Discrimination d'événements par analyse des signaux enregistrés par le projet PICASSO

La matière sombre est un mystère dans le domaine de l’astrophysique depuis déjà plusieurs années. De nombreuses observations montrent que jusqu’à 85 % de la masse gravitationnelle totale de l’univers serait composée de cette matière de nature inconnue. Une théorie expliquant cette masse manquante considérerait les WIMPs (Weakly Interacting Massive Particles), particules stables, non chargées, prédites par des extensions du modèle standard, comme candidats. Le projet PICASSO (Projet d’Identification des CAndidats Supersymétriques à la matière Sombre) est une expérience qui tente de détecter directement le WIMP. Le projet utilise des détecteurs à gouttelettes de fréon (C4F10) surchauffées. La collision entre un WIMP et le noyau de fluor crée un recul nucléaire qui cause à son tour une transition de phase de la gouttelette liquide à une bulle gazeuse. Le bruit de ce phénomène est alors capté par des senseurs piézoélectriques montés sur les parois des détecteurs. Le WIMP n’est cependant pas la seule particule pouvant causer une telle transition de phase. D’autres particules environnantes peuvent former des bulles, telles les particules alpha où même des rayons gamma . Le système d’acquisition de données (DAQ) est aussi en proie à du bruit électronique qui peut être enregistré, ainsi que sensible à du bruit acoustique extérieur au détecteur. Finalement, des fractures dans le polymère qui tient les gouttelettes en place peut également causer des transitions de phase spontanées. Il faut donc minimiser l’impact de tous ces différents bruit de fond. La pureté du matériel utilisé dans la fabrication des détecteurs devient alors très importante. On fait aussi appel à des méthodes qui impliquent l’utilisation de variables de discrimination développées dans le but d’améliorer les limites d’exclusion de détection du WIMP.

Meta-heuristic Solution Methods for Rich Vehicle Routing Problems

Le problème de tournées de véhicules (VRP), introduit par Dantzig and Ramser en 1959, est devenu l'un des problèmes les plus étudiés en recherche opérationnelle, et ce, en raison de son intérêt méthodologique et de ses retombées pratiques dans de nombreux domaines tels que le transport, la logistique, les télécommunications et la production. L'objectif général du VRP est d'optimiser l'utilisation des ressources de transport afin de répondre aux besoins des clients tout en respectant les contraintes découlant des exigences du contexte d’application. Les applications réelles du VRP doivent tenir compte d’une grande variété de contraintes et plus ces contraintes sont nombreuse, plus le problème est difficile à résoudre. Les VRPs qui tiennent compte de l’ensemble de ces contraintes rencontrées en pratique et qui se rapprochent des applications réelles forment la classe des problèmes ‘riches’ de tournées de véhicules. Résoudre ces problèmes de manière efficiente pose des défis considérables pour la communauté de chercheurs qui se penchent sur les VRPs. Cette thèse, composée de deux parties, explore certaines extensions du VRP vers ces problèmes. La première partie de cette thèse porte sur le VRP périodique avec des contraintes de fenêtres de temps (PVRPTW). Celui-ci est une extension du VRP classique avec fenêtres de temps (VRPTW) puisqu’il considère un horizon de planification de plusieurs jours pendant lesquels les clients n'ont généralement pas besoin d’être desservi à tous les jours, mais plutôt peuvent être visités selon un certain nombre de combinaisons possibles de jours de livraison. Cette généralisation étend l'éventail d'applications de ce problème à diverses activités de distributions commerciales, telle la collecte des déchets, le balayage des rues, la distribution de produits alimentaires, la livraison du courrier, etc. La principale contribution scientifique de la première partie de cette thèse est le développement d'une méta-heuristique hybride dans la quelle un ensemble de procédures de recherche locales et de méta-heuristiques basées sur les principes de voisinages coopèrent avec un algorithme génétique afin d’améliorer la qualité des solutions et de promouvoir la diversité de la population. Les résultats obtenus montrent que la méthode proposée est très performante et donne de nouvelles meilleures solutions pour certains grands exemplaires du problème. La deuxième partie de cette étude a pour but de présenter, modéliser et résoudre deux problèmes riches de tournées de véhicules, qui sont des extensions du VRPTW en ce sens qu'ils incluent des demandes dépendantes du temps de ramassage et de livraison avec des restrictions au niveau de la synchronization temporelle. Ces problèmes sont connus respectivement sous le nom de Time-dependent Multi-zone Multi-Trip Vehicle Routing Problem with Time Windows (TMZT-VRPTW) et de Multi-zone Mult-Trip Pickup and Delivery Problem with Time Windows and Synchronization (MZT-PDTWS). Ces deux problèmes proviennent de la planification des opérations de systèmes logistiques urbains à deux niveaux. La difficulté de ces problèmes réside dans la manipulation de deux ensembles entrelacés de décisions: la composante des tournées de véhicules qui vise à déterminer les séquences de clients visités par chaque véhicule, et la composante de planification qui vise à faciliter l'arrivée des véhicules selon des restrictions au niveau de la synchronisation temporelle. Auparavant, ces questions ont été abordées séparément. La combinaison de ces types de décisions dans une seule formulation mathématique et dans une même méthode de résolution devrait donc donner de meilleurs résultats que de considérer ces décisions séparément. Dans cette étude, nous proposons des solutions heuristiques qui tiennent compte de ces deux types de décisions simultanément, et ce, d'une manière complète et efficace. Les résultats de tests expérimentaux confirment la performance de la méthode proposée lorsqu’on la compare aux autres méthodes présentées dans la littérature. En effet, la méthode développée propose des solutions nécessitant moins de véhicules et engendrant de moindres frais de déplacement pour effectuer efficacement la même quantité de travail. Dans le contexte des systèmes logistiques urbains, nos résultats impliquent une réduction de la présence de véhicules dans les rues de la ville et, par conséquent, de leur impact négatif sur la congestion et sur l’environnement.

