In order to study the electronic and optical properties of complex materials an approach providing a reliable estimate of band gaps in combination with the reasonable description of the ground state is required. In the present study of pure and defective perovskite crystals, the fulfillment of such requirements is clearly demonstrated using a simple hybrid HF/DFT scheme containing an admixture of non-local Fock exchange. In present theoretical investigations, a wide class of perovskite oxides is represented by three, the most attractive (from a scientific point of view) crystals of SrTiO3, BaTiO3, and PbTiO3 in their high symmetry cubic phases. These perovskite crystals present a great technological and fundamental interest due to their numerous applications related to ferroelectricity, non-linear and electro-optics, superconductivity, and catalysis. Although the above-mentioned perovskite-type materials have been intensively investigated theoretically and experimentally at least in the last fifteen years, a proper description of their electronic properties is still an area of active research. In order to make a contribution to the explanation of various electro-optical effects observed in perovskite materials, their ground-state properties have been calculated from first principles and analyzed in the present study.

The aim of the current work was to investigate the photo-induced charge transport at low temperatures, allowing more sensitive, detailed measurements of the first steps in the build-up of space charge fields, which modify the refractive index, leading to modern applications like volume holographic storage. We investigated the light-induced properties of SBN:Ce, KTO and KTN materials like origin of trapping centers which are involved in the charge transport process, characterization of trapping centers, like temperature dependence, illumination intensity dependence, evolution with time, spectral response, activation energies, the basic properties of the electronic excitations and photo-carriers localization based on results of absorption, light-induced absorption, photoluminescence, and photocurrent. The main contributions of this dissertation are summarized as follows: The experimental intensity dependence, temperature dependence, and decay process of the light-induced polaron (NIR) and VIS center absorption can be fitted with the help of a simplified charge transfer model (for SBN). The decay observed of the NIR polaron and the VIS centers is present due to the Fourier spectrometer light. The dissociation of the VIS centers into NIR centers under red light was observed. The model proposed for the VIS-centers in SBN is a triad structure related to the simultaneous bonding of two hole polarons and one electronic polaron.In KTN the emergence of the UV-light induced wide absorption bands in the NIR region with maxima at 0.69 0.8 eV at low temperatures is treated as a manifestation of the localization of photo-induced electrons and the formation of small electron polarons in close-neighbor Nb-Nb pair centers. Also, these properties in KTN can be fitted with the help of the simplified charge transfer model.

An extended Hubbard model with large short and long-ranged Coulomb repulsions and distant transfer is numerically investigated by use of the Lanczos exact diagonalization (ED) method to study the charge order and unconditional dimerization of a chain at density rho (ρ)= 0.4. From the analysis of the spin and charge correlation functions, a picture consistent with the formation of a dimer insulating state, which is of Wigner lattice-type (WL) charge order (CO), is obtained. The next-nearest neighbour (NNN) hopping t2 enhances the intradimer correlations and weakens the interdimer correlations. Implications for the CuO2 chains in Sr14Cu24O41 are discussed.We have also introduced a Heisenberg model which parametrically depends on hole positions. If the electrostatic hole-hole repulsion is included such a model allows to evaluate all energy eigenvalues and eigenstates (for small system size) and thus enables us to evaluate thermodynamic properties as function of temperature,magnetic field, and doping. Assuming certain exchange constants we can investigate the influence of the electrostatic hole-hole repulsion on ground state properties as well as on thermal averages like the magnetization which include contributions of low-lying spin-hole configurations.

Recent years have shown a dramatic growth of research activity in searching of materials that exhibit nonlinear optical (NLO) behaviours. Later investigations have shown that molecule-based organic materials and biomaterials possess advantages in NLO characteristics. This thesis is devoted to the theoretical and experimental study of the second-order nonlinear optical properties of native and modified bacteriorhodopsins. A hybrid quantum mechanical/molecular mechanical-configuration interaction (QM/MM-CI) method has been used to determine the nonlinear behaviour of modified BR. The calculated structures are the ground state and M1 state of wild type BR, several BR variants, the BR mutants W86F, W189F, W182F, W138C, Y185F, and Y83F as well as a photoreceptor NpSRII. The first hyperpolarizability of two available BR mutants W86F and D85C has been determined by means of the HRS technique. The experimentally determined first hyperpolarizability value for the mutant W86F is in good agreement with that obtained theoretically. Simultaneously with the time-resolved absorption spectroscopy measurements, the time-dependent HRS measurements were performed. Changes in the HRS signal during the photocycle were detected. The kinetics of time-resolved HRS and flash spectroscopy measurements of BR and the BR mutants T46C, R225C, R227C, D96C, and D85C were compared. The obtained kinetic constant are comparable with those determined by means of absorption spectroscopy. However, an unexpected decrease in the HRS intensity during the M to N transition was observed. The program "MultiFit" (written in the Delphi environment) as well as data acquisition software (written in the C environment) can be found online at: http://repositorium.uni-osnabrueck.de/bitstream/urn:nbn:de:gbv:700-2008020119/4/MultiFit.zip and: http://repositorium.uni-osnabrueck.de/bitstream/urn:nbn:de:gbv:700-2008020119/5/TRAS.zip

