A generalised model and calculation of the hyperfine interaction constant for anomalous muonium in the crystalline lattice of silicon

A new microscopic model of anomalous muonium for the elemental semiconductors is proposed. The relevant configuration consisting of both a diamagrentic molecule Si−Mu and an unpaired orbital e⁻ is contained into a semivacancy of the real lattice. By using the unrestricted Hartree-Fock computational method the principal properties of the system are established. A dynamical version of the model together with a question on the formation of such system are discussed.     

Temperature dependence of the rate constants for reactions of the carbonate radical with organic and inorganic reductants

Rate constants have been measured by pulse radiolysis for the reactions of the carbonate radical, CO₃^·?, with a number of organic and inorganic reactants as a function of temperature, generally over the range 5 to 80°C. The reactants include the substitution-inert cyano complexes of Fe^II, Mo^IV, and W^IV, the simple inorganic anions SO₃^2?, ClO₂^?, NO₂^?, I^?, and SCN^?, several phenolates, ascorbate, tryptophan, cysteine, cystine, methionine, triethylamine, and allyl alcohol. The measured rate constants ranged from less than 10⁵ to 3 × 10⁹ M^?1 s^?1, the activation energies ranged from ?11.4 to 18.8 kJ mol^?1, and the pre-exponential factors ranged from log A = 6.4 to 10.7. The activation energies for the metal complexes and inorganic anions generally decrease with increasing driving force for the reaction, as expected for an outer sphere electron transfer. For highly exothermic reactions, however, the activation energy appears to increase, probably reflecting the temperature dependence of diffusion. For many of the organic reactants, the activation energies were low and independent of driving force, suggesting that the oxidation is via an inner sphere mechanism.     

Separation of screw-sensed particles in a homogeneous shear field

The Stokes motions of three-dimensional screw-sensed slender particles in a homogeneous shear field are investigated, including the effects of buoyancy. Conclusions are drawn about the possibility of achieving a separation of mixtures of right- and left-handed particles. The linearity of the Stokes equations allows complex flows to be solved by adding the effects of the several terms which describe the flow in which the particle is immersed. The homogeneous shear flow considered here consists of three such terms; solutions for a series of 12 unit motions are sufficient to determine the hydrodynamic resistance tensors. The forces and torques experienced by screw-sensed particles are calculated from these 51 resistance tensors, using slender-filament theory. The results allow an estimate of the range of buoyancy parameters for which gravitational sedimentation can be neglected. The fundamental component of the particle motion is a rotation, at approximately the same angular velocity as that of the fluid. Superimposed on this are variations, of large period, in the particle orientation. A phase plane analysis is used to find the terminal orientations. Very long calculation times are required for the phase portrait. An approximate method based on azimuthally-averaged equations is developed to avoid the requirements for long time integration.