Electronic structure and valence-bond band structure of cuprate superconducting materials.

From ab initio calculations on various clusters representing the La2-xSrxCu(1)O(4) and Y(1)Ba(2)Cu(3)O(7) classes of high-temperature superconductors, it is shown that (i) all copper sites have a Cu(II)(d(9))oxidation state with one unpaired spin that is coupled antiferromagnetically to the spins of adjacent Cu(II) sites; (ii) oxidation beyond the cupric (Cu(II)) state leads not to Cu(III) but rather to oxidized oxygen atoms, with an oxygen ppi hole bridging two Cu(II) sites; (iii) the oxygen ppihole at these oxidized sites is ferromagnetically coupled to the adjacent Cu(II)d electrons despite the fact that this is opposed by the direct dd exchange; and (iv) the hopping of these oxygen ppi holes (in CuO sheets or chains) from site to site is responsible for the conductivity in these systems (N-electron band structures are reported for the migration of these localized charges).