The subject of this thesis are channel waveguide lasers in epitaxial garnet films grown by liquid phase epitaxy. Results of this thesis include: The feasibility of a waveguide laser with erbium-doped YIG as the active material is discussed. Nonlinear rate equations that describe the behavior of this laser are formulated and solved numerically. The material parameters that are needed as the input are taken from literature. The simulations reveal that the performance of the laser depends critically on the magnitude of the upconversion parameter W22. A thorough analysis shows, however, that the values of W22 that are found in literature are most likely too small. The other parameter of importance is the background loss of the waveguide. Our results indicate that, unless the absorption losses of the LPE grown iron garnet films can be significantly reduced, the chances to realize such a device are only minimal. The mechanisms behind the absorption losses in LPE grown YIG films are investigated. During the LPE growth process, lead, platinum and other non-trivalent impurities are incorporated into the films in high concentrations. While platinum is tetravalent only, lead can be both di- and tetravalent. Depending on the ratio of the lead and the platinum concentrations, the near infrared absorption can be caused by three entirely different mechanisms. In case the tetravalent impurities are the majority, charge compensation is achieved by the formation of Fe2+ and the absorption is caused by crystal field transitions between the 5E and the 5T2 states of the Fe2+-ion. If the divalent impurities are in the majority, the absorption is due to crystal field transitions between the 5T2 and the 5E states of the Fe4-ion. In LPE-grown iron garnets, however, the impurity with the highest concentration is usually lead. We prove that lead performs self-compensation as it is incorporated in Pb2+/4+ pairs on neighboring lattice sites, and that the optical absorption is caused entirely by a charge transfer transition between the two neighboring lead ions. The electrical conductivity is measured in a temperature range from 300 to 800 K. It is demonstrated that in this temperature range the so-called impurity conduction is the predominant conduction mechanism in all types of films. Around room temperature, the conductivity shows an abnormal temperature behavior as the measured Bohr radius of the impurity ions almost doubles between 295 and 370 K. This can be explained by the fact that film and substrate have different temperature expansion coefficients. As the temperature increases, the stress in the film changes from tensile to compressive. When that happens, the {Pb2+} and the [Pb4+] ions counteract the strain in that they interchange their lattice sites. Also, Fe4+, if present, switches from the tetrahedral to the octahedral site which reduces the lattice constant of the film. This interpretation finds support in the results on the optical absorption, in the lattice mismatch, and in MCD spectra that were previously measured by Milani and Paroli. Based on the above findings, an easy way to eliminate the growth induced absorption in LPE iron garnet films is presented. By co-doping the films with other di- and tetravalent ions like Mg and Ge in high concentrations, the concentration of absorbing Pb2+/Pb4+ centers is greatly reduced due to the formation of non-absorbing Pb2+/Ge4+ and Ca2+/Pb4+ centers. As a result, absorption losses as low as 0.05 cm-1 at 1.3 µm wavelength have been achieved. In the second part of this thesis the fabrication of a channel waveguide laser in epitaxial Nd:GGG films is described. The films are grown by LPE on [111] oriented GGG substrates from a PbO/B2O3 flux. To increase the index contrast between film and substrate, Bi is added to the melt. Initially, the films showed strong brown discoloration and a high defect density. Luminescence lifetime measurements revealed severe quenching problems. The chemical analysis of the films by EPMA shows that platinum from the crucible enters the films but no lead from the flux. It is found that the platinum in GGG, similar to the lead in YIG, forms Pt2+/Pt4+ centers in order to achieve charge compensation. The quenching is caused by the charge transfer transition between the two platinum ions. To eliminate the quenching, MgO is added to the melt. As a result, the brown discoloration, the quenching and the growth defects disappear. From the planar film rib waveguides are fabricated using ion beam etching. The unclad waveguides are cut and the endfaces are polished to couple light in and out. Both endfaces are perpendicular to the waveguide within 0.1°. The losses are derived from the Fabry-Perot interferences. Losses as low as 0.2 dB/cm are achieved for both TE and TM modes. Laser oscillation starts at a launched pump power of 5 mW. The resonator is formed by the polished endfaces of the waveguide, no dielectric mirrors have been applied. Thus, the facet reflectivity is only about 10%. The launched pump power is measured precisely using a novel technique at which the luminescence intensity emitted through the surface is spatially resolved with a beam profile analyzer. Coupling efficiencies of over 90% are measured. The slope efficiency is found to be 48%.

