Relativistic effects in physics and chemistry of element 105. [Part] IV.

Results of relativistic (Dirac-Slater and Dirac-Fock) and nonrelativistic (Hartree-Fock-Slater) atomic and molecular calculations have been compared for the group 5 elements Nb, Ta, and Ha and their compounds MCl_5, to elucidate the influence of relativistic effects on their properties especially in going from the 5d element Ta to the 6d element Ha. The analysis of the radial distribution of the valence electrons of the metals for electronic configurations obtained as a result of the molecular calculations and their overlap with ligands show opposite trends in behavior for ns_1/2, np_l/2, and (n -1 )d_5/2 orbitals for Ta and Ha in the relativistic and nonrelativistic cases. Relativistic contraction and energetic stabilization of the ns_1/2 and np_l/2 wave functions and expansion and destabilization of the (n-1)d_5/2 orbitals make hahnium pentahalide more covalent than tantalum pentahalide and increase the bond strength. The nonrelativistic treatment of the wave functions results in an increase in ionicity of the MCl_5 molecules in going from Nb to Ha making element Ha an analog of V. Different trends for the relativistic and nonrelativistic cases are also found for ionization potentials, electronic affinities, and energies of charge-transfer transitions as well as the stability of the maximum oxidation state.

Solution of the Hartree-Fock-Slater equations for diatomic molecules by the finite-element method

We present the finite-element method in its application to solving quantum-mechanical problems for diatomic molecules. Results for Hartree-Fock calculations of H_2 and Hartree-Fock-Slater calculations for molecules like N_2 and CO are presented. The accuracy achieved with fewer than 5000 grid points for the total energies of these systems is 10^-8 a.u., which is about two orders of magnitude better than the accuracy of any other available method.

Ionization potentials and radii of atoms and ions of element 105 (unnilpentium) and ions of tantalum derived from multiconfiguration Dirac-Fock calculations

Multiconfiguration relativistic Dirac-Fock (MCDF) values were calculated for the first five ionization potentials of element 105 (unnilpentium) and of the other group 5b elements (V, Nb, and Ta). Some of these ionization potentials in electron volts (eV) with uncertainties are: 105(0), 7.4±0.4; 105(1 +), 16.3 ±0.2; 105(2 +), 24.3 ± 0.2; 105(3 + ), 34.9 ± 0.5; and 105(4 + ), 44.9 ± 0.1. Ionization potentials for Ta(1+), Ta(2 +), and Ta(3 + ) were also calculated. Accurate experimental values for these ionization potentials are not available. Ionic radii are presented for the 2+, 3+, 4 +, and 5+ ions of element 105 and for the + 2 ions of vanadium and niobium. These radii for vanadium and niobium are not available elsewhere. The ionization potentials and ionic radii obtained are used to determine some standard electrode potentials for element 105. Born-Haber cycles and a form of the Born equation for the Gibbs free energy of hydration of ions were used to calculate the standard electrode potentials.

The electronic structure of anionic halide complexes of element 105 in aqueous solutions and their extraction by aliphatic amines

To study the complex formation of group 5 elements (Nb, Ta, Ha, and pseudoanalog Pa) in aqueous HCI solutions of medium and high concentrations the electronic structures of anionic complexes of these elements [MCl_6]^-, [MOCl_4]^-, [M(OH)-2 Cl_4]^-, and [MOCl_5]^2- have been calculated using the relativistic Dirac-Slater Discrete-Variational Method. The charge density distribution analysis has shown that tantalum occupies a specific position in the group and has the highest tendency to form the pure halide complex, [TaCl_6-. This fact along with a high covalency of this complex explains its good extractability into aliphatic amines. Niobium has equal trends to form pure halide [NbCl_6]^- and oxyhalide [NbOCl_5]^2- species at medium and high acid concentrations. Protactinium has a slight preference for the [PaOCl_5]^2- form or for the pure halide complexes with coordination number higher than 6 under these conditions. Element 105 at high HCl concentrations will have a preference to form oxyhalide anionic complex [HaOCl_5]^2- rather than [HaCl_6]^-. For the same sort of anionic oxychloride complexes an estimate has been done of their partition between the organic and aqueous phases in the extraction by aliphatic amines, which shows the following succession of the partition coefficients: P_Nb < P_Ha < P_Pa.

