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.     

Generalized exponential functions applied to atomic calculations

The use of a generalized exponential function r ^v?1 exp(?ζr ^μ ) as a radial basis function in atomic calculations is studied with our special interest in the variationally optimum value of the parameter μ, since special cases of μ = 1 and μ = 2 correspond respectively to the radial parts of commonly-used Slater-type and Gaussian-type functions. Roothaan-Hartree-Fock calculations are performed for ground-state neutral atoms with atomic number Z = 2–54, singly-charged cations with Z = 3–55, and anions with Z = 1–53 within the single-zeta (or minimal basis) framework. For all the species examined, the optimtum μ values are found to be smaller than unity and increase towards unity as the atomic number increases. The present results support the use of Slater-type functions when μ is restricted to be an integer, but suggest from the variational point of view that even the exponential decay of Slater-type functions is too “strong” within the single-zeta approximation.     

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.     

Bis[3‐(trimethyl­silyl)prop­yl] ethyl­enebisphospho­nate,H2DTMSP[EBP]

The title compound (H₂DTMSP[EBP]), C₁₄H₃₆O₆P₂Si₂, was crystallized by the slow evaporation of a solution in a 20:1 mixture of pentane and acetone. The H₂DTMSP[EBP] mole­cule lies about an inversion center. In the solid state, the mol­ecule exists in an anti configuration, with the mol­ecular backbone C—C bond located on an inversion center. The compound exists in the solid state as hydrogen‐bonded infinite sheets in the ab plane, unlike the methyl­ene analogue, which exists as hydrogen‐bonded infinite chains, demonstrating an `even–odd' effect of the length of the backbone alkyl chain.     

Aggregated colloids under flow

Summary We have recently reported on a new scaling theory of the rupture of colloid aggregates. The scaling theory is compared with a simulation study of the transient response of sheared 2d aggregates. In this paper we discuss the origins of deviations from the predicted scaling behaviour. We also report some of the steady-state configurations formed post rupture. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Reduction of contact stress by use of relief notches

The photoelastic method is used to investigate the possibility of relieving the large local stresses that develop in the corners of a right angled indenter compressing a semi-infinite body by inducing geometric changes to the indenter/semi-infinite body configuration. It is shown that a circular notch cut along the free edges of the indenter can totally eliminate the large corner stresses. The notch, if placed along the interface edge of the half plane, can reduce the stress concentration, but never eliminate it. The results obtained have wide practical application.     

Two- and three-dimensional analysis of bose-einstein correlations inπ +/K+p interactions at 250 GeV/c

The NA22 data onπ ^? π ^? correlations are analyzed in terms of a number of two- and three-dimensional parametrizations (Gaussian space-time, Goldhaber, Bowler string-like, Bertsch hydrodynamical, Kopylov-Podgoretskii, etc.). Contrary to the results obtained for e⁺e^? andµp collisions, the Goldhaber parametrization, as well as string-like models, fail in describing the hadron-hadron data. Better fits are obtained in the framework of surface-emitting fireball-like models, both when including and excluding hydrodynamical expansion of nuclear matter. Our results indicate that pion radiation occurs at earlier stages of matter evolution than in nuclear collisions.     

Pulsed gas lenses

The concept of a pulsed gas lens is proposed. Potential applications are envisaged and preliminary experiments with pulsed ray refraction are reported.     

Oxyanion derivatives of cuprate superconductors superconducting 123 phosphates

While YSr₂Cu₃O₇ cannot be prepared under ambient conditions, partial substitution of the phosphate group for copper, as in YSr₂Cu_2.8(PO₄)_0.2O_y, stabilizes this phase in the orthorhombic structure, but the material is not superconducting. Superconductivity in YSr₂Cu_2.8(PO₄)_0.2O_y is obtained by increasing the hole concentration through partial substitution of Y by Ca, as in Y_0.7Ca_0.3Sr₂Cu_2.8(PO₄)_0.2O_y (T_c≈40 K). By incorporating the phosphate group in orthorhombic YBaSrCu₃O ₇, a stable tetragonal derivative of the formula YBaSrCu_2.8(PO₄)_0.2O_y (T_c≈ 47 K) has been prepared; the T_c increases to 70 K by partial substitution of Y by Ca as in Y_0.7Ca_0.3BaSrCu_2.8(PO₄)_0.2O_y.