Ground- and excited-state properties of M-center oxygen vacancy aggregates in the bulk and the surface of MgO

Aggregates of oxygen vacancies (F centers) represent a particular form of point defects in ionic crystals. In this study we have considered the combination of two oxygen vacancies, the M center, in the bulk and on the surface of MgO by means of cluster model calculations. Both neutral and charged forms of the defect M and M+ have been taken into account. The ground state of the M center is characterized by the presence of two doubly occupied impurity levels in the gap of the material; in M+ centers the highest level is singly occupied. For the ground-state properties we used a gradient corrected density functional theory approach. The dipole-allowed singlet-to-singlet and doublet-to-doublet electronic transitions have been determined by means of explicitly correlated multireference second-order perturbation theory calculations. These have been compared with optical transitions determined with the time-dependent density functional theory formalism. The results show that bulk M and M+ centers give rise to intense absorptions at about 4.4 and 4.0 eV, respectively. Another less intense transition at 1.3 eV has also been found for the M+ center. On the surface the transitions occur at 1.6 eV (M+) and 2 eV (M). The results are compared with recently reported electron energy loss spectroscopy spectra on MgO thin films.

Electronic structure of a neutral oxygen vacancy in SrTiO3

The electronic structure of an isolated oxygen vacancy in SrTiO3 has been investigated with a variety of ab initio quantum mechanical approaches. In particular we compared pure density functional theory (DFT) approaches with the Hartree-Fock method, and with hybrid methods where the exchange term is treated in a mixed way. Both local cluster models and periodic calculations with large supercells containing up to 80 atoms have been performed. Both diamagnetic (singlet state) and paramagnetic (triplet state) solutions have been considered. We found that the formation of an O vacancy is accompanied by the transfer of two electrons to the 3d(z2) orbitals of the two Ti atoms along the Ti-Vac-Ti axis. The two electrons are spin coupled and the ground state is diamagnetic. New states associated with the defect center appear in the gap just below the conduction band edge. The formation energy computed with respect to an isolated oxygen atom in the triplet state is 9.4 eV.

MgO/Ag(001) interface structure and STM images from first principles

The interface of MgO/Ag(001) has been studied with density functional theory applied to slabs. We have found that regular MgO films show a small adhesion to the silver substrate, the binding can be increased in off-stoichiometric regimes, either by the presence of O vacancies at the oxide film or by a small excess of O atoms at the interface between the ceramic to the metal. By means of theoretical methods, the scanning tunneling microscopy signatures of these films is also analyzed in some detail. For defect free deposits containing 1 or 2 ML and at low voltages, tunnelling takes place from the surface Ag substrate, and at large positive voltages Mg atoms are imaged. If defects, oxygen vacancies, are present on the surface of the oxide they introduce much easier channels for tunnelling resulting in big protrusions and controlling the shape of the image, the extra O stored at the interface can also be detected for very thin films.

Growth And Characterization Of Diammonium Hydrogen Citrate And Citric Acid Monohydrate Single Crystals

Over the past years there has been considerable interest in the growth of single crystals both from the point of view of basic research and technological application. With the revolutionary emergence of solid state electronics which is based on single crystal technolo8Ys basic and applied studies on crystal growth and characterization _have gained a-more significant role in material science. These studies are being carried out for single crystals not only of semiconductor and other electronic materials but also of metals and insulators. Many organic crystals belonging to the orthorhombic class exhibit ferroelectric, electrooptic, triboluminescent and piezoelectric properties. Diammonium Hydrogen Citrate (DAHC) crystals are reported to be piezoelectric and triboluminescent /1/. Koptsik et al. /2/ have reported the piezoelectric nature of Citric Acid Monohydrate (CA) crystals. And since not much work has been done on these crystals, it has been thought useful to grow and characterize these crystals. This thesis presents a study of the growth of these crystals from solution and their defect structures. The results of the microindentation and thermal analysis are presented. Dielectric, fractographic, infrared (IR) and ultraviolet (UV) studies of DAHC crystals are also reported

Cinematographic Licensing

In India, film censorship originated with Cinematograph Act 1918 empowering the Provincial Governments to establish censorial authorities. In 1949, an amendment provided for a Central Board of Film Censors. In 1952, a new legislation gave the Central Government enormous powers, making the Board to function as a department of the Central Government. The Government had control over the Board with the mechanism of issuing 'directions' to the censors and laying down censorship rules. The legislation did not provide any objective criteria for censoring films. The 1959 amendment, aimed at curing this defect, only incorporated the grounds contained in Article 19(2) of the Constitution. Even after expert studies and a significant decision by the Supreme Court, pointing out the inadequacy of the existing system, and governmental attempts to bring reforms by way of fresh directions, appointment of appellate authority and framing of new rules, the system still warrants radical change. The thesis explores them.

