Photodetachment of NO−2; experimental evidence for a new isomer

The relative cross section for the gas phase photodetachment of electrons has been determined for nitrite ions in the wavelength region 280–740 nm (4.43-1.68 eV). The vertical detachment energy for ONO^? has been determined to be ≈ 2.8 eV. Evidence is presented for a new isomer of NO^?₂.     

A coordinate-space study of kowalski's three-term separable approximation for the fully off-shell two-nucleon T-matrix

Using elementary coordinate-space methods, we show that a three-term separable approximate fully off-shell T-matrix proposed by Kowalski can be reduced to a simpler expression. This T-matrix incorporates off-shell unitarity exactly, is exact half off the energy shell, and is free from the spurious poles that arise in the Noyes approximation. However, numerical tests employing the wave-function model of Picker, Redish, and Stephenson show that for realistic ¹S_o interactions, the Noyes approximation is more accurate than Kowalski's approximation except near the spurious pole at 250 MeV. We give a plausible explanation of this result.     

Partition function zeros for the two-dimensional Ising model

The distribution of complex temperature zeros of the partition function of the two-dimensional Ising model in the absence of a magnetic field is investigated. For anisotropic square and triangular lattices the distribution function is two-dimensional and satisfies a partial differential equation derived from a generalized scaling theory. Corresponding results for the isotropic square, triangular and honeycomb lattices are also presented.     

Analytical derivation of a formula for the reduction of computation time by the voxel crossing technique used in room acoustical simulation

Computation times of room acoustical simulation algorithms still suffer from the time consuming search for ray-wall-intersections. Spatial subdivision may speed up ray tracing considerably. For room acoustics, where the number of surface polygons (walls) is not so high, the voxel technique appears suitable. The voxel crossing algorithm is very fast. However, its performance was not yet investigated up to now. Voxels are small cubes by which the space is subdivided periodically. The advantage: Only in the rare case a voxel intersects a wall the intersection point needs to be computed. In this paper, by estimating the probabilities of such intersections, an analytical formula is derived, by which the optimum degree of spatial subdivision and the factor of acceleration of the algorithm can be forecasted. It turns out that the computation time increases only with instead of with K₀ (the number of polygons of the room). Thus, on a modern PC, computation time for a full room acoustical simulation even for highly complicated rooms may be reduced by a factor in the order of 100, i.e. to a few seconds.     

Determination of the interfacial characteristics of a series of bolaamphiphilic poly(fluorooxetane) surfactants through molecular dynamics simulation

Constant surface tension (NgammaT) and constant volume (NVT) molecular dynamics simulations have been conducted on a series of bolaamphiphilic alpha,varpi-(diammonium disulfato)poly(fluorooxetane)s and on a typical "long-chain" anionic fluorosurfactant used to improve the flow-and-leveling characteristics of aqueous coatings, to compare their behavior at a water/air interface. Recent research has shown that the poly(fluorooxetane) surfactants considered in this paper could serve as an effective substitute for traditional fluorosurfactants used in flow-and-leveling applications.(1) From molecular dynamics simulation, we have determined the saturated interfacial area per surfactant, interfacial area per surfactant as a function of surface tension, density profiles, the degree of hydration for various atoms in each surfactant, the degree of counterion binding, and order parameters. Our results for saturated interfacial area per surfactant molecule are greater than what has been obtained by other researchers through parametric fitting of interfacial area from experimental surface tension data using the Davies isotherm. Possible explanations for this difference are discussed. The low interfacial areas occupied by each poly(fluorooxetane) at the water/air interface are the result of their ability to adopt a "looped" conformation, in which the carbon and oxygen backbone of each surfactant and the attached perfluoroalkyl chains are forced into the air phase. A geometrically defined penetration parameter was calculated from the density profiles, which reveals that each poly(fluorooxetane) surfactant is more effective at separating the air and water phases than the "long-chain" anionic fluorosurfactant. The degree of hydration measured for different atoms in poly(fluorooxetane) during simulation confirms that a "looped" conformation is adopted in which the surfactant backbone and the perfluoroalkyl chains are lifted away from the water surface. Calculation of order parameters revealed a much lower degree of ordering for the perfluoroalkyl side chains in each bolaamphiphile than in the "long chain" anionic fluorosurfactant. When viewed in the context of the penetration parameter analysis, the density profiles and hydration data suggest why each poly(fluorooxetane) is capable of significantly reducing surface tension when other fluorosurfactants with similarly short perfluoroalkyl moieties provide inadequate surface tension reduction for practical flow-and-leveling applications.     

Intramolecular asymmetric Heck reactions: evidence for dynamic kinetic resolution effects

[reaction: see text] Enantioselectivity of the cyclization of 1 varies at different stages in the reaction. X-ray crystallography has shown that 1 exists as enantiomerically pure (M) and (P) chiral helical structures defined by the relative orientations of the arene, amide, and alkene. The relative rates of interconversion of the rotamers of 1 have been established, leading to mechanistic proposals to account for the variation of ee based on kinetic resolution effects.     

Nearest neighbour diagnostic statistics on the accuracy of APT solute cluster characterisation

Diagnostic statistics and information theory techniques have been developed to investigate the accuracy to which solute clusters characterised in atom probe tomography (APT) data can reflect the true nature of the physical clusters in the original specimen. Simulated atom-probe datasets representing a range of atomic solute clustering within a pseudo-binary alloy upon an fcc aluminium lattice were generated for the study. The effectiveness of partitioning the APT-like simulated data based upon a binary classification defined by a distance threshold d _max upon the kth nearest neighbour distance distribution was investigated. Information theory was also used to optimise the selection of the threshold d _max. Analysis of variation was performed upon a factorial design of data simulations with low and high levels of: solute concentration; short-range order; and background to the mass-to-charge-state-ratio spectrum. This meta-analysis showed that the background levels have a significant compromising effect upon the binary classification in low solute systems with relatively low or random levels of clustering. Although the random clustering of higher solute concentrations is better analysed, significantly non-random clustering in both low and high solute concentrations is analysed well despite the presence of high levels of background. A meta-analysis of the binary classification upon a simulated dispersion of coherent precipitates within a similar matrix was also undertaken. Optimal k and d _max parameters are likely a dependent upon the physical dimensions of precipitate size as well as the precipitate/matrix solute concentrations.     

A Dual Threat: Redox-Activity and Electronic Structures of Well-Defined Donor–Acceptor Fulleretic Covalent-Organic Materials

The effect of donor (D)–acceptor (A) alignment on the materials electronic structure was probed for the first time using novel purely organic porous crystalline materials with covalently bound two- and three-dimensional acceptors. The first studies towards estimation of charge transfer rates as a function of acceptor stacking are in line with the experimentally observed drastic, eight-fold conductivity enhancement. The first evaluation of redox behavior of buckyball- or tetracyanoquinodimethane-integrated crystalline was conducted. In parallel with tailoring the D-A alignment responsible for “static” changes in materials properties, an external stimulus was applied for “dynamic” control of the electronic profiles. Overall, the presented D–A strategic design, with stimuli-controlled electronic behavior, redox activity, and modularity could be used as a blueprint for the development of electroactive and conductive multidimensional and multifunctional crystalline porous materials.