The role of OH ions in the stabilization of F colour centres in LiF

Thermally Stimulated Depolarisation Current (TSDC) and optical methods are applied to a range of alkali-fluoride crystals in order to establish a model for the stable F ₂ ⁺ - like colour centres in LiF:OH^-. The experimental results for LiF:OH^- suggest that the OH^- defects are partially destroyed under ionising irradiation or during crystal growth. The low-temperature dielectric relaxation signals in LiF:OH^- and LiF:Mg²⁺,OH^- are attributed to highly interacting hydroxide ions and products of their destruction located in extended lattice defects. In LiF:OH^-, in contrast to other alkali halides, the results advocate for a defect-structure model, which considers a neutral defect (ND, probably O₂ or H₂) sited at the anion vacancy of the O^2--V _a ⁺ dipole and which possibly is the “nucleus” for the F ₂ ⁺ centre. The proposed F ₂ ⁺ (ND, O^-) model seems to better explain the dielectric results, compared to the older F ₂ ⁺ (O^2-) and F ₂ ⁺ (O^-) models. The estimate for the electric dipole moment derived from the experimental TSDC bands, gives a value for the F ₂ ⁺ - like centre in LiF:OH^- between those of the F ₂ ⁺ (O^-) and F ₂ ⁺ (O^2-) defects, in good agreement with the proposed F ₂ ⁺ (ND,O^-) model. The reduction of the activation energy barrier of the (re)orientation process of the Mg²⁺V _c ^- (OH^-) complexes in LiF:Mg²⁺,OH^-, and the low-temperature shift of their TSDC band, compared to the single Mg ₂ ⁺ V _c ^- peak in LiF:Mg²⁺, are tentatively ascribed to an increase in the crystal-lattice parameters owing to the presence of OH^- and/or products of its destruction. Received 31 August 2001 / Received in final form 30 March 2002 Published online 9 July 2002     

The hydrogenation of olefins using a polymer supported ruthenium complex

RuCl₂(PPH₃)3 has been attached to a phosphinated polymer support (phosphinated polystyrene crosslinked with 2% divinylbenzene) and the reagent converted to the polymer supported analogue of RuClH(PPH₃)₃ in the presence of base. The polymer supported catalyst efficiently hydrogenates terminal olefins under ambient conditions. Hydrogenation of 1-hexene has revealed that the reaction rate is proportional to [Ru], [H₂] and [olefin]/(1 + [olefin]). The polymer support environment allows for selectivity in olefin hydrogenation and under suitable reaction conditions short chain terminal olefins are hydrogenated more rapidly than long chain terminal olefins. The extent of metal loading on the polymer and the reaction solvent composition also influence the reaction selectivity and these effects are discussed.     

Scaling of Prosocial Behavior in Cities

Previous research has examined how various behaviors scale in cities in relation to their population sizes. Behavior related to innovation and productivity has been found to increase per capita as the size of the city increases, a phenomenon known as superlinear scaling. Criminal behavior has also been found to scale superlinearly. Here we examine a variety of prosocial behaviors (e.g., voting and organ donation), which also would be presumed to be categorized into a single class of scaling with population. We find that, unlike productivity and innovation, prosocial behaviors do not scale in a unified manner. We argue how this might be due to the nature of interactions that are distinct for different prosocial behaviors.     

Conformation of alkanes in the gas phase and pure liquids

Monte Carlo (MC) statistical mechanics simulations have been carried out for the homologous alkane series of n-butane through n-dodecane in the gas phase and for the pure liquids at 298 K and 1 atm using the OPLS-AA force field. The study addresses potential cumulative deviations of computed properties and potential conformational differences between the gas phase and pure liquids, for example, from self-solvation in the gas phase. The average errors in comparison with experimental data for the computed densities and heats of vaporization are modest at 0.7% and 6.9%, respectively. Also, the invariant gas and liquid-phase results for average end-to-end distances and percentages of trans conformations for each nonterminal C-C bond assert that the conformer populations are not altered upon transfer from the gas phase to the pure liquid for the n-alkanes in this size range. Average end-to-end distances were also computed from the results of conformational searches and corroborated the MC findings. Quantitatively, the OPLS-AA result for the trans population of the C3-C4 bond in n-undecane is in close agreement with the findings from (13)C NMR experiments. Finally, previous work on determining the shortest n-alkane that does not have an all-trans global energy minimum has been extended. The smallest n-alkane with a hairpin geometry that is lower in energy than the all-trans conformer occurs for C(22)H(46) with OPLS-AA, though with a correction for GG sequences, the true turning point is likely in the C(16)-C(18) range.     