Analyse et modélisation de la réponse des détecteurs du projet PICASSO pour la recherche de la matière sombre

Les mesures cosmologiques les plus récentes ont montré la présence d’un type de matière exotique constituant 85% de la masse de l’univers. Ce type de matière non baryonique serait formé de particules neutres, non relativistes, massives et interagissant faiblement avec la matière baryonique. L’ensemble des candidats est regroupé sous le nom générique WIMP (Weakly Interactive Massive Particles). L’expérience PICASSO (Projet d’Identification des CAndidats Supersymétriques de la matière SOmbre) est une expérience utilisant des détecteurs à seuil d’énergie contenant des gouttelettes surchauffées constituées de C4F10. Cette technique de détection est basée sur le principe de la chambre à bulles. Le projet PICASSO a pour but de détecter directement une particule de matière sombre. Le principe de détection est qu’une particule de matière sombre interagissant avec le liquide actif engendre un recul nucléaire du 19F. L’énergie de recul serait suffisante pour engendrer une transition de phase accompagnée d’un signal acoustique enregistrée par des senseurs piézoélectriques. Dans le cadre de ce mémoire, une simulation du taux de comptage de l’étalonnage des détecteurs PICASSO soumis à des neutrons monoénergétiques a été effectuée en utilisant la théorie de Seitz qui décrit les critères pour qu’une transition de phase ait lieu pour un liquide en état de surchauffe. De plus, un modèle calculant le signal acoustique émis lors d’une transition de phase engendré par différents types de radiations a été créé permettant de caractériser la discrimination entre différents bruits de fond en fonction de l’énergie de seuil. Finalement, un outil d’analyse, la localisation des évènements, a été utilisé pour appliquer des coupures sur le volume dans le but d’améliorer la discrimination alpha-neutron.

Multipole modes and spin features in the Raman spectrum of nanoscopic quantum rings

We present a systematic study of ground state and spectroscopic properties of many-electron nanoscopic quantum rings. Addition energies at zero magnetic field (B) and electrochemical potentials as a function of B are given for a ring hosting up to 24 electrons. We find discontinuities in the excitation energies of multipole spin and charge density modes, and a coupling between the charge and spin density responses that allow to identify the formation of ferromagnetic ground states in narrow magnetic field regions. These effects can be observed in Raman experiments, and are related to the fractional Aharonov-Bohm oscillations of the energy and of the persistent current in the ring

Optical response of two-dimensional few-electron concentric double quantum rings: A local-spin-density-functional theory study

We have investigated the dipole charge- and spin-density response of few-electron two-dimensional concentric nanorings as a function of the intensity of a erpendicularly applied magnetic field. We show that the dipole response displays signatures associated with the localization of electron states in the inner and outer ring favored by the perpendicularly applied magnetic field. Electron localization produces a more fragmented spectrum due to the appearance of additional edge excitations in the inner and outer ring.

