Dihalodimethyltin(IV) complexes of 2‐(pyrazol‐1‐ylmethyl)pyridine

Reaction of dichloro‐ and dibromodimethyltin(IV) with 2‐(pyrazol‐1‐ylmethyl)pyridine (PMP) afforded [SnMe₂Cl₂(PMP)] and [SnMe₂Br₂(PMP)] respectively. The new complexes were characterized by elemental analysis and mass spectrometry and by IR, Raman and NMR (¹H, ¹³C) spectroscopies. Structural studies by X‐ray diffraction techniques show that the compounds consist of discrete units with the tin atom octahedrally coordinated to the carbon atoms of the two methyl groups in a trans disposition (Sn? C = 2.097(5), 2.120(5) Å and 2.110(6), 2.121(6) Å in the chloro and in the bromo compounds respectively), two cis halogen atoms (Sn? Cl = 2.4908(16), 2.5447(17) Å; Sn? Br = 2.6875(11), 2.7464(9) Å) and the two donor atoms of the ligand (Sn? N = 2.407(4), 2.471(4) Å and 2.360(5), 2.455(5) Å). In both cases, the Sn? N(pyridine) bond length is markedly longer than the Sn? N(pyrazole) distance. Copyright © 2003 John Wiley & Sons, Ltd.     

A p-version finite element method for nonlinear elliptic variational inequalities in 2D

This article introduces and analyzes a p-version FEM for variational inequalities resulting from obstacle problems for some quasi-linear elliptic partial differential operators. We approximate the solution by controlling the obstacle condition in images of the Gauss–Lobatto points. We show existence and uniqueness for the discrete solution u _p from the p-version for the obstacle problem. We prove the convergence of u _p towards the solution with respect to the energy norm, and assuming some additional regularity for the solution we derive an a priori error estimate. In numerical experiments the p-version turns out to be superior to the h-version concerning the convergence rate and the number of unknowns needed to achieve a certain exactness of the approximation.     

Solution of monotone complementarity problems with locally Lipschitzian functions

The paper deals with complementarity problems CP(F), where the underlying functionF is assumed to be locally Lipschitzian. Based on a special equivalent reformulation of CP(F) as a system of equationsφ(x)=0 or as the problem of minimizing the merit functionΘ=1/2∥Φ∥ ₂ ² , we extend results which hold for sufficiently smooth functionsF to the nonsmooth case. In particular, ifF is monotone in a neighbourhood ofx, it is proved that 0 εδθ(x) is necessary and sufficient forx to be a solution of CP(F). Moreover, for monotone functionsF, a simple derivative-free algorithm that reducesΘ is shown to possess global convergence properties. Finally, the local behaviour of a generalized Newton method is analyzed. To this end, the result by Mifflin that the composition of semismooth functions is again semismooth is extended top-order semismooth functions. Under a suitable regularity condition and ifF isp-order semismooth the generalized Newton method is shown to be locally well defined and superlinearly convergent with the order of 1+p.     

Calorimetric measurement of two-photon absorption and color-center formation in ultraviolet-window materials

Intensity-dependent absorption of 25 ns excimer laser pulses in common UV-window materials was investigated. By employing a calorimetric technique which provides greatly enhanced sensitivity compared to transmissive measurements, two-photon absorption coefficients were determined at intensities of 2–80 MW/cm² and found to be in good agreement with previous measurements at 10–100 GW/cm². Also, color-center formation in fused silica was observed. It was possible to quantify transient and cumulative effects as a function of intensity.     

Quasipotentials for simple noisy maps with complicated dynamics

The theory of nonequilibrium potentials or quasipotentials is a physically motivated approach to small random perturbations of dynamical systems, leading to exponential estimates of invariant probabilities and mean first exit times. In the present article we develop the mathematical foundation of this theory for discrete-time systems, following and extending the work of Freidlin and Wentzell, and Kifer. We discuss strategies for calculating and estimating quasipotentials and show their application to one-dimensionalS-unimodal maps. The method proves to be especially suited for describing the noise scaling behavior of invariant probabilities, e.g., for the map occurring as the limit of the Feigenbaum period-doubling sequence. We show that the method allows statements about the scaling behavior in the case of localized noise, too, which does not originally lie within the scope of the quasipotential formalism.     

Particle Characterization by Projected Area Determination

The projected areas of non-spherical particles do not represent an unambiguous particle characteristic. Depending on the orientation towards a constant observational direction, different projected areas result. The spectrum of all projected area values of a particle, if determined representatively, gives the probability with which a certain value is obtained by a single measurement. In this work, the frequency distributions of different examples of test objects were both calculated and measured. The objects were a cube, a rectangular parallelepiped and also three model agglomerates consisting of spheres of the same size. Instead of just one projected area, during each measuring procedure three projected areas from three orthogonal directions can be obtained. A mean value is then calculated to reduce the ambiguity of the particle characteristic and enhance the resolution. A suitable measurement set-up is introduced. The results of calculation and measurement are compared for observation from just one direction and also simultaneous observation from three directions. The frequency distributions of the equivalent diameters of the particle projected areas show a characteristic trend of the total curve with remarkable properties. The simultaneous measurement of three values from mutually orthogonal directions and their mean value calculation result in a much narrower distribution. In this case, a non-sphericity factor can additionally be calculated, whose frequency distribution contains information in a characteristic manner about the degree to which the particle shape differs from a sphere.