Nonadiabatic Ehrenfest molecular dynamics within the projector augmented-wave method

We derive equations for nonadiabatic Ehrenfest molecular dynamics within the projector augmented-wave (PAW) formalism. The discretization of the electrons is time-dependent as the augmentation functions depend on the positions of the nuclei. We describe the implementation of the Ehrenfest molecular dynamics equations within the real-space PAW method. We demonstrate the applicability of our method by studying the vibration of NaCl, the torsional rotation of H(2)C=NH(2)(+) in both the adiabatic and the nonadiabatic regimes, and the hydrogen bombardment of C(40)H(16).     

Convex source support in three dimensions

This work extends the algorithm for computing the convex source support in the framework of the Poisson equation to a bounded three-dimensional domain. The convex source support is, in essence, the smallest (nonempty) convex set that supports a source that produces the measured (nontrivial) data on the boundary of the object. In particular, it belongs to the convex hull of the support of any source that is compatible with the measurements. The original algorithm for reconstructing the convex source support is inherently two-dimensional as it utilizes M?bius transformations. However, replacing the M?bius transformations by inversions with respect to suitable spheres and introducing the corresponding Kelvin transforms, the basic ideas of the algorithm carry over to three spatial dimensions. The performance of the resulting numerical algorithm is analyzed both for the inverse source problem and for electrical impedance tomography with a single pair of boundary current and potential as the measurement data.     

Oriented crosslinked polyethylene pipes by a novel extrusion method

Crosslinking and stretching (2.5 times along the circumferential direction) of the molten polymer during extrusion produced pipes with dominantly circumferential orientation and a lower degree of axial chain orientation. Differential scanning calorimetry (crystallinity and crystal thickness), density measurements (crystallinity), X-ray diffraction (c-axis orientation), infrared dichroism measurements (crystalline and amorphous chain orientation) and contraction measurements (molecular draw ratio) assessed the microstructure of the pipe material. The mechanical properties of the oriented material were assessed by uniaxial tensile tests. The orientation was biaxial with the main orientation in the circumferential direction and a lesser orientation in the axial direction. The maximum degree of circumferential orientation was obtained at the inner wall of the pipe. The lower degree of crosslinking of the core material allowed slippage of chains during the stretching of the molten polymer and it is suggested that this is the cause of the lower degree of orientation of the core material. The oriented pipe material exhibited a 5-10% higher degree of crystallinity and higher crystal thickness than conventionally crosslinked material. The tensile modulus and the tensile strength of the oriented, cross-linked material was greater along the axial direction than along the circumferential direction. The circumferential and axial moduli for the oriented, crosslinked pipe were greater than the corresponding moduli of the non-oriented cross-linked pipe material. Another pipe based on crosslinked PE that were first circumferentially stretched 2.5 times and later axially stretched 10 times (in the molten state) showed, despite the fact that it exhibited pronounced axial orientation almost a balanced tensile modulus (4.3±0.2 GPa) in the axial-circumferential plane. Atomistic modelling showed that the orientational dependence of the density of the amorphous phase is small.     

Tris(benzophenoneimino)phosphane and Related Compounds

A new group of bases with benzophenoneiminyl (bpi) moiety has been synthesized and characterized in this work. The title compound tris(benzophenoneimino)phosphane (P(bpi)₃) 1 was prepared with a convenient one-pot approach: benzophenone imine was deprotonated using MeMgCl and reacted with PBr₃ in diglyme. The method could be considered as a method of choice for preparing other (amino)phosphanes in case lithio-intermediates and/or protonated phosphane is out of consideration. Phosphane 1 is further used to prepare a range of related phosphonium cations and phosphazenes. Phosphonium cations were deprotonated to assess the stability of the resulting phosphonium ylides. In some cases, the bulky substances were capable of forming P−N heterocycles. Experimental (MeCN) and computational (MeCN, THF, gas-phase) basicities of benzophenone imine, phosphane 1 , phosphonium ylides, and phosphazenes, as well as some representative XRD structures, are presented and discussed.