The electronic structure of the group 6 oxyanions [MO_4]^2-, where M = Cr, Mo, W, and element 106

The electronic structure of the group 6 oxyanions [MO_4]^2-, where M = Cr, Mo, W, and element 106 have been calculated using the Dirac-Slater Discrete Variational method. Results of the calculations show a relative decrease in the metal-oxygen bond strengths for the [E106O_4]^2- ion in the solid state compared to that for the [WO_4]^2- anion. Calculated energies of the electronic charge-transfer transitions are indicative of a strong possible luminescence of [El06O_4]^2- in the blue-violet area. In solutions [El06O_4]^2- will be the most stable ion out of the entire series. Estimated reduction potential E^0 (El06O^2-_4/E106O^3-_4) equal to -1.60V shows only a slightly increased stability of the +6 oxidation state for element 106 in comparison with W.

Generic Finite Element Model for Mechanically Consistent Scaling of Composite Beam-to-column Joint with Welded Connection

To study the behaviour of beam-to-column composite connection more sophisticated finite element models is required, since component model has some severe limitations. In this research a generic finite element model for composite beam-to-column joint with welded connections is developed using current state of the art local modelling. Applying mechanically consistent scaling method, it can provide the constitutive relationship for a plane rectangular macro element with beam-type boundaries. Then, this defined macro element, which preserves local behaviour and allows for the transfer of five independent states between local and global models, can be implemented in high-accuracy frame analysis with the possibility of limit state checks. In order that macro element for scaling method can be used in practical manner, a generic geometry program as a new idea proposed in this study is also developed for this finite element model. With generic programming a set of global geometric variables can be input to generate a specific instance of the connection without much effort. The proposed finite element model generated by this generic programming is validated against testing results from University of Kaiserslautern. Finally, two illustrative examples for applying this macro element approach are presented. In the first example how to obtain the constitutive relationships of macro element is demonstrated. With certain assumptions for typical composite frame the constitutive relationships can be represented by bilinear laws for the macro bending and shear states that are then coupled by a two-dimensional surface law with yield and failure surfaces. In second example a scaling concept that combines sophisticated local models with a frame analysis using a macro element approach is presented as a practical application of this numerical model.

Understanding Recreational Services of Urban Riverfront Space for Planning Purposes

In the process of urbanization, natural and semi-natural landscapes are increasingly cherished as open space and recreational resource. Urban rivers are part of this kind of resource and thus play an important role in managing urban resilience and health. Employing the example of Tianjin, this doctoral dissertation research aims at learning to understand how to plan and design for the interface zones between urban water courses and for the land areas adjacent to such water courses. This research also aims at learning how to link waterfront space with other urban space in order to make a recreational space system for the benefit of people. Five questions of this dissertation are: 1) what is the role of rivers in spatial and open space planning? 2) What are the human needs regarding outdoor open space? 3) How do river and water front spatial structures affect people's recreational activities? 4) How to define the recreational service of urban river and waterfront open space? 5) How might answering these question change planning and design of urban open space? Quantitative and qualitative empirical approaches were combined in this study for which literature review and theoretical explorations provide the basis. Empirical investigations were conducted in the city of Tianjin. The quantitative approach includes conducting 267 quantitative interviews, and the qualitative approach includes carrying out field observations and mappings. GIS served to support analysis and visualization of empirical information that was generated through this study. By responding to the five research questions, findings and lessons include the following: 1) In the course of time rivers have gained importance in all levels and scales of spatial planning and decision making. Regarding the development of ecological networks, mainly at national scale, rivers are considered significant linear elements. Regarding regional and comprehensive development, river basins and watersheds are often considered as the structural link for strategic ecological, economic, social and recreational planning. For purposes of urban planning, particularly regarding recreational services in cities, the distribution of urban open spaces often follows the structure of river systems. 2) For the purpose of classifying human recreational needs that relate to outdoor open space Maslow's hierarchy of human needs serves as theoretical basis. The classes include geographical, safety, physiological, social and aesthetic need. These classes serve as references while analyzing river and waterfront open space and other kinds of open space. 3) Regarding the question how river and waterfront spatial structures might affect people's recreational activities, eight different landscape units were identified and compared in the case study area. Considering the thermal conditions of Tianjin, one of these landscape units was identified as affording the optimal spatial arrangement which mostly meets recreational needs. The size and the shape of open space, and the plants present in an open space have been observed as being most relevant regarding recreational activities. 4) Regarding the recreational service of urban river and waterfront open space the results of this research suggest that the recreational service is felt less intensively as the distances between water 183 front and open space user’s places of residence are increasing. As a method for estimating this ‘Service Distance Effect’ the following formula may be used: Y = a*ebx. In this equation Y means the ‘Service Distance’ between homes and open space, and X means the percentage of the people who live within this service distance. Coefficient "a" represents the distance of the residential area nearest to the water front. The coefficient "b" is a comprehensive capability index that refers to the size of the available and suitable recreational area. 5) Answers found to the questions above have implications for the planning and design of urban open space. The results from the quantitative study of recreational services of waterfront open space were applied to the assessment of river-based open space systems. It is recommended that such assessments might be done employing the network analysis function available with any GIS. In addition, several practical planning and designing suggestions are made that would help remedy any insufficient base for satisfying recreational needs. The understanding of recreational need is considered helpful for the proposing planning and designing ideas and for the changing of urban landscapes. In the course of time Tianjin's urban water system has shrunk considerably. At the same time rivers and water courses have shaped Tianjin's urban structure in noticeable ways. In the process of urbanization water has become increasingly important to the citizens and their everyday recreations. Much needs to be changed in order to improve recreational opportunities and to better provide for a livable city, most importantly when considering the increasing number of old people. Suggestions made that are based on results of this study, might be implemented in Tianjin. They are 1) to promote the quality of the waterfront open space and to make all linear waterfront area accessible recreational spaces. Then, 2), it is advisable to advocate the concept of green streets and to combine green streets with river open space in order to form an everyday recreational network. And 3) any sound urban everyday recreational service made cannot rely on only urban rivers; the whole urban structure needs to be improved, including adding small open space and optimize the form of urban communities, finally producing a multi-functional urban recreational network.

