Solvothermal Synthesis, Crystal Structure, and Properties of the First Zinc Containing Thioantimonate(III) [Zn( tren)] 2Sb 4S 8·0.75 H 2O

Yellow crystals of the title compound were obtained under solvothermal conditions reacting elemental Zn, Sb, and S in a solution of tris(2-aminoethyl)amine (=tren) and water. The compound crystallises in the monoclinic space group P2₁/c with a=13.0247(7), b=22.308(2), c=12.1776(6) Å, and =105.352(6)°. In the structure of [Zn(tren)]₂Sb₄S₈·0.75 H₂O two [Zn(tren)]²⁺ cations are bound to the [Sb₄S₈]^4– anion via S atoms. The Zn²⁺ ions are in a trigonal bipyramidal environment of four N atoms of the tetradentate tren ligand and one S atom of the [Sb₄S₈]^4– anion. The anion is formed by SbS₃ and SbS₄ units which share common corners and edges. The interconnection mode yields three different non-planar Sb₂S₂ heterorings. The shortest intermolecular Sb–S distance amounts to about 3.7Å, and taking this long separation into account undulated chains running along [001] are formed with the water molecules residing in the pocket-like cavities. Upon heating the compound decomposes in one step starting at about 240°C. The final decomposition product was identified as ZnS and Sb₂S₃ by X-ray powder diffractometry. Additionally, spectroscopic data as well as synthetic procedures for [Zn(tren)]₂Sb₄S₈·0.75 H₂O are reported.     

Interparticle interactions in agglomerates of alpha-Fe2O3 nanoparticles: influence of grinding

We have chemically prepared a sample of antiferromagnetic alpha-Fe2O3 nanoparticles by a gel-sol technique. M?ssbauer spectra of the as-prepared sample showed that superparamagnetic relaxation was suppressed due to strong magnetic interparticle interactions even at room temperature. However, subsequent grinding of the sample by hand in a mortar for some minutes resulted in fast superparamagnetic relaxation of some of the particles. The effect was even more dramatic if the alpha-Fe2O3 powder was ground for a longer time or together with nonmagnetic eta-Al2O3 nanoparticles. Similar effects were found after low-energy ball milling. Thus it is found that the agglomeration of the nanoparticles during preparation under wet conditions results in strong magnetic interparticle interaction, but a relatively gentle mechanical treatment is sufficient to break up the agglomerates, resulting in much weaker interactions. We show that these effects can also be seen when a soil sample containing magnetic nanoparticles is ground.     

On a conjecture of R. E. Miles about the convex hull of random points

Denoty byp _d+i (B _d ,d+m) the probability that the convex hull ofd+m points chosen independently and uniformly from ad-dimensional ballB _d possessesd+i(i=1,...,m) vertices. We prove Mile's conjecture that, given any integerm, p _d+m (B _d ,d+m)»1 asd». This is obvious form=1 and was shown by Kingman form=2 and by Miles form=3. Further, a related result by Miles is generalized, and several consequences are deduced.Dedicated to Professor E. Halwaka on the occasion of his seventieth     

Transient behavior of a nonequilibrium plasma formed by merged beams

A low density, low temperature plasma formed by two merged beams of electrons and ions at near zero relative velocity is studied by solving a set of time-dependent rate equations. In particular, we investigate the role played by the radiative recombination (RR) and three-body recombination (TBR) on the population of excited states during the initial stage of plasma rearrangement and relaxation. It is found in the case of hydrogenic plasmas that low-lying states are filled predominantly by RR, while high Rydberg states are populated mainly by TBR. As the plasma further relaxes, the collisional excitation and de-excitation, and radiative decays become important, filling the median excited states. The dependence of the TBR and RR rates on ionic chargeZ is discussed to extend the result to plasmas of highZ ions.     

X-ray structure and variable temperature NMR spectra of [meso-triarylcorrolato]copper(III)

The diamagnetic square planar d(8) complexes [meso-arylcorrolato]copper(III) become paramagnetic upon warming, indicative of the equilibrium between the [corrolato]copper(III) and the [corrolato](+)* copper(II) forms of the complex. [meso-Triphenylcorrolato]copper(III) was structurally characterized and found to be saddled.