Heavy-Atom Tunneling in Semibullvalenes: How Driving Force,Substituents, and Environment Influence the Tunneling Rates

The Cope rearrangement of selectively deuterated isotopomers of 1,5-dimethylsemibullvalene 2 a and 3,7-dicyano-1,5-dimethylsemibullvalene 2 b were studied in cryogenic matrices. In both semibullvalenes the Cope rearrangement is governed by heavy-atom tunneling. The driving force for the rearrangements is the small difference in the zero-point vibrational energies of the isotopomers. To evaluate the effect of the driving force on the tunneling probability in 2 a and 2 b , two different pairs of isotopomers were studied for each of the semibullvalenes. The reaction rates for the rearrangement of 2 b in cryogenic matrices were found to be smaller than the ones of 2 a under similar conditions, whereas differences in the driving force do not influence the rates. Small curvature tunneling (SCT) calculations suggest that the reduced tunneling rate of 2 b compared to that of 2 a results from a change in the shape of the potential energy barrier. The tunneling probability of the semibullvalenes strongly depends on the matrix environment; however, for 2 a in a qualitatively different way than for 2 b .     

Four-wave mixing in semiconductor laser amplifiers: Applications for optical communication systems

Four-wave mixing in semiconductor laser amplifiers enables various applications in photonic switching including wavelength conversion, space and time switching, optical phase conjugation, and demultiplexing. Switching times faster than 1 ps are possible.     

Algebraic properties and the finite rank problem for Toeplitz operators on the Segal-Bargmann space

We study three different problems in the area of Toeplitz operators on the Segal-Bargmann space in Cn. Extending results obtained previously by the first author and Y.L. Lee, and by the second author, we first determine the commutant of a given Toeplitz operator with a radial symbol belonging to the class Sym_>0(Cn) of symbols having certain growth at infinity. We then provide explicit examples of zero-products of non-trivial Toeplitz operators. These examples show the essential difference between Toeplitz operators on the Segal-Bargmann space and on the Bergman space over the unit ball. Finally, we discuss the “finite rank problem”. We show that there are no non-trivial rank one Toeplitz operators Tf for f∈Sym_>0(Cn). In all these problems, the growth at infinity of the symbols plays a crucial role.     

Influence of the annealing atmosphere on the properties of LiCoPO4–graphitic carbon foams composites

The investigation on the properties of LiCoPO₄–graphitic carbon foams (LCP-GCF) composites is reported in this work. The diffraction analysis (XRD) on powders confirmed the presence of LiCoPO₄ as major crystalline phase and Li₄P₂O₇ and Co₂P as secondary phases. The morphological investigation of the composites shows a layer of crystalline spongy-like material on the surface of the GCF for t?=?0 h and of acicular crystallites with different dimensions (5–50 μm) for t?≥?0.1 h. The voltammetric curves (cyclic voltammogramms) show mean values of reduction potential above 5.0 V independently of the annealing time. The LCP-GCF composites deliver a discharge-specific capacity of 76mAh g^?1 (t?=?0 h) and of 102mAh g^?1 (t?=?0.1 h) at a discharge rate of C/10 and room temperature. The electrochemical impedance spectroscopy data reveal a decrease of the electrical resistance and the improvement of the Li-ion conductivity as a function of the annealing time.     