Quantum decay of metastable states in small magnetic particles

We present an imaginary-time path-integral study of the problem of quantum decay of a metastable state of a uniaxial magnetic particle placed in the magnetic field at an arbitrary angle. Our findings agree with earlier results of Zaslavskii obtained by mapping the spin Hamiltonian onto a particle Hamiltonian. In the limit of low barrier, weak dependence of the decay rate on the angle is found, except for the field which is almost normal to the anisotropy axis, where the rate is sharply peaked, and for the field approaching the parallel orientation, where the rate rapidly goes to zero. This distinct angular dependence, together with the dependence of the rate on the field strength, provides an independent test for macroscopic spin tunneling.

Resonant spin tunneling in small antiferromagnetic particles

The paper reports a detailed experimental study on magnetic relaxation of natural horse-spleen ferritin. ac susceptibility measurements performed on three samples of different concentration show that dipole-dipole interactions between uncompensated moments play no significant role. Furthermore, the distribution of relaxation times in these samples has been obtained from a scaling of experimental X" data, obtained at different frequencies. The average uncompensated magnetic moment per protein is compatible with a disordered arrangement of atomic spins throughout the core, rather than with surface disorder. The observed field dependence of the blocking temperature suggests that magnetic relaxation is faster at zero field than at intermediate field values. This is confirmed by the fact that the magnetic viscosity peaks at zero field, too. Using the distribution of relaxation times obtained independently, we show that these results cannot be explained in terms of classical relaxation theory. The most plausible explanation of these results is the existence, near zero field, of resonant magnetic tunneling between magnetic states of opposite orientation, which are thermally populated.

Evidence of aging in spin glass mean-field models

We study numerically the out-of-equilibrium dynamics of the hypercubic cell spin glass in high dimensionalities. We obtain evidence of aging effects qualitatively similar both to experiments and to simulations of low-dimensional models. This suggests that the Sherrington-Kirkpatrick model as well as other mean-field finite connectivity lattices can be used to study these effects analytically.

Erasing the glassy state in magnetic fine particles

BaFe10.4Co0.8Ti0.8O19 magnetic fine particles exhibit most of the features attributed to glassy behavior, e.g., irreversibility in the hysteresis loops and in the zero-field-cooling and field-cooling curves extends up to very high fields, and aging and magnetic training phenomena occur. However, the multivalley energy structure of the glassy state can be strongly modified by a field-cooling process at a moderate field. Slow relaxation experiments demonstrate that the intrinsic energy barriers of the individual particles dominate the behavior of the system at high cooling fields, while the energy states corresponding to collective glassy behavior play the dominant role at low cooling fields.

Adsorption energy and spin state of first-row transition metals adsorbed on MgO(100)

Slab and cluster model spin-polarized calculations have been carried out to study various properties of isolated first-row transition metal atoms adsorbed on the anionic sites of the regular MgO(100) surface. The calculated adsorption energies follow the trend of the metal cohesive energies, indicating that the changes in the metal-support and metal-metal interactions along the series are dominated by atomic properties. In all cases, except for Ni at the generalized gradient approximation level, the number of unpaired electron is maintained as in the isolated metal atom. The energy required to change the atomic state from high to low spin has been computed using the PW91 and B3LYP density-functional-theory-based methods. PW91 fails to predict the proper ground state of V and Ni, but the results for the isolated and adsorbed atom are consistent within the method. B3LYP properly predicts the ground state of all first-row transition atom the high- to low-spin transition considered is comparable to experiment. In all cases, the interaction with the surface results in a reduced high- to low-spin transition energy.

