Versatile binding properties of a di-2-pyridyl ketone nicotinoylhydrazone ligand: Crystal structure of a Cu(II) complex

Six new copper complexes of di-2-pyridyl ketone nicotinoylhydrazone (HDKN) have been synthesized. The complexes have been characterized by a variety of spectroscopic techniques and the structure of [Cu(DKN)2]·H2O has been determined by single crystal X-ray diffraction. The compound [Cu(DKN)2]·H2O crystallized in the monoclinic space group P21 and has a distorted octahedral geometry. The IR spectra revealed the presence of variable modes of chelation for the investigated ligand. The EPR spectra of compounds [Cu2(DKN)2( -N3)2] and [Cu2(DKN)2( -NCS)2] in polycrystalline state suggest a dimeric structure as they exhibited a half field signal, which indicate the presence of a weak interaction between two Cu(II) ions in these complexes

An approximation method using approximate approximations

The aim of this paper is to extend the method of approximate approximations to boundary value problems. This method was introduced by V. Maz'ya in 1991 and has been used until now for the approximation of smooth functions defined on the whole space and for the approximation of volume potentials. In the present paper we develop an approximation procedure for the solution of the interior Dirichlet problem for the Laplace equation in two dimensions using approximate approximations. The procedure is based on potential theoretical considerations in connection with a boundary integral equations method and consists of three approximation steps as follows. In a first step the unknown source density in the potential representation of the solution is replaced by approximate approximations. In a second step the decay behavior of the generating functions is used to gain a suitable approximation for the potential kernel, and in a third step Nyström's method leads to a linear algebraic system for the approximate source density. For every step a convergence analysis is established and corresponding error estimates are given.

Beschreibung von Oberflächenphänomenen durch relativistische Clusterrechnungen unter Verwendung eines Einbettungsverfahrens

For the theoretical investigation of local phenomena (adsorption at surfaces, defects or impurities within a crystal, etc.) one can assume that the effects caused by the local disturbance are only limited to the neighbouring particles. With this model, that is well-known as cluster-approximation, an infinite system can be simulated by a much smaller segment of the surface (Cluster). The size of this segment varies strongly for different systems. Calculations to the convergence of bond distance and binding energy of an adsorbed aluminum atom on an Al(100)-surface showed that more than 100 atoms are necessary to get a sufficient description of surface properties. However with a full-quantummechanical approach these system sizes cannot be calculated because of the effort in computer memory and processor speed. Therefore we developed an embedding procedure for the simulation of surfaces and solids, where the whole system is partitioned in several parts which itsself are treated differently: the internal part (cluster), which is located near the place of the adsorbate, is calculated completely self-consistently and is embedded into an environment, whereas the influence of the environment on the cluster enters as an additional, external potential to the relativistic Kohn-Sham-equations. The basis of the procedure represents the density functional theory. However this means that the choice of the electronic density of the environment constitutes the quality of the embedding procedure. The environment density was modelled in three different ways: atomic densities; of a large prepended calculation without embedding transferred densities; bulk-densities (copied). The embedding procedure was tested on the atomic adsorptions of 'Al on Al(100) and Cu on Cu(100). The result was that if the environment is choices appropriately for the Al-system one needs only 9 embedded atoms to reproduce the results of exact slab-calculations. For the Cu-system first calculations without embedding procedures were accomplished, with the result that already 60 atoms are sufficient as a surface-cluster. Using the embedding procedure the same values with only 25 atoms were obtained. This means a substantial improvement if one takes into consideration that the calculation time increased cubically with the number of atoms. With the embedding method Infinite systems can be treated by molecular methods. Additionally the program code was extended by the possibility to make molecular-dynamic simulations. Now it is possible apart from the past calculations of fixed cores to investigate also structures of small clusters and surfaces. A first application we made with the adsorption of Cu on Cu(100). We calculated the relaxed positions of the atoms that were located close to the adsorption site and afterwards made the full-quantummechanical calculation of this system. We did that procedure for different distances to the surface. Thus a realistic adsorption process could be examined for the first time. It should be remarked that when doing the Cu reference-calculations (without embedding) we begun to parallelize the entire program code. Only because of this aspect the investigations for the 100 atomic Cu surface-clusters were possible. Due to the good efficiency of both the parallelization and the developed embedding procedure we will be able to apply the combination in future. This will help to work on more these areas it will be possible to bring in results of full-relativistic molecular calculations, what will be very interesting especially for the regime of heavy systems.