Growth And Characterization Of Te-Se System And Some Tei.I.Urioes

The physical properties of solid matter are basically influenced by the existence of lattice defects; as a result the study of crystal defects has assumed a central position in solid state physics and materials science. The study of dislocations ixa single crystals can yield a great deal of information on the mechanical properties of materials. In order to secure a full understanding of the processes taking place in semiconducting materials, it is important to investigate the microhardness of these materials-—the most reliable method of determining the fine structure of crystals, the revelation of micro—inhomogenities in the distribution of impurities, the effect of dislocation density on the mechanical properties of crystals etc. Basically electrical conductivity in single crystals is a defect controlled phenomenon and hence detailed investigation of the electrical properties of these materials is one of the best available methods for the study of defects in them. In the present thesis a series of detailed studies carried out in Te—Se system, Bi2Te3 and In2Te3 crystals using surface topographical, dislocation and microindentation analysis as well as electrical measurements are presented

Non-destruct|ve testing of non-metallic materials using microwaves

The motivatitni for" the present work is from .a project sanctioned by TSRO. The work involved the development of a quick and reliable test procedure using microwaves, for tflue inspection of cured propellant samples and a method to monitor the curing conditions of propellant mix undergoing the curing process.Normal testing CHE the propellant samples involvecuttimg a piece from each carton and testing it for their tensile strength. The values are then compared with standard ones and based on this result the sample isaccepted or rejected. The tensile strength is a measure ofdegree of cure of the propellant mix. But this measurementis a destructive procedure as it involves cutting of the sample. Moreover, it does not guarantee against nonuniform curing due to power failure, hot air-line failure,operator error etc. This necessitated the need for the development of a quick and reliable non-destructive test procedure.

Acid-Base. Surface Electron Donatin6 &.Catai.Ytlc Properties Of Some Binary Mixed Oxides Containing Rare Earth Elements

Catalysis research underpins the science of modern chemical processing and fuel technologies. Catalysis is commercially one of the most important technologies in national economies. Solid state heterogeneous catalyst materials such as metal oxides and metal particles on ceramic oxide substrates are most common. They are typically used with commodity gases and liquid reactants. Selective oxidation catalysts of hydrocarbon feedstocks is the dominant process of converting them to key industrial chemicals, polymers and energy sources.[1] In the absence of a unique successfiil theory of heterogeneous catalysis, attempts are being made to correlate catalytic activity with some specific properties of the solid surface. Such correlations help to narrow down the search for a good catalyst for a given reaction. The heterogeneous catalytic performance of material depends on many factors such as [2] Crystal and surface structure of the catalyst. Thermodynamic stability of the catalyst and the reactant. Acid- base properties of the solid surface. Surface defect properties of the catalyst.Electronic and semiconducting properties and the band structure. Co-existence of dilferent types of ions or structures. Adsorption sites and adsorbed species such as oxygen.Preparation method of catalyst , surface area and nature of heat treatment. Molecular structure of the reactants. Many systematic investigations have been performed to correlate catalytic performances with the above mentioned properties. Many of these investigations remain isolated and further research is needed to bridge the gap in the present knowledge of the field.