Ferromagnetic instabilities in neutron matter at finite temperature with the Skyrme interaction

The properties of spin-polarized neutron matter are studied at both zero and finite temperature using Skyrme-type interactions. It is shown that the critical density at which ferromagnetism takes place decreases with temperature. This unexpected behavior is associated to an anomalous behavior of the entropy that becomes larger for the polarized phase than for the unpolarized one above a certain critical density. This fact is a consequence of the dependence of the entropy on the effective mass of the neutrons with different third spin component. A new constraint on the parameters of the effective Skyrme force is derived if this behavior is to be avoided.

Pionic branches in neutron matter and the problem of pion condensation

The pion spectrum for charged and neutral pions is investigated in pure neutron matter, by letting the pions interact with a neutron Fermi sea in a self-consistent scheme that renormalizes simultaneously the mesons, considered the source of the interaction, and the nucleons. The possibility of obtaining different kinds of pion condensates is investigated with the result that they cannot be reached even for values of the spin-spin correlation parameter, g', far below the range commonly accepted.

Synthesis, Characterization and Applications of Modified TiO2 Systems

This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.

New studies on the versatile roles of Polyaniline and its composites in polymer based optoelectronic and energy storage devices

From the early stages of the twentieth century, polyaniline (PANI), a well-known and extensively studied conducting polymer has captured the attention of scientific community owing to its interesting electrical and optical properties. Starting from its structural properties, to the currently pursued optical, electrical and electrochemical properties, extensive investigations on pure PANI and its composites are still much relevant to explore its potentialities to the maximum extent. The synthesis of highly crystalline PANI films with ordered structure and high electrical conductivity has not been pursued in depth yet. Recently, nanostructured PANI and the nanocomposites of PANI have attracted a great deal of research attention owing to the possibilities of applications in optical switching devices, optoelectronics and energy storage devices. The work presented in the thesis is centered around the realization of highly conducting and structurally ordered PANI and its composites for applications mainly in the areas of nonlinear optics and electrochemical energy storage. Out of the vast variety of application fields of PANI, these two areas are specifically selected for the present studies, because of the following observations. The non-linear optical properties and the energy storing properties of PANI depend quite sensitively on the extent of conjugation of the polymer structure, the type and concentration of the dopants added and the type and size of the nano particles selected for making the nanocomposites. The first phase of the work is devoted to the synthesis of highly ordered and conducting films of PANI doped with various dopants and the structural, morphological and electrical characterization followed by the synthesis of metal nanoparticles incorporated PANI samples and the detailed optical characterization in the linear and nonlinear regimes. The second phase of the work comprises the investigations on the prospects of PANI in realizing polymer based rechargeable lithium ion cells with the inherent structural flexibility of polymer systems and environmental safety and stability. Secondary battery systems have become an inevitable part of daily life. They can be found in most of the portable electronic gadgets and recently they have started powering automobiles, although the power generated is low. The efficient storage of electrical energy generated from solar cells is achieved by using suitable secondary battery systems. The development of rechargeable battery systems having excellent charge storage capacity, cyclability, environmental friendliness and flexibility has yet to be realized in practice. Rechargeable Li-ion cells employing cathode active materials like LiCoO2, LiMn2O4, LiFePO4 have got remarkable charge storage capacity with least charge leakage when not in use. However, material toxicity, chance of cell explosion and lack of effective cell recycling mechanism pose significant risk factors which are to be addressed seriously. These cells also lack flexibility in their design due to the structural characteristics of the electrode materials. Global research is directed towards identifying new class of electrode materials with less risk factors and better structural stability and flexibility. Polymer based electrode materials with inherent flexibility, stability and eco-friendliness can be a suitable choice. One of the prime drawbacks of polymer based cathode materials is the low electronic conductivity. Hence the real task with this class of materials is to get better electronic conductivity with good electrical storage capability. Electronic conductivity can be enhanced by using proper dopants. In the designing of rechargeable Li-ion cells with polymer based cathode active materials, the key issue is to identify the optimum lithiation of the