Improved growth of solution‐deposited thin films on polycrystalline Cu(In,Ga)Se2

CdS and Zn(O,S) grown by chemical bath deposition (CBD) are well established buffer materials for Cu(In,Ga)Se₂ (CIGS) solar cells. As recently reported, a non‐contiguous coverage of CBD buffers on CIGS grains with {112} surfaces can be detected, which was explained in terms of low surface energies of the {112} facets, leading to deteriorated wetting of the chemical solution on the CIGS surface. In the present contribution, we report on the effect of air annealing of CIGS thin films prior to the CBD of CdS and Zn(O,S) layers. In contrast to the growth on the as‐grown CIGS layers, these buffer lay‐ ers grow densely on the annealed CIGS layer, even on grains with {112} surfaces. We explain the different growth behavior by increased surface energies of CIGS grains due to the annealing step, i.e., due to oxidation of the CIGS surface. Reference solar cells were processed and completed by i‐ZnO/ZnO:Al layers for CdS and by (Zn,Mg)O/ZnO:Al for Zn(O,S) buffers. For solar cells with both, CdS and Zn(O,S) buffers, air‐annealed CIGS films with improved buffer coverage resulted in higher power‐conversion efficiencies, as compared with the devices containing as‐grown CIGS layers. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Concurrent stochastic methods for global optimization

The global optimization problem, finding the lowest minimizer of a nonlinear function of several variables that has multiple local minimizers, appears well suited to concurrent computation. This paper presents a new parallel algorithm for the global optimization problem. The algorithm is a stochastic method related to the multi-level single-linkage methods of Rinnooy Kan and Timmer for sequential computers. Concurrency is achieved by partitioning the work of each of the three main parts of the algorithm, sampling, local minimization start point selection, and multiple local minimizations, among the processors. This parallelism is of a coarse grain type and is especially well suited to a local memory multiprocessing environment. The paper presents test results of a distributed implementation of this algorithm on a local area network of computer workstations. It also summarizes the theoretical properties of the algorithm.Research supported by AFOSR grant AFOSR-85-0251, ARO contract DAAG 29-84-K-0140, NSF grant DCR-8403483, and NSF cooperative agreement DCR-8420944.     

X‐ray excited optical luminescence from crystalline silicon

Synchrotron based X‐ray excited optical luminescence (XEOL) has been measured with many direct bandgap semiconductors. We present XEOL measurements on crystalline silicon (Si), obtained despite of its indirect bandgap and the consequently low luminescence efficiency. Spectra of monocrystalline and multicrystalline (mc) Si at room temperature are compared to theoretical spectra. A possible application in the synchrotron‐based research on mc‐Si is exemplified by combining XEOL, X‐ray fluorescence (XRF) spectroscopy, photoluminescence (PL) spectroscopy, and microscope images of grain boundaries. This approach can be utilized to investigate the recombination activity of metal precipitates, to analyze areas of different lifetimes on mc‐Si samples and to correlate additional material parameters to XRF measurements. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ends of iterated function systems

Guided by classical concepts, we define the notion of ends of an iterated function system and prove that the number of ends is an upper bound for the number of nondegenerate components of its attractor. The remaining isolated points are then linked to idempotent maps. A commutative diagram illustrates the natural relationships between the infinite walks in a semigroup and components of an attractor in more detail. We show in particular that, if an iterated function system is one-ended, the associated attractor is connected, and ask whether every connected attractor (fractal) conversely admits a one-ended system.     

Azole. 44.

The structure analyses of racemic 3‐chloro‐1‐(4‐morpholino‐5‐nitro­imidazol‐1‐yl)­propan‐2‐ol, C₁₀H₁₅ClN₄O₄, (II), and 3‐chloro‐1‐(5‐morpholino‐4‐nitro­imidazol‐1‐yl)­propan‐2‐ol, C₁₀H₁₅ClN₄O₄, (III), have been undertaken in order to determine the position of the morpholine residue in these two isomers. The morpholine residue in (II) is connected at the 4‐position, while in (III), it is connected at the 5‐position of the imidazole ring. The morpholine mean planes and nitro groups in the two compounds deviate from the imidazole planes to different extents. The nitro groups in (II) and (III) take part in the conjugation system of the imidazole rings. In consequence, the exocyclic C—N bonds are significantly shorter than the normal single Csp²—NO₂ bond and the nitro groups in (II) and (III) show an extraordinary stability on treatment with morpholine and piperidine [Gzella, Wrzeciono & Pöppel (1999). Acta Cryst. C 55 , 1562–1565]. In the crystal lattice, the mol­ecules of both compounds are linked by O—H?N and C—H?O intermolecular hydrogen bonds.