Non-destructive evaluation of photovoltaic materials and solar cells using Photoluminescence

Photoluminescence (PL) spectroscopy is an optical technique that has emerged successful in the field of semiconductor material and device characterization. This technique is quite a powerful one which gives idea about the defect levels in a material, the band gap of the material, composition as well as material quality. Over the recent years it has received an elevation as a mainstream characterization technique. This thesis is an attempt to characterize each individual layer used in a thin film solar cell with special focus on the electrical properties. This will be highly beneficial from the lab as well as industrial point of view because electrical measurements generally are contact mode measurements which tend to damage the surface. As far as a thin film solar cell is concerned, the constituent layers are the transparent conducting oxide (TCO), absorber layer, buffer layer and top electrode contact. Each layer has a specific role to play and the performance of a solar cell is decided and limited by the quality of each individual layer. Various aspects of PL spectroscopy have been employed for studying compound semiconductor thin films [deposited using chemical spray pyrolysis (CSP)] proposed for solar cell application. This thesis has been structured in to seven chapters

Enhanced UV emission from ZnO nanoflowers synthesized by the hydrothermal process

ZnO nanoflowers were synthesized by the hydrothermal process at an optimized growth temperature of 200 ◦C and a growth/reaction time of 3 h. As-prepared ZnO nanoflowers were characterized by x-ray diffraction, scanning electron microscopy, UV–visible and Raman spectroscopy. X-ray diffraction and Raman studies reveal that the as-synthesized flower-like ZnO nanostructures are highly crystalline with a hexagonal wurtzite phase preferentially oriented along the (1 0 1 1) plane. The average length (234–347 nm) and diameter (77–106 nm) of the nanorods constituting the flower-like structure are estimated using scanning electron microscopy studies. The band gap of ZnO nanoflowers is estimated as 3.23 eV, the lowering of band gap is attributed to the flower-like surface morphology and microstructure of ZnO. Room temperature photoluminescence spectrum shows a strong UV emission peak at 392 nm, with a suppressed visible emission related to the defect states, indicating the defect free formation of ZnO nanoflowers that can be potentially used for UV light-emitting devices. The suppressed Raman bands at 541 and 583 cm−1 related to defect states in ZnO confirms that the ZnO nanoflowers here obtained have a reduced presence of defects

Energy bandstructureinvestigationofblueandgreenlightemitting Mg dopedSnO2 nanostructuressynthesizedbycombustionmethod

Tin oxide(SnO2) andMgdoped(2,4,6,and8wt%)SnO2 nanoparticles weresynthesizedbytheself- propagating solutioncombustionsynthesisusingcitricacidasfuel.Thecharacterizationofsampleswas done byX-raydiffractionspectroscopy(XRD),transmissionelectronmicroscopy(TEM),UV–visible spectroscopy,SAEDandphotoluminescence(PL).XRDpatternandTEMstudiesshowthatthe synthesized particlesareofaveragesize30nmandtheyareintetragonalrutilestructureofSnO2. Combined blueandgreenemissionisseenin4wt%MgdopedSnO2 and intensityofbluebandis increased withrespecttoincreaseinMgdopantconcentrationwhichisattributedtoincreasein population ofoxygenvacancies.ThePLemissioninblueandgreenregionisduetothedoublycharged state (Vo 2þ) ofoxygenandtininterstitialdefectsrespectivelyandisexplainedwithanenergyband diagram

Photoluminescence Studies Of Microwave Assisted Synthesized Zno Micro Structures

ZnO micro particles in the range 0.4-0.6 μm were synthesized by microwave irradiation method. The XRD analysis reveals that the sample is in the wurtzite phase with orientation along the (101) plane. SAED pattern of the sample reveals the single crystalline nature of the micro grains. TEM images show the formation of cylindrical shaped ZnO micro structures with hexagonal faces. The optical phonon modes were slightly shifted in the Raman spectrum,attributed to the presence of various crystalline defects and laser induced local heating at the grain boundaries. A broad transmission profile was observed in the FTIR spectrum from 1550-3400 cm-1 which falls in the atmospheric transparency window region. PL spectrum centered at 500 nm with a broad band in the region 420-570 nm comprised of different emission peaks attributed to transition between defect levels. Various emission levels in the sample were expliained with a band diagram

Funktionsanalysen der Domänen des Vacuolin B und die Rolle des filamentösen Actins am Vacuolin B-positiven Kompartiment im endocytotischen Transit in Dictyostelium discoideum

