1,928 research outputs found

    Ab initio studies on photorelaxation

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    This work addresses relaxation mechanisms of photoexcited organic molecules of small and medium size, up to 62 atoms. For most systems it is investigated theoretically, how modifications, often in the form of substituents, influence the decay processes. The research in large parts is done in close collaboration with groups providing experimental data, which allows to formulate robust hypotheses and models. Four systems are discussed in this context. We find the formation of the dewar lesion in deoxyribonucleic acid (DNA) to only occur, when the nucleobase is embedded in the DNA backbone, which sterically hinders accessing alternative channels. Substituting hydroxy groups at certain points of thioindigo is shown to open up an efficient deactivation channel via excited state intramolecular proton transfer, and greatly enhance the photostability of the molecule. By substituting electron donating groups to the stilbene moiety of the hemithioindigo photoswitch and correlating their effect to their Hammett parameters, the isomerization speed of hemithioindigo is optimized. And lastly, when adding an aldehyde group to furan, an additional pathway is found for its derivatives furfural and β-furfural. Their relaxation is slowed down regardless. The effects on the excited state potential energy surfaces are described as general means, by which the surfaces can be influenced, and likely can be translated to other molecules as well. This eventually allows to predict properties and tailor molecules to yield desired behavior. In this context, for example for furan, furfural and β-furfural the structural implications of the aldehyde substituent on one conical intersection are deducted from the extended two-electron two-orbital model prior to any calculations or experiments. Alongside the system specific investigations, an interface for the on-the-fly dynamics package NewtonX to the quantum chemistry package Molpro was programmed. Non-adiabatic semiclassical on-the-fly dynamics are a powerful tool to simulate complete relaxation processes without constraints in the dimensionality. For the interface, which in its primary setup uses complete active space self consistent field theory calculations, a number of features has been implemented. Most notably, it enables non-adiabtatic dynamics on complete active space perturbation and ONIOM level of theory

    Ab initio studies on photorelaxation

    Get PDF
    This work addresses relaxation mechanisms of photoexcited organic molecules of small and medium size, up to 62 atoms. For most systems it is investigated theoretically, how modifications, often in the form of substituents, influence the decay processes. The research in large parts is done in close collaboration with groups providing experimental data, which allows to formulate robust hypotheses and models. Four systems are discussed in this context. We find the formation of the dewar lesion in deoxyribonucleic acid (DNA) to only occur, when the nucleobase is embedded in the DNA backbone, which sterically hinders accessing alternative channels. Substituting hydroxy groups at certain points of thioindigo is shown to open up an efficient deactivation channel via excited state intramolecular proton transfer, and greatly enhance the photostability of the molecule. By substituting electron donating groups to the stilbene moiety of the hemithioindigo photoswitch and correlating their effect to their Hammett parameters, the isomerization speed of hemithioindigo is optimized. And lastly, when adding an aldehyde group to furan, an additional pathway is found for its derivatives furfural and β-furfural. Their relaxation is slowed down regardless. The effects on the excited state potential energy surfaces are described as general means, by which the surfaces can be influenced, and likely can be translated to other molecules as well. This eventually allows to predict properties and tailor molecules to yield desired behavior. In this context, for example for furan, furfural and β-furfural the structural implications of the aldehyde substituent on one conical intersection are deducted from the extended two-electron two-orbital model prior to any calculations or experiments. Alongside the system specific investigations, an interface for the on-the-fly dynamics package NewtonX to the quantum chemistry package Molpro was programmed. Non-adiabatic semiclassical on-the-fly dynamics are a powerful tool to simulate complete relaxation processes without constraints in the dimensionality. For the interface, which in its primary setup uses complete active space self consistent field theory calculations, a number of features has been implemented. Most notably, it enables non-adiabtatic dynamics on complete active space perturbation and ONIOM level of theory

