Optical analysis of the light emission from porous silicon: a hybrid polyatom surface-coupled fluorophor

The most extensive data set yet generated correlating photoluminescence excitation (PLE) and photoluminescence (PL) spectra is presented for aged (equilibrated) porous silicon (PS) samples. The observed features, which are temperature independent over the range 10-300 K, show a detailed correlation with the results of photoacoustic spectroscopy (PAS) and with molecular electronic structure calculations. The observed energy level patterns are reproduced in the photoabsorption (PA) of PS films released after the etching of a silicon wafer. It is concluded that the energy level pattern found for the photoluminescing surface of PS results from a structure which is neither uniquely molecule- or bulk-like but represents a hybrid form for which the density of states associated with a polyatomic vibrationally excited surface-bound fluorophor dominates the nature of the observed features which are not those of a semiconductor. These fluorophor features are broadened and shifted to lower excitation energy as a result of the intimate presence of the silicon surface to which the fluorophor is bound. The dominance of the surface-bound fluorophor accounts for the temperature-independent PLE and PL features. The observed spectral features are thus suggested to be the result of a strong synergistic interaction in which the silicon surface influences the location of surface-bound fluorophor excited states whereas the nature of the vibrationally excited surface-bound fluorophor coupling to the silicon surface provides the mechanism for an enhanced vibronic structure dominated interaction and energy transfer. The observed PLE, PL, PAS, and PA measurements are found to be consistent with previous photovoltaic and photoconductivity measurements, correlating well with a surface-bound oxyhydride-like emitter. This study suggests the important role that the overtone structure of a molecule bound to a surface can play as one forms a hybrid system.     

Warmstarting the homogeneous and self-dual interior point method for linear and conic quadratic problems

We present two strategies for warmstarting primal-dual interior point methods for the homogeneous self-dual model when applied to mixed linear and quadratic conic optimization problems. Common to both strategies is their use of only the final (optimal) iterate of the initial problem and their negligible computational cost. This is a major advantage when compared to previously suggested strategies that require a pool of iterates from the solution process of the initial problem. Consequently our strategies are better suited for users who use optimization algorithms as black-box routines which usually only output the final solution. Our two strategies differ in that one assumes knowledge only of the final primal solution while the other assumes the availability of both primal and dual solutions. We analyze the strategies and deduce conditions under which they result in improved theoretical worst-case complexity. We present extensive computational results showing work reductions when warmstarting compared to coldstarting in the range 30–75% depending on the problem class and magnitude of the problem perturbation. The computational experiments thus substantiate that the warmstarting strategies are useful in practice.     

On the solid solution of the spinel phase in the system NiO-Al2O3

The solid solubility of Al₂O₃ in NiAl₂O₄ spinel has been investigated by powder X-ray diffraction of samples prepared by solid state synthesis. The solid solution region found was in agreement with a previous report. The cubic cell parameter of the spinel solid solution was observed to decrease with increasing alumina content. Spinel with high alumina content was shown to be close to an inverse spinel as previously reported for stoichiometric NiAl₂O₄ and the inversion parameter proved to be relatively independent of the overall composition.     

Types of von Neumann algebras associated with extremal invariant states

A globalized version of the following is proved. Let be a factor acting on a Hilbert space ,G a group of unitary operators on inducing automorphisms of ,x a vector separating and cyclic for which is up to a scalar multiple the unique vector invariant under the unitaries inG. Then either is of type III or _x is a trace of . The theorem is then applied to study the representations due to invariant factors state of asymptotically abelianC*-algebras, and to show that in quantum field theory certain regions in the Minkowski space give type III factors.     

On the completeness of eigenfunctions of some higher order operators

The completeness of diverse eigenfunction systems is of interest, e.g., in connection with their use for expansion purposes. Whereas second-order operators have been treated extensively, it is more difficult to find valid proofs even for comparatively simple fourth- and higher-order operators. A criterion is developed that allows known properties of second-order differential operators to be used as a basis for conclusions regarding the completeness of the eigenfunctions of related fourth-order operators. The completeness of the “flatclamped-plate modes” is proved as an example, and it is demonstrated that the detailed form of the “conditions of finiteness at the singular point” can be crucial for the definition of operators corresponding to differential expressions with singular points.     