Adsorption of atrazine on soils: model study

The adsorption of the widely used herbicide atrazine onto three model inorganic soil components (silica gel, gamma-alumina, and calcite (CaCO(3)) was investigated in a series of batch experiments in which the aqueous phase equilibrated with the solid, under different solution conditions. Atrazine did not show discernible adsorption on gamma-alumina (theta=25 degrees C, 3.8相似文献   

A complex parabolic type monge-ampère equation

The complex parabolic type Monge-Ampère equation we are dealing with is of the form inB × (0,T),u=ϕ on Γ, whereB is the unit ball in ℂ ^d ,d>1, and Γ is the parabolic boundary ofB × (0,T). Solutionu is proved unique in the class .     

Calcium sulfate precipitation in the presence of water-soluble polymers

The effect of four different polymers on the precipitation of calcium sulfate was investigated in the present work. The degree of inhibition was estimated from measurements of the calcium ion activity and from specific solution conductivity measurements in the supersaturated solutions during the course of the precipitation process. The effects of polyacrylic acid (PAA, three different polymers with average molecular weight 2000, 50,000, and 240,000, respectively) and of a co-polymer of PAA with polystyrene sulfonic acid (PSA, average molecular weight<20,000) were investigated with respect to their effect on the kinetics of spontaneous precipitation of calcium sulfate salts. The results of the kinetics experiments suggested that the spontaneous precipitation from supersaturated calcium sulfate solutions at 25 degrees C yielded exclusively calcium sulfate dihydrate (gypsum) both in the absence and in the presence of the polymeric additives. The induction times, preceding the formation of the solid increased in all cases in the presence of the polymeric additives. Polymer concentrations as low as 2.0 ppm increased induction time from practically zero to 10 min. The rates of precipitation were reduced according to the solutions content in the polymers added and precipitation was completely suppressed in the presence of 6.0 ppm of the polymers tested, depending on their molecular weight. The lower the molecular weight of PAA, the more efficient was the threshold inhibition and the stronger the reduction of the rates of spontaneous precipitation. PSA yielded the poorest inhibition efficiency in comparison with the PAA, possibly because of the relatively lower affinity of the sulfonate groups for the calcium ions of the surface of the solid forming. The kinetics results analysis assuming Langmuir-type adsorption of the polymeric molecules on the growing supercritical gypsum nuclei showed different affinity for the polymers tested in agreement with the respective inhibition efficiency, in the order: PAA1>PAA2>PSA>PAA3. The presence of the polymers in the supersaturated solutions resulted in modification of the precipitated gypsum crystals morphology.     

Flexible working arrangements in context: An empirical investigation through self-organizing maps

This is one of the first studies to utilize Kohonen’s self-organizing maps on flexible work arrangements (FWAs), employee turnover and absenteeism within different national contexts and an array of organizational factors. While the majority of FWAs did not reduce significantly employee turnover or absenteeism, country and industry were significant contextual variables in FWA use: we deciphered six main country regions, where service and manufacturing organizations were important to FWA preferences. We found a curvilinear relationship between turnover and shift-work among manufacturing firms regardless of country: turnover decreases at low levels and increases at high levels of shift-work. We also found strong positive relationships between weekend work and turnover among manufacturing firms regardless of country and firms in the region comprising of Germany, Austria, Sweden, Finland, Denmark, Czech Republic and Belgium. Finally, we found consistently high concentration of organizations with low absenteeism throughout certain industries and countries: noteworthy are service organizations in the Netherlands and manufacturing organizations in Australia. The results demonstrate the contextuality of FWA use across countries and industries, and the usefulness of SOMs for research within human resource management.     

Acceleration of the leastpth algorithm for minimax optimization with engineering applications

Over the past few years a number of researchers in mathematical programming and engineering became very interested in both the theoretical and practical applications of minimax optimization. The purpose of the present paper is to present a new method of solving the minimax optimization problem and at the same time to apply it to nonlinear programming and to three practical engineering problems. The original problem is defined as a modified leastpth objective function which under certain conditions has the same optimum as the original problem. The advantages of the present approach over the Bandler-Charalambous leastpth approach are similar to the advantages of the augmented Lagrangians approach for nonlinear programming over the standard penalty methods.This work was supported by the National Research Council of Canada under Grant A4414, and from the University of Waterloo.