Ähnlich wie in Säugerzellen ist das neutrale Postlysosom in Dictyostelium discoideum von einem Coat aus filamentösem Actin umgeben. In dieser Arbeit wurde der Frage nach der Funktion dieses Actin-Cytoskeletts am späten Endosom nachgegangen. Hierzu wurde zunächst eine Analyse der Domänen des Vacuolin B durchgeführt, das als bisher spätester bekannter Marker im Endocytoseweg in Dictyostelium discoideum das neutrale, postlysosomale Kompartiment dekoriert. In einer Yeast Two Hybrid-Analyse wurden die Bereiche des Vacuolin B identifiziert, die für eine Selbst-Interaktion des Proteins notwendig und ausreichend sind. Es handelt sich dabei um die coiled-coil-Domäne und einen daran anschließenden, 18 Aminosäuren langen, alpha-helicalen Abschnitt. Diesem helicalen Bereich scheint die Funktion einer modifizierenden, die coiled-coil-Ausbildung vermittelnden oder initiierenden Faltungseinheit zuzukommen. Sie weist jedoch nicht die typischen Merkmale einer trigger-Helix auf. Lokalisationsuntersuchungen mit GFP-Deletionskonstrukten zeigten, dass es einen Zusammenhang zwischen Interaktionsfähigkeit und Bindung des Vacuolin an die Oberfläche später Endosomen gibt: Eine korrekte Lokalisation und Membranassoziation waren nur dann zu beobachten, wenn in der Yeast Two Hybrid-Analyse eine Interaktion nachgewiesen werden konnte. Es wurden die für die Lokalisation und Assoziation mit der vacuolären Membran notwendigen Sequenzbereiche identifiziert; diese waren jedoch nicht hinreichend. Vermutlich sind hierfür auch Sequenzen des N-Terminus notwendig. Die erhobenen Daten legen weiterhin eine Bedeutung der hydrophoben Domäne des Vacuolin B für die korrekte Faltung des Proteins nahe. Im Anschluss an die Domänenanalyse wurde Vacuolin dazu benutzt, durch Herstellung von Hybridproteinen Actin-interagierende Proteine gezielt an das späte Endosom zu transportieren. Es wurde deren Einfluss auf den lokalen Actin Coat und den endocytotischen Transit untersucht. Zwei Actin-bindende Proteine mit depolymerisierender Wirkung konnten im Rahmen dieser Arbeit getestet werden, nämlich Severin und Cofilin. Die Schwächung des lokalen Actin Coats durch das Vorhandensein von Severin an der späten Vacuole war nicht eindeutig festzustellen. Severin am Postlysosom führte nicht zu einer Veränderung der Transitkinetik von Flüssigphasenmarker. Allerdings konnte ein Defekt in der Phagocytose festgestellt werden. Es könnte hierbei ein Zusammenhang zwischen der Mobilisierung von intrazellulärem Calcium während der Partikelaufnahme und der Calcium-abhängigen Regulation der Severin-Aktivität bestehen. Das Hybridprotein aus Vacuolin und Cofilin zeigte neben einer Assoziation mit der vacuolären Membran auch eine Lokalisation im Cytoplasma und Cortex der Zellen. Mit der Lokalisation im Cytoplasma und Cortex korrelierte eine Veränderung der endocytotischen Aktivität. Das Vacuolin-Cofilin-Fusionsprotein am Postlysosom rief einen Verlust des lokalen Actin Coats hervor. Dies führte zu einer traubenförmigen Assoziation der späten Endosomen; exocytotische Parameter blieben jedoch unbeeinflusst. Aufgrund der hier erhobenen Daten kann vermutet werden, dass der Actin Coat am Postlysosom dazu dient, eine Agglutination dieser Endosomen zu inhibieren. Dies könnte ein Schutzmechanismus zum Ausschluss von Docking- und Fusionsereignissen sein.

