We have performed an ab initio study of the surface core-level binding energy shift (SCLS) for 11 of the simple metals by means of a Green’s-function technique within the tight-binding linear-muffin-tin-orbitals method. Initial- and final-state effects are included within the concept of complete screening, whereby a SCLS becomes equivalent to the surface segregation energy of a core-ionized atom, a quantity we obtain by separate bulk and surface impurity calculations. The results are in good agreement with experiment in most of those cases where the data originates from single-crystal measurements. We discuss the surface shifts of the electrostatic potentials and the band centers in order to trace the microscopic origin of the SCLS in the simple metals and find that the anomalous subsurface core-level shifts in beryllium are caused by charge dipoles, which persist several layers into the bulk. We furthermore conclude that the unexpected negative sign of the SCLS in beryllium is predominantly an initial-state effect and is caused by the high electron density in this metal.
Physical Review B Condensed Matter, 1994, Vol 50, Issue 16, p. 12118-12130