    Visual Analysis of High-Dimensional Point Clouds using Topological Abstraction

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    This thesis is about visualizing a kind of data that is trivial to process by computers but difficult to imagine by humans because nature does not allow for intuition with this type of information: high-dimensional data. Such data often result from representing observations of objects under various aspects or with different properties. In many applications, a typical, laborious task is to find related objects or to group those that are similar to each other. One classic solution for this task is to imagine the data as vectors in a Euclidean space with object variables as dimensions. Utilizing Euclidean distance as a measure of similarity, objects with similar properties and values accumulate to groups, so-called clusters, that are exposed by cluster analysis on the high-dimensional point cloud. Because similar vectors can be thought of as objects that are alike in terms of their attributes, the point cloud\''s structure and individual cluster properties, like their size or compactness, summarize data categories and their relative importance. The contribution of this thesis is a novel analysis approach for visual exploration of high-dimensional point clouds without suffering from structural occlusion. The work is based on implementing two key concepts: The first idea is to discard those geometric properties that cannot be preserved and, thus, lead to the typical artifacts. Topological concepts are used instead to shift away the focus from a point-centered view on the data to a more structure-centered perspective. The advantage is that topology-driven clustering information can be extracted in the data\''s original domain and be preserved without loss in low dimensions. The second idea is to split the analysis into a topology-based global overview and a subsequent geometric local refinement. The occlusion-free overview enables the analyst to identify features and to link them to other visualizations that permit analysis of those properties not captured by the topological abstraction, e.g. cluster shape or value distributions in particular dimensions or subspaces. The advantage of separating structure from data point analysis is that restricting local analysis only to data subsets significantly reduces artifacts and the visual complexity of standard techniques. That is, the additional topological layer enables the analyst to identify structure that was hidden before and to focus on particular features by suppressing irrelevant points during local feature analysis. This thesis addresses the topology-based visual analysis of high-dimensional point clouds for both the time-invariant and the time-varying case. Time-invariant means that the points do not change in their number or positions. That is, the analyst explores the clustering of a fixed and constant set of points. The extension to the time-varying case implies the analysis of a varying clustering, where clusters appear as new, merge or split, or vanish. Especially for high-dimensional data, both tracking---which means to relate features over time---but also visualizing changing structure are difficult problems to solve

    Marine aquaculture in the Commonwealth of Virginia

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    Heating Soft Crab Shedding Systems

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    The molting of blue crabs, and ultimately soft shell crab production, is regulated by water temperature. A certain threshold or minimum water temperature must be reached before blue crabs begin to molt (shed). Although crabs begin shedding at temperatures in the mid-60\u27sF (18-19°C), water temperatures near 70°F (21°C) are optimum for active shedding. As the water temperature increases, the time required for a crab to progress through the stages leading to molting decreases (the time needed to go from a white-line, to a pink-line and finally red-line crab). The time needed for a complete molt--for a soft crab to exit from its old shell--also decreases with increasing water temperature. More ....

    Dynamic recrystallization and deformation mechanisms of naturally deformed Carrara Marble: a study on one- and two-phase carbonate rocks

