Crystal deformation during the growth of kink bands in oriented polyethylene

When oriented polyethylene is sheared at an angle to the orientation axis, kink bands often develop and grow, with a resulting change of the crystalline orientation. Beside the crystalline reorientation, the following changes within the kink bands have been observed with wide-angle x-rays: (a) partial transformation to a monoclinic from the normal orthorhombic unit cell; (b) partial alignment of the orthorhombic b axes; (c) rotation of the orthorhombic c axes of a fraction of the crystals around the kinks by an extra 40 to 60° beyond that of the fibrils; and (d) misalignment of the orthorhombic (hk0) planes by a few degrees. These results are suggested to arise, at least in part, from crystal flattening and from crystal twinning or pseudotwinning on planes intersecting the molecular axes.     

Formation of fluoro-meisenheimer complexes using homogeneous and heterogeneous fluoride ion sources

1-Chloro-2,4-dinitrobenzene, 1-fluoro-2,4-dinitrobenzene and 1,3-dinitrobenzene form Meisenheimer complexes with tetra-n-butylammonium fluoride and alumina supported alkali metal fluorides. Both kinetically controlled and thermodynamically controlled complexes are observed.     

The structure of amorphous GeSe and GeTe

We present the results of electronic structure calculations on model 3:3 and 4:2 co-ordinated networks of amorphous GeSe and GeTe. The calculations show that a- GeTe has a predominantly 4:2 chemically ordered structure and suggest that GeSe may be 3:3 co-ordinated. They emphasize how it is often easier to discriminate between different models on the basis of electronic structure rather than other information.     

Spatial redistribution of energy in a nanosecond laser pulse by an organic optical limiter

The spatial redistribution of energy resulting from the interaction between a near-diffraction-limited nanosecond laser pulse and the nonlinear absorbing optical limiting dye silicon naphthalocyanine is described, for what is to our knowledge the first time, in an optical geometry that is likely to be found in practical applications. For input fluences above that required for nonlinear absorption but below that for bubble growth, a plane wave or Gaussian spatial input evolves unexpectedly to a sharp central spike and a well-defined outer ring. The observed energy redistribution is thought to rely on a combination of nonlinear processes, since a pure absorptive process alone cannot explain the profiles presented. A model involving nonlinear absorption and nonlinear refraction qualitatively reproduces the observed spatial profiles. It is clear from the results that the performance of optical limiting dyes in representative optical geometries, even at fluences well below that required for bubble growth, cannot be described solely by nonlinear absorption.     

MOON for neutrino-less double beta decays

The MOON (Majorana/Mo Observatory Of Neutrinos) project aims at studies of the Majorana nature of the neutrino (ν) and the ν-mass spectrum by spectroscopic experiments of neutrino-less double beta decays (0νββ) with the ν-mass sensitivity of 〈m _ν ^m 〉 = 100−30 meV. The solid scintillator option of the MOON detector is a super ensemble of multi-layer modules, each being composed by PL scintillator plates and position-sensitive detector planes with good overall energy resolution of σ ≈ 2% at the Q _ββ ≈ 3 MeV. Thin ββ source films are interleaved between the detector planes. High localization of the two β tracks enables one to select true signals and reject BG ones. The multi-layer structure of the detector makes it realistic to build a compact ton-scale detector. MOON with detector ≠ ββ source is used for studying 0νββ decays from ¹⁰⁰Mo, ⁸²Se and other ββ isotopes with large Q _ββ . Real-time exclusive measurements of low energy solar neutrinos can be made by observing inverse β rays from solar-ν captures of ¹⁰⁰Mo in delayed coincidence with the subsequent β decay of ¹⁰⁰Tc.     

Large harmonic softening of the phonon density of states of uranium

Phonon density-of-states curves were obtained from inelastic neutron scattering spectra from the three crystalline phases of uranium at temperatures from 50 to 1213 K. The alpha-phase showed an unusually large thermal softening of phonon frequencies. Analysis of the vibrational power spectrum showed that this phonon softening originates with the softening of a harmonic solid, as opposed to vibrations in anharmonic potentials. It follows that thermal excitations of electronic states are more significant thermodynamically than are the classical volume effects. For the alpha-beta and beta-gamma phase transitions, vibrational and electronic entropies were comparable.     

One-step synthesis of reusable, polymer-supported tri-alkyl phosphine ligands. Application in Suzuki-Miyaura and alkoxycarbonylation reactions

A simple, efficient one-step route to polystyrene-supported trialkylphosphine ligands is reported. These polymer-supported alkyl phosphine ligands proved to be highly active for Suzuki-Miyaura reactions and in alkoxycarbonylation reactions. The palladium loaded polymer-supported catalysts can be recycled several times with only minimal loss of catalyst activity.     

Highly diastereoselective templated complexation of dipyrromethenes

[reaction: see text] Bis(dipyrromethene)s with relatively long spacers (>5 atoms) form helical monomeric complexes as the two binding units of the bis(dipyrromethene) chelate around the same tetrahedrally coordinated metal ion. Herein we report the first highly diastereoselective mononuclear helicate-forming complexation reactions of bis(dipyrromethene)s using homochiral binol and tartrate motifs which serve as both linkers and asymmetric templates.     

Investigating magnetostructural correlations in the pseudooctahedral trans-[Ni(II){(OPPh2)(EPPh2)N}2(sol)2] complexes (E = S, Se; sol = DMF, THF) by magnetometry, HFEPR, and ab initio quantum chemistry

In this work, magnetometry and high-frequency and -field electron paramagnetic resonance spectroscopy (HFEPR) have been employed in order to determine the spin Hamiltonian (SH) parameters of the non-Kramers, S = 1, pseudooctahedral trans-[Ni(II){(OPPh(2))(EPPh(2))N}(2)(sol)(2)] (E = S, Se; sol = DMF, THF) complexes. X-ray crystallographic studies on these compounds revealed a highly anisotropic NiO(4)E(2) coordination environment, as well as subtle structural differences, owing to the nature of the Ni(II)-coordinated solvent molecule or ligand E atoms. The effects of these structural characteristics on the magnetic properties of the complexes were investigated. The accurately HFEPR-determined SH zero-field-splitting (zfs) D and E parameters, along with the structural data, provided the basis for a systematic density functional theory (DFT) and multiconfigurational ab initio computational analysis, aimed at further elucidating the electronic structure of the complexes. DFT methods yielded only qualitatively useful data. However, already entry level ab initio methods yielded good results for the investigated magnetic properties, provided that the property calculations are taken beyond a second-order treatment of the spin-orbit coupling (SOC) interaction. This was achieved by quasi-degenerate perturbation theory, in conjunction with state-averaged complete active space self-consistent-field calculations. The accuracy in the calculated D parameters improves upon recovering dynamic correlation with multiconfigurational ab initio methods, such as the second-order N-electron valence perturbation theory NEVPT2, the difference dedicated configuration interaction, and the spectroscopy-oriented configuration interaction. The calculations showed that the magnitude of D (～3-7 cm(-1)) in these complexes is mainly dominated by multiple SOC contributions, the origin of which was analyzed in detail. In addition, the observed largely rhombic regime (E/D = 0.16-0.33) is attributed to the highly distorted metal coordination sphere. Of special importance is the insight by this work on the zfs effects of Se coordination to Ni(II). Overall, a combined experimental and theoretical methodology is provided, as a means to probe the electronic structure of octahedral Ni(II) complexes.