Crystallization Temperature Limit of (Ba,Sr)TiO<Subscript>3</Subscript> Thin Films Prepared by a Non Oxocarbonate Phase Forming CSD Route

A new chemical solution deposition (CSD) route for the fabrication of Ba_0.7Sr_0.3TiO₃ (BST) thin films has been developed which completely prevents the formation of an intermediate oxo-carbonate phase. The latter has been reported previously by several authors to be responsible for increased crystallization temperatures. Barium and strontium diaminoethoxides were synthesized starting from pure barium and strontium metal and aminoethanol. These alkoxides were found to be readily soluble in a wide range of solvents and thus were excellent candidates for the CSD process. To prepare a stable precursor solution the aminoalkoxides were dissolved in 2-butoxyethanol and then used for the deposition of BST thin films. We conclude that the minimum crystallization temperature of 600C to be independent of the formation of the oxo-carbonate phase. DTA-TGA were performed on the precursors and their solutions to study their decomposition behaviour. All films annealed at different temperatures were physically characterized by XRD, IR, and SEM. The films prepared by this route at 650C were found to have high dielectric constant and the leakage currents were comparable to BST films prepared by normal carboxylate based routes at 750C.     

Electrostatic lattice coefficients and binding energy of orthorhombic La2-x Sr x CuO4

Three valency models for orthorhombic La_2-x Sr _x CuO₄ were investigated for increasing Sr concentrationsx (0x0.21): 1. Cu²⁺Cu³⁺, 2. apex O^2–O^– and 3. in-plane O^2–O^–. All calculations were done by using structural parameters valid for the temperature range from 10 to 22 K. We thereby calculated the electrostatic interaction energy which, next to ionization potentials and electron affinities, comprises a major of the binding energyE _B of crystals. Second-order effects were accounted for by calculating the strength of ionic dipole moments induced by crystal electric fields at relevant lattice sites. Their largest strengths are comparable to the dipole moment of the water molecule. Three out of five dipoles in La_2-x Sr _x CuO₄ vanish during the transition from the orthorhombic to the tetragonal phase. The binding energy differences between the different models suggest that the system is in a state of model 1. However, the differences are very small, being in the order of 0.3 to 0.76 eV atx=0.13.     

The distribution of the likelihood ratio for mixtures of densities from the one-parameter exponential family

We here consider testing the hypothesis ofhomogeneity against the alternative of a two-component mixture of densities. The paper focuses on the asymptotic null distribution of 2 log _n , where _n is the likelihood ratio statistic. The main result, obtained by simulation, is that its limiting distribution appears pivotal (in the sense of constant percentiles over the unknown parameter), but model specific (differs if the model is changed from Poisson to normal, say), and is not at all well approximated by the conventional ₍₂₎ ² -distribution obtained by counting parameters. In Section 3, the binomial with sample size parameter 2 is considered. Via a simple geometric characterization the case for which the likelihood ratio is 1 can easily be identified and the corresponding probability is found. Closed form expressions for the likelihood ratio _n are possible and the asymptotic distribution of 2 log _n is shown to be the mixture giving equal weights to the one point distribution with all its mass equal to zero and the ²-distribution with 1 degree of freedom. A similar result is reached in Section 4 for the Poisson with a small parameter value (0.1), although the geometric characterization is different. In Section 5 we consider the Poisson case in full generality. There is still a positive asymptotic probability that the likelihood ratio is 1. The upper precentiles of the null distribution of 2 log _n are found by simulation for various populations and shown to be nearly independent of the population parameter, and approximately equal to the (1–2)100 percentiles of ₍₁₎ ² . In Sections 6 and 7, we close with a study of two continuous densities, theexponential and thenormal with known variance. In these models the asymptotic distribution of 2 log _n is pivotal. Selected (1–) 100 percentiles are presented and shown to differ between the two models.     

On the integrated density of states for crystals with randomly distributed impurities

In the present paper, we discuss spectral properties of a periodic Schrödinger operator which is perturbed by randomly distributed impurities; such operators occur as simple models for crystals (or semi-conductors) with impurities. While the spectrum itself is independent of the concentrationp of impurities, for 0<p<1, we focus our attention on the limiting behavior of the integrated density of states _p of the random Schrödinger operator, inside a spectral gap of the periodic operator, asp0. Denoting byU ₀ the set of eigenvalues (in the gap) of the reference problem having precisely one impurity (located at the origin, say), we show that the integrated density of states concentrates around the points ofU ₀, in the sense that _p (U ) is of orderp, for any fixed -neighborhoodU ofU ₀, while _p (K)C·p ², for any compact subsetK of the gap which does not intersectU .Research partially supported by Deutsche Forschungsgemeinschaft     

