The chemical bond in polyphosphides: crystal structures, the electron localization function, and a new view of aromaticity in P4(2-) and P5(-)

The incongruent solvation of M(I)4P6 species (M(I) = K, Rb, Cs) in liquid ammonia leads to a broad variety of polyphosphides such as P7(3-), P11(3-), and the putatively aromatic P4(2-) and P5(-), which we investigated by using NMR spectroscopy and single-crystal X-ray structure analysis. The structures of Cs2P4 x 2 NH3, (K@[18]crown-6)3K3(P7)2 x 10 NH3, Rb3P7 x 7 NH3, and (Rb@[18]crown-6)3P7 x 6 NH3 are discussed and compared. The electron localization function ELF is used in a comparison of the chemical bonding of various phosphorus species. The variances of the basin populations provide a well-established measure for electron delocalization and therefore aromaticity. While comparable variance is calculated for P4(2-) and P5(-) it is observed in the lone pairs rather than in the basin populations of the bonds as in the prototypical aromatic hydrocarbons such as benzene or the cyclopentadienide anion. For this behavior, the term "lone pair aromaticity" is proposed.     

Wall modeling for implicit large-eddy simulation and immersed-interface methods

We propose and analyze a wall model based on the turbulent boundary layer equations (TBLE) for implicit large-eddy simulation (LES) of high Reynolds number wall-bounded flows in conjunction with a conservative immersed-interface method for mapping complex boundaries onto Cartesian meshes. Both implicit subgrid-scale model and immersed-interface treatment of boundaries offer high computational efficiency for complex flow configurations. The wall model operates directly on the Cartesian computational mesh without the need for a dual boundary-conforming mesh. The combination of wall model and implicit LES is investigated in detail for turbulent channel flow at friction Reynolds numbers from Re _τ  = 395 up to Re _τ =100,000 on very coarse meshes. The TBLE wall model with implicit LES gives results of better quality than current explicit LES based on eddy viscosity subgrid-scale models with similar wall models. A straightforward formulation of the wall model performs well at moderately large Reynolds numbers. A logarithmic-layer mismatch, observed only at very large Reynolds numbers, is removed by introducing a new structure-based damping function. The performance of the overall approach is assessed for two generic configurations with flow separation: the backward-facing step at Re _h = 5,000 and the periodic hill at Re _H = 10,595 and Re _H = 37,000 on very coarse meshes. The results confirm the observations made for the channel flow with respect to the good prediction quality and indicate that the combination of implicit LES, immersed-interface method, and TBLE-based wall modeling is a viable approach for simulating complex aerodynamic flows at high Reynolds numbers. They also reflect the limitations of TBLE-based wall models.     

A new two-point deformation tensor and its relation to the classical kinematical framework and the stress concept

Starting from the issue of what is the correct form for a Legendre transformation of the strain energy in terms of Eulerian and two-point tensor variables we introduce a new two-point deformation tensor, namely H=(F−F^−T)/2, as a possible deformation measure involving points in two distinct configurations. The Lie derivative of H is work conjugate to the first Piola–Kirchhoff stress tensor P. The deformation measure H leads to straightforward manipulations within a two-point setting such as the derivation of the virtual work equation and its linearization required for finite element implementation. The manipulations are analogous to those used for the Lagrangian and Eulerian frameworks. It is also shown that the Legendre transformation in terms of two-point tensors and spatial tensors require Lie derivatives. As an illustrative example we propose a simple Saint Venant–Kirchhoff type of a strain-energy function in terms of H. The constitutive model leads to physically meaningful results also for the large compressive strain domain, which is not the case for the classical Saint Venant–Kirchhoff material.     

A novel approach to the determination of the crosslink density in rubber materials with the dipolar correlation effect in low magnetic fields

We present a novel NMR approach to the determination of crosslink densities in rubber materials. The method is based on the dipolar correlation effect (DCE) on the stimulated echo examined in a series of rubber samples and linear polyisoprene. The parameter evaluated from the echo attenuation curves is the mean‐squared dipolar fluctuation associated with anisotropic reorientations of macromolecular backbones. The contributions to the DCE of the constraints due to excluded volume effects and chemical crosslinks are estimated. A strong dependence of the mean‐squared dipolar fluctuation on the crosslink density of rubber combined with the simplicity of performing the measurements with inexpensive low‐field instruments suggests that the DCE is a useful tool for routine applications. The potential and problems of performing DCE measurements in low‐magnetic‐field conditions are discussed in detail. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2207–2216, 2001     

Über die Minima von positiven ternären Hermiteschen Formen

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Quadratische Zahlkörper ohne euklidischen Algorithmus

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