related to the important role of men in the handling of natural hazards. Our Planet is an unstable and dynamical system highly sensitive to initial conditions, as proposed by Chaos theory (González-Miranda 2004); it is a complex organic whole, which responds to minimal variations which can affect several natural phenomena such as plate tectonics, solar flares, fluid turbulences, landscape formation, forest fires, growth and migration of populations and biological evolution. This is known as the “butterfly effect” (Lorenz 1972), which means that a small change of the system causes a chain of events leading to large-scale unpredictable consequences. The aim of this work is dwelling on the importance of the knowledge of these natural and catastrophic geological, biological and human systems so much sensible to equilibrium conditions, to prevent, avoid and mend their effects, and to face them in a resilient way