Die Elektronen-Spin-Resonanz (ESR) Spektroskopie hat sich in Verbindung mit der Spinsondentechnik (SDSL) bereits seit einigen Jahren zur Struktur- und Dynamikanalyse von Biomakromolekülen etabliert. Diese Dissertation beschäftigt sich mit dem Aufbau eines Hochfeld-/Hochfrequenz-ESR-Spektrometers bei 3,4T/95GHz (W-Band) und drei attraktiven Anwendungen auf spinmarkierte Proteine. Als eine Anwendung wird die Bestimmung von Polaritäten und Protizitäten spinmarkierter Positionen des sensorischen Rhodopsin-Transducer-Komplexes (SRII/HtrII) aus Natronomonas pharaonis mit Hilfe von cw-Messungen bei Temperaturen <190 K präsentiert. Es werden Rückschlüsse auf die Struktur der HAMP-Domäne des Proteinkomplexes durchgeführt. Positionsabhängige Unterschiede der Protizität werden auf verschiedene Anteile mit null bis zwei Wasserstoffbrücken zum Nitroxid zurückgeführt. Als nächste Anwendung wird die Gewinnung von Reorientierungspotentialen der Spinträgerseitenkette mit dem SRLS-Model und in Kombination mit X- und Q-Bandmessungen bei Raumtemperatur demonstriert. Für die spinmarkierte Position einer Konformation des SRII/HTrII ergibt sich ein Potential, dass mit Ergebnissen von Molekulardynamiksimulationen eines helikalen Polypeptids gut übereinstimmt. Ebenfalls durchgeführt wurde die Bestimmung des Potentials an Position 166 der Kanal bildenden Domäne des Colicin A aus E. coli. Schließlich werden im Temperaturbereich von 120 bis 220 K die Einflüsse verschiedener (Isotopen-)Derivate des Spinlabels und der Einfluss der Wasserprotonen auf den Hahn-Echozerfall zur Bestimmung orientierungsabhängiger Librationsamplituden an einer weiteren SRII/HtrII-Probe und der gleichen Colicin A-Probe wie oben vorgestellt. Es werden Folgerungen für die Struktur der Proteine gezogen und, im Fall der Colicin A-Probe, ein Bezug zur Kristallstruktur hergestellt.

In dieser Arbeit wurden zwei verschiedene Wärmebadankopplungen an klassische Spin-Systeme realisiert. Zum einen wurde ein stochastischer Ansatz mittels Landau-Lifshitz-Dämpfung und Fluktuationen numerisch realisiert und zum anderen wurde ein vollkommen deterministischer Ansatz entworfen und optimiert. Mit Hilfe dieser Ankopplungsmethoden ist es möglich, sowohl statische magnetische Eigenschaften klassischer Spin-Systeme als auch deren dynamische magnetische Eigenschaften zu simulieren. Als Anwendung wurden Spin-Gitter-Relaxationszzeiten und Neutronenstreuquerschnitte für molekulare Magneten wie z.B. dem "ferric wheel" berechnet und mit aktuellen experimentellen Ergebnissen verglichen. Als zweite Anwendung wird die Magnetisierungsumkehr in einem sphärischen Teilchen diskutiert.