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    Carrara marble is a greenschist facies metamorphic marble from the Alpi Apuane, Tuscany, Italy. It is widely known for its chemical purity, its homogenous microstructure and isotropic texture (crystallographic preferred orientation). During two deformation events (D1 and D2) the Liassic sedimentary precursor of Carrara marble was metamorphosed and deformed. Besides statically recrystallized microstructures, two end members of dynamically recrystallized microstructures are preserved in Carrara marble (Molli et al. 1997, Molli & Heilbronner 1999, Molli et al. 2000). Both end members can be related either to sub grain rotation (SGR) recrystallization or to grain boundary migration (GBM) recrystallization, respectively. In order to characterize the different dynamically recrystallized microstructures and to relate them to mesoscopical structures of D1 and D2 a combined study of structural field geology and microstructural analysis was carried out. On the basis of a detailed structural mapping overprinting relationships between D1 and D2 were investigated and typical deformation structures were sampled. The microstructural analysis of theses shear zones and folds revealed that D1 structures are generally characterized by GBM microstructures and D2 structures by SGR microstructures. Systematic determination of deformation temperatures of D1 and D2 shear zones along a profile parallel to the main tectonic transport direction by calcite-dolomite thermometry shows two individual temperature trends for D1 and D2. The D1 deformation temperatures decrease from West to East from 430°C to 370°C and those of D2 decrease from 370°C in the East to 295°C in the West. This continuous temperature gradient makes it possible to study dynamic recrystallization microstructures over a temperature range of approximately 150°C. In order to investigate the influence of strain on the formation of microstructure and texture in naturally deformed Carrara marble a mm-scaled D2 shear zone was analyzed. The shear zone was active at a constant temperature of 325°C and cross-cut the S1 main foliation, which acted as a passive strain marker. Therefore, the observed variations of microstructure and texture are solely a function of the accommodated strain and the strain rate. The protolith is characterized by a core-mantle microstructure with coarse porphyroclasts, which are embedded in a matrix of small recrystallized grains. With increasing strain the microstructure becomes progressively recrystallized, so that the center of the shear zone is completely recrystallized and a fine-grained matrix of equally shaped recrystallized grains is developed. At the same time the texture changes from an e-twinning type (single c-axes point maximum parallel to the compression direction) in the protolith to a basal texture (single c-axes maximum perpendicular to the shear plane) in the center of the shear zone. This texture transition is caused by SGR recrystallization, which forms continuously new grains with slightly rotated crystallographic orientations in the same sense as the overall shear deformation. Strain rate estimates on the basis of experimentally derived flow laws suggest that the shear zone is highly localized in space and in time. Localization of deformation was probably caused by the presence of a pre-existing coarse-grained calcite vein. According to the Hall-Petch relationship dislocation glide is favoured by coarse-grained materials, which is why deformation may started in the vein calcite by twining. After a certain amount of strain twinning is exhausted and the deformation continued by dislocation creep associated by dynamic recrystallization. Many calcite shear zones in the Alpi Apuane contain substantial amounts of dolomite, representing a second phase in ‘pure’ Carrara marble. Second phases are considered to influence the mechanical behaviour of a mono-mineralic rock, so that the strength of the phase mixture deviates from the one of the pure end members (Tullis et al. 1991, Dresen et al. 1998, Bruhn et al. 1999). In order to investigate the influence of dolomite on microstructure, texture and the dominant deformation mechanism of calcite a shear zone from the Eastern Alpi Apuane was analyzed. The shear zone is composed of alternating calcite and dolomite rich layers. Dolomite is presumably derived from dolomite veins, which become progressively fractured and sheared so that at the highest strains completely mixed layers of calcite and dolomite are developed. Pure calcite layers are characterized by a GBM microstructure and a strong basal texture, indicating that they have deformed dominantly by dislocation creep. With increasing dolomite content the calcite grains become smaller and less lobate, while the dolomite grains maintain their initial size and shape. Also the texture of calcite becomes weaker and the initial orthorhombic symmetry (with respect to the shear plane) is almost randomized at a dolomite content of ~50 vol%. This transition suggests that the mixed layers deform dominantly by diffusion creep. Heterogeneous nucleation (Kruse & Stünitz 1999) of dolomite along calcite grain boundaries and triple junctions leads to a dispersion of calcite and dolomite, supporting the activity of diffusion creep and grain boundary sliding. The progressive addition of dolomite to calcite may lead to the transition from dislocation creep dominated deformation in the pure calcite layers to diffusion creep dominated deformation in the mixed layers. The rheological behaviour of each layer was estimated with the help of a deformation mechanism map. It turned out that the mixed layers deform either by higher strain rates and constant stresses or at lower stresses and a constant strain rate, both suggesting a localization of deformation in the mixed layers

    Manual for Handling and Shedding Blue Crabs (Callinectes sapidus)

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    This manual is intended to present a practical approach to constructing and operating a Chesapeake Bay crab shedding facility. Included are portions of an earlier VIMS publication by Paul A. Haefner, Jr. and David Garten (1974), Methods of handling and shedding blue crabs, (Callinectes sapidus), as well as a compilation of other scientific and industry experiences. Techniques described may not apply to all situations; in many cases general recommendations are made. Additionally, descriptions of various facility designs refer mainly to those in use in Chesapeake Bay; other areas of the country may use varying, but similar designs. Although the information in this manual will be very helpful in establishing a soft crab shedding operation, the prudent person will seek out additional assistance. In all soft crab producing states there are Sea Grant Marine Advisory Programs (Appendix 1) or other organizations willing to provide personalized services. These people should be searched out and contacted for guidance in entering the soft crab industry. Suggestions for additional reading are provided in Appendix 2. The use of trade names in this publication is solely for the purpose of providing specific information. It is not an endorsement of the products named and does not signify that they are approved to the exclusion of others
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