Intramolecular motion and isotope effects in muonium‐substituted chloroalkyl radicals

Muon irradiation of pure liquid 3‐chloropropene, CH₂=CH-CH₂Cl, yields a primary radical, \dot\mboxCH₂-CHMu-CH₂Cl, and a secondary radical, MuCH₂-\rm\dot\mboxCH-CH₂Cl. 2‐methyl‐3‐chloropropene yields only the tertiary radical, MuCH₂-\rm\dot\mboxC(CH₃)-CH₂Cl. These three chloroalkyl radicals have been characterized by μSR and μLCR, and the hyperfine coupling constants (hfcs) have been determined over a range of temperatures, either in the pure liquid precursor or in concentrated solution. The temperature variation of the hfcs has been analyzed to obtain estimates of the barrier to internal rotation about the C_\alpha-C_\beta axis for various alkyl groups, and also their minimum energy conformations, i.e. their orientations with respect to the axis of the 2p_z orbital of the unpaired electron. The tertiary radical is particularly interesting because all three methyl‐like groups, -CH₃,-CH₂Cl and -CH₂Mu, are represented. The results can be compared to electron spin resonance data for analogous radicals, to provide information on the effects of Mu substitution for H. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanosynthesis of YIG and GdIG: A Structural and Mössbauer Study

We have investigated the mechanosynthesis of gadolinium and yttrium iron garnets by high-energy ball-milling of α-Fe₂O₃ and Gd₂O₃ or α-Fe₂O₃ and Y₂O₃, respectively, followed by short thermal annealings conducted at moderate temperatures. The samples were characterized by X-ray diffraction and Mössbauer spectroscopy, in order to determine the influence of the milling time and annealing conditions on the final products. For as-milled samples of each rare-earth system, the results revealed the formation of perovskite phases, in relative amounts that depend on the milling time. The formation of garnet phases was observed in as-annealed samples treated at 1000°C for 2 h or 1100°C for 3 h, i.e., at very modest annealing requirements when compared with ordinary solid-state-reaction processes performed without previous high-energy milling. Also, the occurrence was verified of a milling time for which the relative amount of garnet phases formed by annealing was maximized. This time depends on the rare-earth composing the garnet phase and on the annealing temperature.     

Mimicking catalase and catecholase enzymes by copper(II)-containing complexes

An imidazolate-bridged copper(II)-zinc(II) complex (Cu(II)-diethylenetriamino-μ-imidazolato-Zn(II)-tris(2-aminoethyl)amine perchlorate (denoted as “Cu,Zn complex”) and a simple copper(II) complex (Cu(II)-tris(2-aminoethyl) amine chloride (“Cu-tren”) were prepared and immobilised on silica gel (by hydrogen or covalent bonds) and montmorillonite (by ion exchange). The immobilised substances were characterised by FT-IR spectroscopy and their thermal characteristics were also studied. The obtained materials were tested in two probe reactions: catalytic oxidation of 3,5-di-tert-butyl catechol (DTBC) (catecholase activity) and the decomposition of hydrogen peroxide (catalase activity). It was found that the catecholase activity of the Cu,Zn complex increased considerably upon immobilization on silica gel via hydrogen bonds and intercalation by ion exchange among the layers of montmorillonite. The imidazolate-bridged copper(II)-zinc(II) complex and its immobilised versions were inactive in hydrogen peroxide decomposition. The Cu(II)-tris(2-aminoethyl)amine chloride complex displayed good catalase activity; however, immobilisation could not improve it.     

Magnetization and Specific Heat of UCo0.95T0.05Al (T = Fe, Ni) Single Crystals

We present the first single-crystal study of Fe and Ni doped U(Co_1-x T _x )Al compounds in comparison to the parent compound, the itinerant 5f-electron metamagnet UCoAl. Magnetization and specific-heat data measured in the temperature range of (1.8-300) K and in fields up to 10 T are analyzed and discussed. Both compounds exhibit a strong uniaxial anisotropy with the dominating magnetic response along the c-axis of the hexagonal ZrNiAl-type structure. Ni substitution yields an increase of the critical field for metamagnetism; UCo_0.95Fe_0.05Al is ferromagnetic below 30 K. Temperature evolution of the entropy change between 0 and 10 T points to involvement of magnetic correlations or spin fluctuations in the paramagnetic compounds UCoAl and UCo_0.95Ni_0.05Al.     

Spectroscopic investigation of 4f correlations in CeAg; comparison between LDA and many-body descriptions

High resolution photoemission and bremsstrahlung isochromat spectroscopy experiments have been carried out on CeAg and LaAg. From a comparison between these two compounds, we extract the cerium 4f spectral function, we compare it with band structure calculations and with many-body model simulations based on the single-impurity Anderson Hamiltonian. We show that the localized 4f charge estimated from previous band structure calculations cannot be identified with the 4f occupation number deduced from the Anderson model.     

Staffing Rosters with Breaks — A Case Study

A complex manual rostering system for directory assistance, telephone operators has been rationalized and the technique of integer programming used to automatically generate staff rosters. These rosters can be generated by relatively unskilled clerical staff. They result in operator costs comparable to manually generated rosters and can be produced in a fraction of the time taken to produce their manual counterparts. Implementation is reported.