Magnetic Properties of Monomer and Dimer Tetrahedral VO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Entities Dispersed on Amorphous Silica-based Materials: Prediction of EPR Parameters from Relativistic DFT Calculations and Broken Symmetry Approach to Exchange Couplings

Molecular structures of the isolated tetrahedral oxovanadium(IV) and bridged μ-oxo-divanadium(IV) complexes hosted by the clusters mimicking surfaces of amorphous silica-based materials were investigated using density functional theory (DFT) calculations. Principal values of the g and A tensors for the monomer vanadyl species were obtained using the coupled-perturbed DFT level of theory and the spin–orbit mean-field approximation (SOMF). Magnetic exchange interaction for the μ-oxo bridged vanadium(IV) dimer was investigated within the broken symmetry approach. An antiferromagnetic coupling of the individual magnetic moments of the vanadium(IV) centers in the [VO–O–VO]²⁺ bridges was revealed and discussed in detail. The coupling explains pronounced decrease of the electron paramagnetic resonance signal (EPR) intensity, observed for the reduced VO _x /SiO₂ samples with the increasing coverage of vanadia, in terms of transformation of the paramagnetic monomer species into the dimers with S = 0 ground state.     

Highly conducting solid electrolytes based on poly (ethylene oxide-co-propylene oxide)

The conducting properties of solid electrolytes comprising random poly(ethylene oxide-co-propylene oxide) (of 84 : 16 monomer units mole ratio) and lithium, sodium, potassium, cesium, and rubidium salts have been studied. The systems containing some lithium or sodium salts achieved conductivity levels as high as 10^?5–10^?4 S/cm at ambient temperature and greater than 10^?3 S/cm at 100°C. However, the systems with rubidium and cesium salts exhibit conductivities a few orders of magnitude smaller. DSC studies show that the electrolytes studied are characterized by a high content of an amorphous phase (95–100%). It is suggested that the copolymer exhibits lower complexing abilities than that of poly(ethylene oxide), which results in a higher flexibility of electrolytes containing small cations and poor dissociation of the salts having large cations. © 1995 John Wiley & Sons, Inc.     

A Unified Approach to Shifts Induced by Right Invertible Operators

In this paper, shifts for a right invertible operator D induced by an analytic function acting in a linear complete metric space are considered. The case when these shifts coincide with the operator - valued function on a set which contains the set of all D-polynomials and the set of all exponentials is studied. It is shown that in this case these shifts are R-shifts and D-shifts (cf. [1], [10]).     

Infrared study on electrolyte solutions in acetone part III. reactivity of acetone in aldolic condensation

Infrared spectra of perchlorate, halide and nitrate solutions in acetone are studied. The CO and CCC band frequency changes are discussed in terms of the electronic structure of acetone molecules complexed with cation and anion. The correlation between the shift of the CO and CCC bands and the reactivity of acetone molecules in aldolic condensation reaction is given. An explanation of the anion effect in aldolic condensation is proposed.     

Temperature dependence and anisotropy of the hole drift mobility in monoclinic tetracyanoethylene

The tensor of the hole drift mobility is determined in monoclinic tetracyanoethylene by the transient photoconductivity technique. The principal tensor components amount to μ₁ = 0.21, μ₂ = 0.10 and μ₃ = 0.15 cm²/V s at room temperature. Above 250 K the mobility is a decreasing function of temperature and follows an exp(E/kT) dependence (E = 0.08 eV) which is inconsistent with both band and hopping models. Below 250 K the mobility is controlled by a hole trapping level of 0.28 eV deep. The photogeneration efficiency is found to be independent of temperature and proportional to the light intensity.     

Diastereomeric non-equivalence of (−)-ω-camphanic esters of chiral secondary alcohols in 13C NMR spectroscopy

The diastereomeric differences (Δδ) were measured by ¹³C NMR spectroscopy for a series of 11 (?)-ω-camphanic esters of secondary alcohols of known absolute configuration. This method cannot be used for the determination of the absolute configuration, but it can be applied to the estimation of the enantiomeric purity of chiral alcohols.     

On resolvable tree-decompositions of complete graphs

A partition of the edge set of a graph H into subsets inducing graphs H₁,…,H_s isomorphic to a graph G is said to be a G-decomposition of H. A G-decomposition of H is resolvable if the set {H₁,…,H_s} can be partitioned into subsets, called resolution classes, such that each vertex of H occurs precisely once in each resolution class. We prove that for every graceful tree T of odd order the obvious necessary conditions for the existence of a resolvable T-decomposition of a complete graph are asymptotically sufficient. This generalizes the results of Horton and Huang concerning paths and stars.     

Formation of radical anions and not deprotonation starts the reaction of gamma-butyrolactone with potassium anions

A mechanism is proposed for the reaction of gamma-butyrolactone with the potassium anion as a two-electron-transfer reagent. Potassium hydride and potassium 4-potassiobutyrate are formed in this process as intermediates. These compounds deprotonate gamma-butyrolactone. Potassium lactone enolate, potassium butyrate, and hydrogen are the final reaction products.