Interface issues in the ESCHER visual database editor

Presentation at the 1997 Dagstuhl Seminar "Evaluation of Multimedia Information Retrieval", Norbert Fuhr, Keith van Rijsbergen, Alan F. Smeaton (eds.), Dagstuhl Seminar Report 175, 14.04. - 18.04.97 (9716). - Abstract: This presentation will introduce ESCHER, a database editor which supports visualization in non-standard applications in engineering, science, tourism and the entertainment industry. It was originally based on the extended nested relational data model and is currently extended to include object-relational properties like inheritance, object types, integrity constraints and methods. It serves as a research platform into areas such as multimedia and visual information systems, QBE-like queries, computer-supported concurrent work (CSCW) and novel storage techniques. In its role as a Visual Information System, a database editor must support browsing and navigation. ESCHER provides this access to data by means of so called fingers. They generalize the cursor paradigm in graphical and text editors. On the graphical display, a finger is reflected by a colored area which corresponds to the object a finger is currently pointing at. In a table more than one finger may point to objects, one of which is the active finger and is used for navigating through the table. The talk will mostly concentrate on giving examples for this type of navigation and will discuss some of the architectural needs for fast object traversal and display. ESCHER is available as public domain software from our ftp site in Kassel. The portable C source can be easily compiled for any machine running UNIX and OSF/Motif, in particular our working environments IBM RS/6000 and Intel-based LINUX systems. A porting to Tcl/Tk is under way.

Analysen der beiden cis-regulierenden Sequenzelemente translational control element (TCE) und cytoplasmic polyadenylation element (CPE) in der Drosophila-Spermatogenese