Funktionelle Analyse der LC-FACS in Dictyostelium discoideum

"Funktionelle Analyse der LC-FACS in Dictyostelium discoideum" Das Dictyostelium discoideum Gen fcsA kodiert für ein 75 kDa großes Protein. Es kann durch Homologieanyalysen der Amino-säuresequenz zu den "long-chain fatty acyl-CoA"-Synthetasen ge-rechnet werden, die lang-kettige Fettsäuren durch die kovalente Bindung von Coenzym A akti-vie-ren und damit für diverse Reak-tionen in Stoffwechsel und Molekül-Synthese der Zelle verfügbar machen. Die hier untersuchte D. discoideum LC-FACS lokalisiert als peripher assoziiertes Protein an der cytosolischen Seite der Membran von Endo-somen und kleiner Vesikel. Bereits kurz nach der Bildung in der frühen sauren Phase kann die Lokalisation der LC-FACS auf Endosomen ge-zeigt werden. Sie dissoziiert im Laufe ihrer Neutra-li-sierung und kann auf späten Endosomen, die vor ihrer Exocytose stehen nicht mehr nach-gewiesen werden. Ein Teil der kleinen die in der gesamte Zelle verteilten kleinen Vesikel zeigt eine Kolokalisation mit lysosomalen Enzymen. Trotz des intrazellulären Verteilungs-mus-ters, das eine Beteiligung dieses Pro-teins an der Endocytose nahe-legt, konnte kein signifikanter Rückgang der Pino- und Phagocytose-Rate in LC-FACS Nullmutanten beobachtet werden. Der endo-cy-to-ti-sche Transit ist in diesen Zellen etwas verlängert, außerdem zeigen die Endosomen einen deutlich erhöhten pH-Wert, was zu einer weniger effektiven Prozessierung eines lysosomalen Enzyms führt (a-Mannosidase). Die Funktion der LC-FACS ist die Aufnahme von langkettigen Fettsäuren aus dem Lumen der Endosomen.

Molecular studies on a Dictyostelium homolog of the tafazzin gene, the cause of Barth syndrome in humans

Der eukaryotische Mikroorganismus Dictyostelium discoideum lebt als einzellige Amöbe solange ausreichende Nahrungsressourcen zur Verfügung stehen. Sobald Nahrungsmangel eintritt, entwickeln sich die Zellen von einem einzelligen zu einem mehrzelligen Zustand, der mit einem multizellulären Fruchtkörper abschließt. Dieser Prozess wird durch eine Reihe aufeinanderfolgender Signale organisiert, die eine differentielle Genexpression regulieren. Die Gene der Discoidin I Familie gehören zu den Ersten, die im Laufe des Wachstums-Differenzierungs-Übergangs (engl. GDT) aktiviert werden. Sie eignen sich daher vorzüglich als Marker für den Beginn der Entwicklung. Mit Hilfe einer REMI-Mutagenese und Discoidin I als molekularem Marker sind verschiedene Komponenten des Wachstums-Differenzierungs-Übergangs in unserer Arbeitsgruppe identifiziert worden (Zeng et al., 2000 A und B; Riemann und Nellen, persönliche Mitteilung). Mit demselben Ansatz wurde in der vorliegenden Arbeit eine REMI-Mutante identifiziert, die eine Fehl-Expression von Discoidin zeigte und einen axenischen Wachstumsdefekt bei 15 °C aufwies. Das Gen wurde als Homolog zum humanen Tafazzin-Gen identifiziert. Dieses Gen wurde zur Rekonstruktion des Phänotyps über homologe Rekombination erneut disruptiert, was wie erwartet zu dem zuerst beschriebenen Phänotyp führte. Folgerichtig ergab eine Überexpression des Gens in den Mutanten eine Komplementation des Phänotyps. Immunfluoreszenz-Experimente zeigten eine mitochondriale Lokalisation des Dictyostelium discoideum Taffazzin Proteins. Dass ein mitochondriales Protein in Zusammenhang mit dem Wachstums-Differenzierungs-Übergang steht, ist ein unerwarteter Befund, der aber als Hinweis darauf gewertet werden kann, dass Mitochondrien einen direkten Einfluss auf die entwicklungsspezifische Signaltransduktion ausüben. Die Taffazzin Disruptions-Mutante in Dictyostelium führte zu einem abnormalen Cardiolipin Metabolismus. Dieses Phospholipid ist ein charakteristischer Bestandteil der inneren Mitochondrienmembran und für die Funktion verschiedener Enzyme erforderlich. Unsere vorläufigen Analysen des Phospholipid-Gehalts zeigten Übereinstimmung mit Daten von Patienten mit Barth-Syndrom, einer humanen Erkrankung, bei der das Taffazzin-Gen Mutationen aufweist, und mit Hefe-Mutanten dieses Gens. Dies zeigt den Wert von Dictyostelium discoideum als einen weiteren Modelorganismus zur Untersuchung des Barth-Syndroms und zur Erprobung möglicher Therapieansätze.