polymer cathode which can ensure the highest electronic conductivity and specific charge capacity possible The development of conducting polymer based rechargeable Li-ion cells with high specific capacity and excellent cycling characteristics is a highly competitive area among research and development groups, worldwide. Polymer based rechargeable batteries are specifically attractive due to the environmentally benign nature and the possible constructional flexibility they offer. Among polymers having electrical transport properties suitable for rechargeable battery applications, polyaniline is the most favoured one due to its tunable electrical conducting properties and the availability of cost effective precursor materials for its synthesis. The performance of a battery depends significantly on the characteristics of its integral parts, the cathode, anode and the electrolyte, which in turn depend on the materials used. Many research groups are involved in developing new electrode and electrolyte materials to enhance the overall performance efficiency of the battery. Currently explored electrolytes for Li ion battery applications are in liquid or gel form, which makes well-defined sealing essential. The use of solid electrolytes eliminates the need for containment of liquid electrolytes, which will certainly simplify the cell design and improve the safety and durability. The other advantages of polymer electrolytes include dimensional stability, safety and the ability to prevent lithium dendrite formation. One of the ultimate aims of the present work is to realize all solid state, flexible and environment friendly Li-ion cells with high specific capacity and excellent cycling stability. Part of the present work is hence focused on identifying good polymer based solid electrolytes essential for realizing all solid state polymer based Li ion cells.The present work is an attempt to study the versatile roles of polyaniline in two different fields of technological applications like nonlinear optics and energy storage. Conducting form of doped PANI films with good extent of crystallinity have been realized using a level surface assisted casting method in addition to the generally employed technique of spin coating. Metal nanoparticles embedded PANI offers a rich source for nonlinear optical studies and hence gold and silver nanoparticles have been used for making the nanocomposites in bulk and thin film forms. These PANI nanocomposites are found to exhibit quite dominant third order optical non-linearity. The highlight of these studies is the observation of the interesting phenomenon of the switching between saturable absorption (SA) and reverse saturable absorption (RSA) in the films of Ag/PANI and Au/PANI nanocomposites, which offers prospects of applications in optical switching. The investigations on the energy storage prospects of PANI were carried out on Li enriched PANI which was used as the cathode active material for assembling rechargeable Li-ion cells. For Li enrichment or Li doping of PANI, n-Butyllithium (n-BuLi) in hexanes was used. The Li doping as well as the Li-ion cell assembling were carried out in an argon filled glove box. Coin cells were assembled with Li doped PANI with different doping concentrations, as the cathode, LiPF6 as the electrolyte and Li metal as the anode. These coin cells are found to show reasonably good specific capacity around 22mAh/g and excellent cycling stability and coulombic efficiency around 99%. To improve the specific capacity, composites of Li doped PANI with inorganic cathode active materials like LiFePO4 and LiMn2O4 were synthesized and coin cells were assembled as mentioned earlier to assess the electrochemical capability. The cells assembled using the composite cathodes are found to show significant enhancement in specific capacity to around 40mAh/g. One of the other interesting observations is the complete blocking of the adverse effects of Jahn-Teller distortion, when the composite cathode, PANI-LiMn2O4 is used for assembling the Li-ion cells. This distortion is generally observed, near room temperature, when LiMn2O4 is used as the cathode, which significantly reduces the cycling stability of the cells.

Effect of dressing on high-order harmonic generation in vibrating H2 molecules

Wir entwickeln die Starkfeldnäherung für die Erzeugung hoher Harmonischer in Wasserstoffmolekülen, wobei die Vibrationsbewegung berücksichtigt wird, sowie die laserinduzierte Kopplung zwischen den beiden untersten Born-Oppenheimer-Zuständen im Molekülion, das durch die anfängliche Ionisation des Moleküls erzeugt wird. Wir zeigen, dass die Kopplung bei längeren Laserwellenlängen (≈ 2 μm) wichtig wird und zu einer Reduzierung der Erzeugung von Harmonischen führt, sowie zu einer Änderung des Verhältnisses von Harmonischen in verschiedenen Isotopen. ----------------------------------------------------------------------- We develop the strong-field approximation for high-order harmonic generation in hydrogen molecules, including the vibrational motion and the laser-induced coupling of the lowest two Born-Oppenheimer states in the molecular ion that is created by the initial ionization of the molecule. We show that the field dressing becomes important at long laser wavelengths (≈ 2 μm), leading to an overall reduction of harmonic generation and modifying the ratio of harmonic signals from different isotopes.