Ground state correlation energy of the Be-sequence for Z = 4-20 in MCDF approximation

The ground state (J = 0) electronic correlation energy of the 4-electron Be-sequence is calculated in the Multi-Configuration Dirac-Fock approximation for Z = 4-20. The 4 electrons were distributed over the configurations arising from the 1s, 2s, 2p, 3s, 3p and 3d orbitals. Theoretical values obtained here are in good agreement with experimental correlation energies.

Precise calculations of atomic electron binding energies in fermium

The comparison between the experimental binding energies for the K, L, and M electrons for fermium and the results of our Dirac-Fock calculation, taking into account all tractable corrections, leads to agreement within about 20 eV. This shows that the present method of calculation is an adequate description of this problem and that nonlinear electrodynamical effects will not be present in nature or will be smaller than 1% compared to the values recently proposed. It is found that the energies of electronic transitions can now be used to estimate the nuclear radius.

Zur Approximation der Gleichungen von Navier-Stokes

In der vorliegenden Arbeit betrachten wir die Strömung einer zähen, inkompressiblen, instationären Flüssigkeit in einem dreidimensionalen beschränkten Gebiet, deren Verhalten wird mit den instationären Gleichungen von Navier-Stokes beschrieben. Diese Gleichungen gelten für viele wichtige Strömungsprobleme, beispielsweise für Luftströmungen weit unterhalb der Schallgeschwindigkeit, für Wasserströmungen, sowie für flüssige Metalle. Im zweidimensionalen Fall konnten für die Navier-Stokes-Gleichungen bereits weitreichende Existenz-, Eindeutigkeits- und Regularitätsaussagen bewiesen werden. Im allgemeinen dreidimensionalen Fall, falls also die Daten keinen Kleinheitsannahmen unterliegen, hat man bisher lediglich Existenz und Eindeutigkeit zeitlich lokaler starker Lösungen nachgewiesen. Außerdem existieren zeitlich global so genannte schwache Lösungen, deren Regularität für den Nachweis der Eindeutigkeit im dreidimensionalen Fall allerdings nicht ausreicht. Somit bleibt die Lücke zwischen der zeitlich lokalen, eindeutigen starken Lösung und den zeitlich globalen, nicht eindeutigen schwachen Lösungen der Navier-Stokes-Gleichungen im dreidimensionalen Fall weiterhin offen. Das renommierte Clay Mathematics Institute hat dieses Problem zu einem von sieben Millenniumsproblemen erklärt und für seine Lösung eine Million US-Dollar ausgelobt. In der vorliegenden Arbeit wird ein neues Approximationsverfahren für die Navier-Stokes-Gleichungen entwickelt, das auf einer Kopplung der Eulerschen und Lagrangeschen Beschreibung zäher Strömungen beruht.

Asymptotic model for shape resonance control of diatomics by intense non-resonant light: universality in the single-channel approximation

Non-resonant light interacting with diatomics via the polarizability anisotropy couples different rotational states and may lead to strong hybridization of the motion. The modification of shape resonances and low-energy scattering states due to this interaction can be fully captured by an asymptotic model, based on the long-range properties of the scattering (Crubellier et al 2015 New J. Phys. 17 045020). Remarkably, the properties of the field-dressed shape resonances in this asymptotic multi-channel description are found to be approximately linear in the field intensity up to fairly large intensity. This suggests a perturbative single-channel approach to be sufficient to study the control of such resonances by the non-resonant field. The multi-channel results furthermore indicate the dependence on field intensity to present, at least approximately, universal characteristics. Here we combine the nodal line technique to solve the asymptotic Schrödinger equation with perturbation theory. Comparing our single channel results to those obtained with the full interaction potential, we find nodal lines depending only on the field-free scattering length of the diatom to yield an approximate but universal description of the field-dressed molecule, confirming universal behavior.

