Electronic Structure of the c(2x2)O/Cu(001) System

Abstract

The locally self-consistent real space multiple scattering technique has been applied to calculate the electronic structure and chemical binding for the c(2x2)O/Cu(001) system, as a function of $d_{O-Cu1}$ -- the height of oxygen above the fourfold hollow sites. It is found that the chemical binding between oxygen and copper has a mixed ionic-covalent character for all plausible values of $d_{O-Cu1}$. Furthermore, the electron charge transfer from Cu to O depends strongly on $d_{O-Cu1}$ and is traced to the variation of the long-range electrostatic part of the potential. A competition between the hybridization of Cu1-$d_{xz}$ with O-$p_x,p_y$ and Cu1-$d_{x^2-y^2}$ with O-$p_z$ states controls modification of the electronic structure when oxygen atoms approach the Cu(001) surface. The anisotropy of the oxygen valence electron charge density is found to be strongly and non-monotonically dependent on $d_{O-Cu1}$.