The formation of the Ba(CuOx)1−y(CO3)y

Carbocuprate compounds are generally described as multiple perovskites with CO ₃ ² - and Cu-O alternating layers containing Ba and/or Sr; they have gained an unexpected importance in the high temperature superconductivity field, because many compounds with transition temperature above 100 K belong to this class of materials.We have started a systematic study on phase formation and stabilisation in the Ba-Cu-C-O system in the temperature range 20-600°C, by using thermal analysis techniques. Starting from a BaCO₃-BaO₂-CuO mixture (311 mol), a new phase isomorphic with BaCO₃ formed after heat treatment above 390°C in air. TG, DSC, EGA and high temperature XRD were employed to follow the complex interaction of the reactants with the atmosphere and the formation of the new phase.     

The properties of the metal complex hydrides

The essential features (geometries of the minima and of the saddle points, energy barriers) of the potential energy surface of the four hydrides YXH₄ mentioned in the title have been determined with two basis sets, of minimal and DZ quality respectively. The importance of the different extent of the deformation of the XH₄ group in the different structures of the four hydrides is brought out and discussed. The aspects of charge distribution and bonding are examined drawing on population analysis, comparison of the electrostatic molecular potentials and decomposition of the interaction energy (this last referred to the Y⁺ + XH ₄ ^– YXH₄ process). The capability of XH₃ in effecting the etherolytic disruption of the Y-H bond is finally brought out.     

Alternative paths in the ring opening of oxadiaziridine: The diimide N-oxide versus the oxodiimide rearrangement

The ring opening of the oxadiaziridine by cleavage of the N-N bond has been theoretically investigated by SCF calculations improved with limited CI. The possible competition of this reaction with the better known ones (N-O bond cleavage, inversion of the N atom) is discussed. The chemical implications of the formation of a new type of 1,3-dipole are examined.     

Fractal nanochannels as the basis of the ionic transport in AgI-based glasses

We propose a new model to explain the transport properties of AgI-based fast ion conducting glasses. The main factor affecting the ionic conductivity is the mobility of the Ag+ carriers, that is controlled by the Ag local environment. We model the ionic conductivity in terms of a percolation between a low-conducting phase (purely oxygen-coordinated sites), and a high-conducting one (iodine/oxygen, I/O, coordinated sites). The percolation takes place along pathways with fractal structure. The nature of the glass network, and namely its connectivity and dimensionality, plays a significant role only for low I/O values, originating the transport and thermal anomalies observed in borate and phosphate glasses.