Exchange coupling in halo-bridged dinuclear Cu(II) compounds: a density functional study

A density functional study of exchange coupling in halo-bridged dinuclear copper(II) compounds has been carried out. Coupling constants calculated for full unmodeled structures, as determined by X-ray diffraction, are in excellent agreement with experimental data, confirming the ability of the computational strategy used in this work to predict the magnetic behavior of such compounds. Model calculations have been used to examine the influence of several factors on the coupling constant: the nature of the bridging and terminal ligands, the coordination environment around copper atoms, and some structural distortions frequently found in this family of complexes. A ferromagnetic coupling is predicted when N-donor terminal ligands are present, especially for bromo-bridged systems, an interesting synthetic target.     

Early-late transition metal ferromagnetic coupling mediated by hydrogen bonding

Hydrogen bonding between early and late transition metal complexes is proposed as a strategy to obtain ferromagnetic interactions based on a theoretical study using density functional calculations.     

Non-Gaussian nature of the alpha relaxation of glass-forming polyisoprene

We report quasielastic neutron scattering experiments exploring the alpha relaxation in polyisoprene over an unprecedented range in momentum transfer. Corroborating and validating earlier molecular dynamics simulations, the measurements reveal a crossover from a Gaussian regime of sublinear diffusion to a strongly non-Gaussian regime at short distances. We show that a consistent interpretation in terms of a distribution of finite jumps underlying the alpha process is possible. This model leads to a time-dependent non-Gaussian parameter exhibiting all features revealed so far from various simulations.     

Anomalous thermal conductivity of frustrated heisenberg spin chains and ladders

We study the thermal transport properties of several quantum-spin chains and ladders. We find indications for a diverging thermal conductivity at finite temperatures for the models examined. The temperature at which the nondiverging prefactor kappa((th))(T) peaks is, in general, substantially lower than the temperature at which the corresponding specific heat c(V)(T) is maximal. We show that this result of the microscopic approach leads to a substantial reduction for estimates of the magnetic mean-free path lambda extracted by analyzing recent experiments, as compared to similar analyses by phenomenological theories.     

Phase diagram of a model for diluted magnetic semiconductors beyond mean-field approximations

A lattice spin-fermion model for diluted magnetic semiconductors (DMS) is investigated numerically, improving on previously used mean-field approximations. Curie temperatures are obtained varying the Mn spin x and hole n densities, and the impurity-hole exchange J in units of the hop-ping t. Optimal values are found in the subtle intermediate regime between itinerant and localized carriers. At intermediate and large J/t, a "clustered" state is observed above the Curie temperature and ferromagnetism is suppressed. Formal analogies between DMS and manganites are discussed.     

First identification of excited states in 59Zn

Excited states in ⁵⁹Zn were observed for the first time following the fusion-evaporation reaction ²⁴Mg + ⁴⁰Ca at a beam energy of 60 MeV. The GASP array in conjunction with the ISIS Silicon ball and the NeutronRing allowed for the detection of γ-rays in coincidence with evaporated light particles. The mirror symmetry of ⁵⁹Zn and ⁵⁹Cu is discussed. Received: 28 May 2002 / Accepted: 10 July 2002 / Published online: 3 December 2002 RID="a" ID="a"Present address: Oliver Lodge Laboratory, University of Liverpool, P.O. Box 147, Liverpool, L69 7ZE, United Kingdom; e-mail: ca@ns.ph.liv.ac.uk. RID="b" ID="b"Present address: Physik-Departament, Technische Universit?t München, D-85748 Garching, Germany. Communicated by W. Henning     

In beam measurements of the F colouring curves for NaCl at and above room temperature

In beam measurements have been made of the F colouring curves in NaCl between 20 and 300°C. The first colouring stage has been empirically fitted by up to three exponential components which become smaller and faster with increasing temperature. A model is presented which gives physical significance to the fitting parameters.     

The Stille reaction in the synthesis of carotenoid butenolides: synthesis of 6'-epi-peridinin

A new strategy for carotenoid butenolides has been developed that is based in part in halogen-selective Stille cross-coupling of dihalogenated ylidenebutenolide segment 2 and highly functionalized alkenylstannanes. [reaction: see text]     

The isobutylene-isobutane alkylation process in liquid HF revisited

Details on the mechanism of HF catalyzed isobutylene-isobutane alkylation were investigated. On the basis of available experimental data and high-level quantum chemical calculations, a detailed reaction mechanism is proposed taking into account solvation effects of the medium. On the basis of our computational results, we explain why the density of the liquid media and stirring rates are the most important parameters to achieve maximum yield of alkylate, in agreement with experimental findings. The ab initio Car-Parrinello molecular dynamics calculations show that isobutylene is irreversibly protonated in the liquid HF medium at higher densities, leading to the ion pair formation, which is shown to be a minimum on the potential energy surface after optimization using periodic boundary conditions. The HF medium solvates preferentially the fluoride anion, which is found as solvated [FHF](-) or solvated F(-.)(HF)(3). On the other hand, the tert-butyl cation is weakly solvated, where the closest HF molecules appear at a distance of about 2.9 Angstrom with the fluorine termination of an HF chain.