Ein essentieller Bestandteil in dem Mechanismus der Translationskontrolle sind RNA-Pro­tein-Wechselwirkungen. Solche Interaktionen konnten in Translationssystemen an zwei unabhängigen cis-regulierenden Elementen durch in vitro-Bindungsanalysen mit individu­ellen rekombinanten Proteinen dokumentiert werden. Im Fall des translational control elements (TCE), welches ein konserviertes Sequenz-Ele­ment in der Mst(3)CGP-Genfamilie darstellt, wird eine negative Translationskontrolle durch die Bindung der Proteine CG3213, CG12470, CG1898, dFMR1, Exuperantia und Orb2 an diese Sequenz vermittelt (Stinski, 2011). Neben den in Bindungsstudien positiv getesteten Kandidaten dFMR1 und Orb2 (Stinski, 2011) wurde in der vorliegenden Dis­sertation CG3213 als weiterer direkter Bindungspartner an das TCE dokumentiert. Ein Abgleich der genomweiten Zusammenstellung von Proteininteraktionen in der Datenbank InterologFinder lieferte zwei weitere potentielle Kandidaten: CG34404 und CG3727. Al­lerdings schließen Northern-Analysen und das Proteinexpressionsmuster eine zentrale Rolle in der Drosophila-Spermatogenese für diese nahezu aus. In Kolokalisationsstudien einiger TCE-Komplex-Kandidaten mit CG3213 als Referenz konnten eindeutige Überein­stimmungen der Fluoreszenzmuster mit CG12470 in der postmeiotischen Phase be­schrieben werden, wohingegen mit Orb2 (postmeiotisch) und CG1898 (prämeiotisch) nur eine geringe Kolokalisation erkannt wurde. Punktstrukturen in den Verteilungsmustern sowohl von CG3213 als auch von CG12470 ließen sich nicht mit ER- und mitochondrien­spezifischen Markern korrelieren. Im Anschluss der Meiose konnte eine deutliche Intensitätserhöhung des CG3213-Proteins beobachtet werden, was eventuell durch eine veränderte Translationseffizienz zustande kommen könnte. Exuperantia (Exu) stellt einen bekannten Regulator für eine Reihe von translationskontrollierten mRNAs dar (Wang und Hazelrigg, 1994). Die Quantifizierungen der CG3213-mRNA in exu-mutantem Hintergrund bestätigen, dass auch die Transkript­menge der CG3213-mRNA durch Exu reguliert wird, was die obige Interpretation stützen würde. Für das zweite cis-regulierende Element, das cytoplasmic polyadenylation element (CPE), konnte eine direkte Bindung mit dem CPEB-Homolog in Drosophila (Orb2) gezeigt wer­den, welches auch eine Komponente des mst87F-RNP-Komplexes ist. Ein vermuteter Interaktionspartner dieses CPEBs ist Tob, weshalb die Verteilung beider Proteine in einem Kombinationsstamm verglichen wurde. In dem teilweise übereinstimmenden Fluoreszenz­muster ist Tob an den distalen Spermatidenenden auffallend konzentriert. Das gesamte Tob-Muster jedoch legt eine Verteilung in den Mitochondrien nahe, wie die MitoTracker®-Färbung belegt. Somit wurde erstmals ein Mitglied der Tob/BTG-Genfamilie in der Droso­phila-Spermatogenese mit Mitochondrien in Verbindung gebracht. Die Lokalisierung die­ser Proteine ist bislang unklar, jedoch konnte eine Kernlokalisation trotz der N-terminalen NLS-Sequenz mit Hilfe einer Kernfärbung ausgeschlossen werden.

Pi: A Parallel Architecture Interface for Multi-Model Execution

This thesis defines Pi, a parallel architecture interface that separates model and machine issues, allowing them to be addressed independently. This provides greater flexibility for both the model and machine builder. Pi addresses a set of common parallel model requirements including low latency communication, fast task switching, low cost synchronization, efficient storage management, the ability to exploit locality, and efficient support for sequential code. Since Pi provides generic parallel operations, it can efficiently support many parallel programming models including hybrids of existing models. Pi also forms a basis of comparison for architectural components.

An Immersed Interface Method for the Incompressible Navier-Stokes Equations in Irregular Domains

We present an immersed interface method for the incompressible Navier Stokes equations capable of handling rigid immersed boundaries. The immersed boundary is represented by a set of Lagrangian control points. In order to guarantee that the no-slip condition on the boundary is satisfied, singular forces are applied on the fluid at the immersed boundary. The forces are related to the jumps in pressure and the jumps in the derivatives of both pressure and velocity, and are interpolated using cubic splines. The strength of singular forces is determined by solving a small system of equations at each time step. The Navier-Stokes equations are discretized on a staggered Cartesian grid by a second order accurate projection method for pressure and velocity.

Reforç d’un element estructural mitjançant l’adhesió de làmines de compòsits reforçats amb fibres (FRP)

Aquest treball final de carrera és un estudi del reforç d’un element estructural de formigó per mitjà de fibres FRP. Podem assimilar-lo a una guia pràctica per tal que un enginyer amb coneixements de construcció, pugui reforçar un membre que ha sofert danys produïts per aguantar càrregues, oscil·lacions, etc.per les que no havia estat dissenyat. El projecte conté teoria del FRP per tal de conèixer el material que utilitzarem pel nostre reforç, les normatives i prenormatives que s’utilitzen per fer el disseny, i un exemple pràctic de càlcul del reforç d’una biga sotmesa a flexió i el confinament d’un pilar, que són les dues opcions més utilitzades per reforçar amb FRP. El reforç d’estructures de formigó és el camp de la construcció on més ràpidament i amb major èxit s’estan aplicant els reforços amb FRP, degut a les propietats tant avantatjoses que presenten, entre altres, resistència a la corrosió i lleugeresa, que es tradueix en estalvi de transport i posada en obra

El Bosc, element clau d'un paisatge i d'una comunitat

Aquest treball és un resum de la Memòria de Llicenciatura El Bosc, element clau d’un paisatge i d’una comunitat. La seva percepció per part dels pagesos de l’Alta Garrotxa. Assaig metodològic, llegida el 18 de desembre de 1981 a la Universitat Autònoma de Barcelona