In dieser Arbeit werden kleine Schwefelcluser (S2 bis S8) untersucht. Es werden Massenspektren von gasförmigem Schwefel in Abhängigkeit von der Temperatur und der anregenden Photonenenergie vorgestellt. Es werden Photoionenausbeuten der Schwefelcluster im Anregungsenergiebereich der S 2p- und S 2s-Kante vorgestellt. Zudem werden Dreifachkoinzidenz-Experimente mit resonanter S 2p-Anregung durchgeführt.Diese experimentellen Techniken werden angewandt um die geometrische und elektronische Struktur, sowie die Fragmentationswege von einfach und mehrfach geladenen Schwefelclustern im Anregungsbereich der S 2p-Kante zu studieren. Die Photoionenausbeuten werden mit simulierten Photoabsorptionsspektren verglichen, die mit semiempirischen Extended-Hückel-Rechnungen ebenfalls im Rahmen dieser Arbeit bestimmt werden. Sie ermöglichen es, aus den Absorptionsquerschnitten im Bereich der Valenzübergänge Informationen über die Geometrie des Schwefelclusters zu erhalten.Vervollständigt wird die Arbeit durch die Untersuchung der besetzten elektronischen Niveaus. Es werden die S 2p-Ionisationsenergien von S2 und S8 untersucht. Dabei kommt eine Technik der Nullvolt-Photoelektronen-Spektroskopie zum Einsatz, bei der die Photoelektronen gemessen werden, die nach S 2p-Anregung auf das Ionisationspotenzial angehoben werden und somit keine kinetische Energie besitzen. Die Technik ist als ZEKE-Photoelektronen-Spektroskopie bekannt.

Als Aerosol bezeichnet man ein Ensemble aus festen oder flüssigen Partikeln, getragen von einem gasförmigen Medium. Zur Untersuchung von einzelnen über längere Zeit berührungsfrei gespeicherten Modellaerosolpartikeln wurde ein Experiment aufgebaut und charakterisiert. Eine elektrodynamische Falle nach Paul dient zur berührungsfreien Speicherung. In verschiedenen Rezipienten können Umweltparameter, wie die Temperatur, der Druck und die Gaszusammensetzung kontrolliert werden. Mit Hilfe der elastischen Mie-Streung und der inelastischen Raman-Streuung monochromatischen Lichts wird auf die Zusammensetzung, die Größe und den Brechungsindex in situ rückgeschlossen. Eine Computer-basierte Mess- und Regelungstechnik ermöglicht Prozessstudien mit Messdauern von einigen Sekunden bis zu mehreren Tagen, in denen die Änderung oben genannter Partikeleigenschaften unter Vorgabe bestimmter Umweltparameter beobachtet werden können. Zur Abschätzung der Größe von sphärischen und kristallinen Partikeln wurde eine Methode entwickelt, die die Musteranalyse des Streulichtfernfelds mit Hilfe der räumlichen Fourier-Transformation als Grundlage hat.Schnelle Prozesse, wie z.B. die Bewegung des Teilchens in der Falle oder Phasenübergänge von gespeicherten Partikeln, können mit einer Hochgeschwindigkeitskamera aufgenommen und mit Musteranalyseverfahren charakterisiert werden.Schließlich wird die chemische Totalanalyse von einzelnen Partikeln unter Anwendung eines time-of-flight-Massenspektrometers beschrieben. Einzelne Partikel werden dazu mit Hilfe eines Transfersystems aus der Speicherumgebung in das Massenspektrometer überführt und anschließend ex situ analysiert.

The photosensitive unit triggering the negative phototaxis in the haloarchaeum Natronomonas pharaonis consists of the receptor sensory rhodopsin II (NpSRII) and its cognate transducer (NpHtrII) in a 2:2 stoichiometry. Upon light excitation, a structural rearrangement in the receptor initiates a displacement/rotation of the transducer helix TM2, which can be considered as starting event for the signal transduction. This signal is further transmitted to the cytoplasmic signaling domain through the signal transduction unit comprising two HAMP domains.Structural information already exists for the transmembrane region of this complex (crystal structure) as well as for the rod shaped cytoplasmic part of NpHtrII due to its high homologies with chemoreceptors. Moreover, the solution NMR structure of the isolated HAMP domain from A. fulgidus recently obtained shows a homodimeric, four-helical, parallel coiled-coil with an unusual interhelical packing, that is thought to propagate a signal by virtue of concerted helix rotations. Here, an electron paramagnetic resonance (EPR) investigation of site-directed spin labeled transducers in the NpSRII/NpHtrII complex has been carried out for structural and functional elucidation of the N. pharaonis HAMP. For this purpose, cw as well as pulse EPR techniques have been used in terms of mobility, accessibility and intra-transducer dimer distance analyses. Conformational changes induced by environmental inputs, namely salt, temperature and pH, give insight into the two-state equilibrium existing between a highly dynamic (dHAMP) and a more compact (cHAMP) conformation of this linker region.