The UV absorption spectrum of the phenyl radical isolated in solid argon

Phenyl radicals have been generated by photodecomposition of nitrosobenzene isolated in solid argon at 12 K. In this medium the origin of the first UV absorption band of nitrosobenzene corresponding to theS ₀ S ₂ transition is found at 30260 cm^–1. Excitation with an excess energy of 2200 cm^–1 results in very efficient photodissociation. The fragments NO and phenyl are stable for many hours. Annealing of the sample above 35 K led to partial recombination and recovery of the absorption spectrum of nitrosobenzene. The UV spectrum of the phenyl radical was obtained in the wavenumber range 25000–45000 cm^–1, apparently without contamination by other species. It shows sharp lines at 25220, 33880, and 34820 cm^–1 and two broader maxima at 38360 and 41060 cm^–1. Of these only the line at 34820 cm^–1 had been assigned to the phenyl radical in earlier work. These data are compared to recent molecular orbital calculations.Dedicated to Prof. F. P. Schäfer on the occasion of his 65th birthday.     

On noise reduction methods for chaotic data

Recently proposed noise reduction methods for nonlinear chaotic time sequences with additive noise are analyzed and generalized. All these methods have in common that they work iteratively, and that in each step of the iteration the noise is suppressed by requiring locally linear relations among the delay coordinates, i.e., by moving the delay vectors towards some smooth manifold. The different methods can be compared unambiguously in the case of strictly hyperbolic systems corrupted by measurement noise of infinitesimally low level. It was found that all proposed methods converge in this ideal case, but not equally fast. Different problems arise if the system is not hyperbolic, and at higher noise levels. A new scheme which seems to avoid most of these problems is proposed and tested, and seems to give the best noise reduction so far. Moreover, large improvements are possible within the new scheme and the previous schemes if their parameters are not kept fixed during the iteration, and if corrections are included which take into account the curvature of the attracting manifold. Finally, the fact that comparison with simple low-pass filters tends to overestimate the relative achievements of these nonlinear noise reduction schemes is stressed, and it is suggested that they should be compared to Wiener-type filters.     

Stochastic dominance with nonadditive probabilities

Choquet expected utility which uses capacities (i.e. nonadditive probability measures) in place of-additive probability measures has been introduced to decision making under uncertainty to cope with observed effects of ambiguity aversion like the Ellsberg paradox. In this paper we present necessary and sufficient conditions for stochastic dominance between capacities (i.e. the expected utility with respect to one capacity exceeds that with respect to the other one for a given class of utility functions). One wide class of conditions refers to probability inequalities on certain families of sets. To yield another general class of conditions we present sufficient conditions for the existence of a probability measureP with f dC= f dP for all increasing functionsf whenC is a given capacity. Examples includen-th degree stochastic dominance on the reals and many cases of so-called set dominance. Finally, applications to decision making are given including anticipated utility with unknown distortion function.     

Two-photon spectroscopy of the low-lying singlet states of naphthalene and acenaphthene

Two-photon excitation spectra of naphthalene and acenaphthene have been measured up to 50000 cm^?1. In naphthalene. three two-photon allowed states are observed for which the symmetry assignment is confirmed by polarization. The corre- sponding transitions are also seen in acenaphthene. The experimental data are in excellent agreement with theoretical predictions.     

Chemistry of λ-2H-azaphosphirene metal complexes

In this review, important aspects of λ³-2H-azaphosphirene metal complexes are discussed in relation to synthesis, physical properties and synthetic applications; ab-initio calculations on relative energies of CH₂NP isomers and of λ³-2H-azaphosphirene metal complexes (Cr, Mo, W) are also presented. Currently, there are three routes to this unsaturated three-membered ring system, which are discussed in detail: two of them use a rearrangement of metal carbene complexes, whereas the other relies on [2+1] cycloaddition reactions of electrophilic terminal phosphanediyl complexes and carbonitriles. The structural data show characteristics of a very strained heterocyclic ring system, which partially helps to understand the reactivity of this heterocycle complex in solution. The synthetic potential of λ³-2H-azaphosphirene metal complexes is illustrated by selected examples, which demonstrate their ability to serve, under very mild conditions as precursor for various new building blocks, i.e. nitrilium phosphanylide complexes, electrophilic terminal phosphanediyl complexes and phosphavinyl-nitrene complexes.