Towards a generalized vision of oxides: disclosing the role of cations and anions in determining unit-cell dimensions.
Theoretical calculations of the electron-localization function show that, at the volumes of the two CaO phases (rocksalt and CsCl type), the parent Ca structures (fcc: face-centred cubic and sc: simple cubic, respectively) exhibit charge concentration zones which coincide with the positions occupied by the O atoms in their oxides. Similar features, also observed for the pairs Ca/CaF(2) and BaSn/BaSnO(3), are supported by recent high-pressure experiments as well as electron-localization function (ELF) calculations, carried out on elemental K. At very high pressures, the elemental K adopts the hP4 structure, topologically identical to that of the K atoms in high-pressure K(2)S and high-temperature alpha-K(2)SO(4). Moreover, the ELF for the hP4 structure shows charge concentration (approximately 2 electrons) at the sites occupied by the S atoms in the high-pressure K(2)S phase. All these features confirm the oxidation/high-pressure equivalence as well as the prediction of how cation arrays should be metastable phases of the parent metals. For the first time to our knowledge, the structure type, dimension and topology of several oxides and fluorides (CaO, CaF(2) and BaSnO(3)) are explained in univocal physical terms.
Vegas
Angel
A
Instituto de Química Física Rocasolano, CSIC, C/Serrano 119, Madrid E-28006, Spain. avegas@iqfr.csic.es
Mattesini
Maurizio
M