The nature of isostructural spinodal decomposition in the Al-Zn system

The electronic structure and thermodynamic properties of disordered Al-Zn alloys are investigated in the coherent potential approximation by the KKR-ASA method. Analysis of the electronic density of states and the Fermi surfaces of disordered alloys reveals the presence of eight electronic topological transitions in the concentration interval from 0 to 70 at. % Zn. It is shown that the passage of the Fermi level through two minima of the density of states, which are due to the superposition of different types of electronic topological transitions, gives rise to singularities in the concentration dependence of the second derivative of the thermodynamic potential at points corresponding to the boundaries of the region of isostructural decomposition of the high-temperature solid solution, according to the phase diagram of the Al-Zn system. Fiz. Tverd. Tela (St. Petersburg) 39, 593–596 (April 1997)     

Cu(I) complexes with oligo- and polyarylene phosphites

Monovalent copper complexes with oligo- and polyarylene phosphites were obtained. Complexation takes place due to coordination of copper with the phosphorus atom.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1198–1201, May, 1991.     

Intramolecular dynamics and its mathematical description in molecular spectroscopy and gas-phase electron diffraction problems

We describe a procedure for using the mathematical apparatus of tensor analysis for construction of model molecular Hamiltonians in overtone spectroscopy and gas-phase electron diffraction problems, and establishment of the connection between the calculation formulas when using different systems of curvilinear coordinates best describing the intramolecular dynamics.     

Modeling of Electroluminescence of Thin Organic Films

We propose a simple model for describing the electroluminescence in a single-layer thin-film organic electroluminescent cell on the assumption that the luminophore molecules are directly excited by electron impact and are the result of recombination. The calculated luminescence and efficiency curves are in qualitative and quantitative agreement with experimental data. To attain a high efficiency, it is necessary to use cathodes with a low work function and a high Fermi energy and relatively small electric fields.     

Macrocyclic receptor showing extremely high Sr(II)/Ca(II) and Pb(II)/Ca(II) selectivities with potential application in chelation treatment of metal intoxication

Herein we report a detailed investigation of the complexation properties of the macrocyclic decadentate receptor N,N'-Bis[(6-carboxy-2-pyridil)methyl]-4,13-diaza-18-crown-6 (H(2)bp18c6) toward different divalent metal ions [Zn(II), Cd(II), Pb(II), Sr(II), and Ca(II)] in aqueous solution. We have found that this ligand is especially suited for the complexation of large metal ions such as Sr(II) and Pb(II), which results in very high Pb(II)/Ca(II) and Pb(II)/Zn(II) selectivities (in fact, higher than those found for ligands widely used for the treatment of lead poisoning such as ethylenediaminetetraacetic acid (edta)), as well as in the highest Sr(II)/Ca(II) selectivity reported so far. These results have been rationalized on the basis of the structure of the complexes. X-ray crystal diffraction, (1)H and (13)C NMR spectroscopy, as well as theoretical calculations at the density functional theory (B3LYP) level have been performed. Our results indicate that for large metal ions such as Pb(II) and Sr(II) the most stable conformation is Δ(δλδ)(δλδ), while for Ca(II) our calculations predict the Δ(λδλ)(λδλ) form being the most stable one. The selectivity that bp18c6(2-) shows for Sr(II) over Ca(II) can be attributed to a better fit between the large Sr(II) ions and the relatively large crown fragment of the ligand. The X-ray crystal structure of the Pb(II) complex shows that the Δ(δλδ)(δλδ) conformation observed in solution is also maintained in the solid state. The Pb(II) ion is endocyclically coordinated, being directly bound to the 10 donor atoms of the ligand. The bond distances to the donor atoms of the pendant arms (2.55-2.60 ?) are substantially shorter than those between the metal ion and the donor atoms of the crown moiety (2.92-3.04 ?). This is a typical situation observed for the so-called hemidirected compounds, in which the Pb(II) lone pair is stereochemically active. The X-ray structures of the Zn(II) and Cd(II) complexes show that these metal ions are exocyclically coordinated by the ligand, which explains the high Pb(II)/Cd(II) and Pb(II)/Zn(II) selectivities. Our receptor bp18c6(2-) shows promise for application in chelation treatment of metal intoxication by Pb(II) and (90)Sr(II).