Muñoz-Rojas D, Subías G, Fraxedas J, Gómez-Romero P, Casañ-Pastor N
Institut de Ciencia de materials de Barcelona, CSIC, Campus UAB, 08193 Bellaterra, Barcelona, Spain.
J Phys Chem B. 2005 Apr 7;109(13):6193-203. doi: 10.1021/jp044493w.
The electronic structure of the recently isolated silver copper oxide Ag(2)Cu(2)O(4) is analyzed along with its precursor Ag(2)Cu(2)O(3) and similar binary oxides, Ag(2)O, AgO, CuO, and NaCuO(2), using X-ray photoemission (XPS) and X-ray absorption (XAS) measurements. The results for Ag(2)Cu(2)O(4) reveal an electronic distribution in which silver and copper share a delocalized valence scheme with both metals in formal oxidation states larger than the usual Ag(I) and Cu(II). Only one type of crystallographic silver or copper is found, but disorder-strain parameters are considerable and the possibilities of thermal disorder, atomic motion, oxygen contribution, mixed valence, and internal charge delocalization are considered. Classical coordination descriptions for oxidized silver are revisited in terms of this new internal charge delocalization framework found for the electronic structure.