Polymerization of vinyl chloride at reduced monomer accessibility. III. Polymerization kinetics and molecular structure using PVC latex as seed

Vinyl chloride was polymerized at 53–97% of the saturation pressure in a water-suspended system at 55°C with an emulsion PVC latex as seed. A water-soluble initiator was used in various concentrations. The monomer was continuously charged as vapor from a storage vessel kept at lower temperature. Characterization included determination of molecular weight distribution and degree of long-chain branching by gel chromatography and viscometry and by thermal dehydrochlorination. To avoid diffusion control intense agitation was necessary. At a certain conversion, aggregation of primary particles resulted in restricted polymerization rate. Before aggregation, formation of new particles did not occur as the number of particles was high enough to ensure capture of all oligoradicals. The kinetic equation accepted for ordinary emulsion polymerization of vinyl chloride was qualitatively found to be valid after the pressure drop as well. Decreased termination rate may result in increased polymerization rate at reduced monomer concentration, i.e., a gel effect, especially at low particle numbers and high polymer contents. The molecular weight decreased with decreasing monomer concentration. This is in accordance with the new mechanism suggested for chain transfer to monomer starting with occasional head-to-head additions.     

Ozonolysis of naphthoquinones—I Ozonolysis of 1:4-naphthoquinone in chloroform

During ozonisation of 1:4-naphthoquinone in chloroform at −5 to −8° about 70 per cent undergoes anomalous ozonolysis forming phenylglyoxal-o-carboxylic acid and probably carbon monoxide. The remaining 30 per cent forms a normal ozonide which rearranges to a mixed anhydride of formic acid and phenylglyoxal-o-carboxylic acid. Sodium iodide reduction of the normal ozonide produces o-phenylenediglycolaldehyde. An intramolecular benzoin condensation of this substance is discussed.     

REPAIR OF PSORALEN PLUS NEAR ULTRAVIOLET LIGHT DAMAGE IN BACTERIOPHAGES T3 AND T4

Abstract— Repair of T3 and T4 DNA damaged by treatment with 8-methoxypsoralen plus near UV (PNUV) has been investigated. It is shown that the excision repair mechanisms of the host cell can repair a substantial fraction of the psoralen-DNA mono-adducts in T3 DNA, but cannot by themselves repair crosslinks. In contrast neither the excision repair system of the host nor the phage coded v gene endonuclease is involved in the repair of psoralen adducts in T4 DNA. Multiplicity reactivation is effective in the recovery of T4 DNA containing psoralen-DNA mono-adducts, but is ineffective in the recovery of crosslinked phages. Comparisons of the lethality of PNUV treatment and the number of crosslinks induced in T4 DNA show clearly that mono-adducts are lethal to this phage. Both T3 and T4, however, appear to effectively repair many mono-adducts by postreplicational repair.     

The central role of the metal ion for photoactivity: Zn– vs. Ni–Mabiq

Photoredox catalysts are integral components of artificial photosystems, and have recently emerged as powerful tools for catalysing numerous organic reactions. However, the development of inexpensive and efficient earth-abundant photoredox catalysts remains a challenge. We here present the photochemical and photophysical properties of a Ni–Mabiq catalyst ([Ni^II(Mabiq)]OTf (1); Mabiq = 2-4:6-8-bis(3,3,4,4-tetramethyldihydropyrrolo)-10-15-(2,2-biquinazolino)-[15]-1,3,5,8,10,14-hexaene1,3,7,9,11,14-N₆)—and of a Zn-containing analogue ([Zn^II(Mabiq)OTf] (2))—using steady state and time resolved optical spectroscopy, time-dependent density functional theory (TDDFT) calculations, and reactivity studies. The Ni and Zn complexes exhibit similar absorption spectra, but markedly different photochemical properties. These differences arise because the excited states of 2 are ligand-localized, whereas metal-centered states account for the photoactivity of 1. The distinct properties of the Ni and Zn complexes are manifest in their behavior in the photo-driven aza-Henry reaction and oxidative coupling of methoxybenzylamine.

The development of earth-abundant photoredox catalysts remains a challenge. Studies of Ni- and Zn-Mabiq complexes demonstrate how the coordinating metal ion influences the photochemistry, photodynamics and reactivity of photocatalysts.