A Government-Binding Based Parser for Warlpiri, a Free-Word Order Language

Free-word order languages have long posed significant problems for standard parsing algorithms. This thesis presents an implemented parser, based on Government-Binding (GB) theory, for a particular free-word order language, Warlpiri, an aboriginal language of central Australia. The words in a sentence of a free-word order language may swap about relatively freely with little effect on meaning: the permutations of a sentence mean essentially the same thing. It is assumed that this similarity in meaning is directly reflected in the syntax. The parser presented here properly processes free word order because it assigns the same syntactic structure to the permutations of a single sentence. The parser also handles fixed word order, as well as other phenomena. On the view presented here, there is no such thing as a "configurational" or "non-configurational" language. Rather, there is a spectrum of languages that are more or less ordered. The operation of this parsing system is quite different in character from that of more traditional rule-based parsing systems, e.g., context-free parsers. In this system, parsing is carried out via the construction of two different structures, one encoding precedence information and one encoding hierarchical information. This bipartite representation is the key to handling both free- and fixed-order phenomena. This thesis first presents an overview of the portion of Warlpiri that can be parsed. Following this is a description of the linguistic theory on which the parser is based. The chapter after that describes the representations and algorithms of the parser. In conclusion, the parser is compared to related work. The appendix contains a substantial list of test cases ??th grammatical and ungrammatical ??at the parser has actually processed.

Feature Point Detection and Curve Approximation for Early Processing of Freehand Sketches

Freehand sketching is both a natural and crucial part of design, yet is unsupported by current design automation software. We are working to combine the flexibility and ease of use of paper and pencil with the processing power of a computer to produce a design environment that feels as natural as paper, yet is considerably smarter. One of the most basic steps in accomplishing this is converting the original digitized pen strokes in the sketch into the intended geometric objects using feature point detection and approximation. We demonstrate how multiple sources of information can be combined for feature detection in strokes and apply this technique using two approaches to signal processing, one using simple average based thresholding and a second using scale space.

Measure Fields for Function Approximation

The computation of a piecewise smooth function that approximates a finite set of data points may be decomposed into two decoupled tasks: first, the computation of the locally smooth models, and hence, the segmentation of the data into classes that consist on the sets of points best approximated by each model, and second, the computation of the normalized discriminant functions for each induced class. The approximating function may then be computed as the optimal estimator with respect to this measure field. We give an efficient procedure for effecting both computations, and for the determination of the optimal number of components.

An Equivalence Between Sparse Approximation and Support Vector Machines

In the first part of this paper we show a similarity between the principle of Structural Risk Minimization Principle (SRM) (Vapnik, 1982) and the idea of Sparse Approximation, as defined in (Chen, Donoho and Saunders, 1995) and Olshausen and Field (1996). Then we focus on two specific (approximate) implementations of SRM and Sparse Approximation, which have been used to solve the problem of function approximation. For SRM we consider the Support Vector Machine technique proposed by V. Vapnik and his team at AT&T Bell Labs, and for Sparse Approximation we consider a modification of the Basis Pursuit De-Noising algorithm proposed by Chen, Donoho and Saunders (1995). We show that, under certain conditions, these two techniques are equivalent: they give the same solution and they require the solution of the same quadratic programming problem.

Convergence Rates of Approximation by Translates

In this paper we consider the problem of approximating a function belonging to some funtion space Φ by a linear comination of n translates of a given function G. Ussing a lemma by Jones (1990) and Barron (1991) we show that it is possible to define function spaces and functions G for which the rate of convergence to zero of the erro is 0(1/n) in any number of dimensions. The apparent avoidance of the "curse of dimensionality" is due to the fact that these function spaces are more and more constrained as the dimension increases. Examples include spaces of the Sobolev tpe, in which the number of weak derivatives is required to be larger than the number of dimensions. We give results both for approximation in the L2 norm and in the Lc norm. The interesting feature of these results is that, thanks to the constructive nature of Jones" and Barron"s lemma, an iterative procedure is defined that can achieve this rate.

A First approximation to the realism/idealism debate about the external world

El text intenta fer una primera aproximació al debat contemporani entre realistes i anti-realistes sobre el món empíric, centrant-se en les posicions de Putnam i Nagel. El seu objectiu principal és el d'entendre les motivacions de les posicions i l'estructura actual del debat, i el d'establir les característiques que hauria de tenir qualsevol posició satisfactòria