Electronic structure effects in transition metal surface chemistry

Based on density functional theory and the Newns-Anderson model we present a detailed study of how an inclusion of higher order moments of the density of states can explain observed fine structure variations in oxygen bonding at metal surfaces. The many and sometimes closely coupled parameters that define the band-structure and its position are shown to force the very late transition metals to change shape abruptly. This induces variations in bond-strengths, which are not captured by the simple but successful d-band model. We demonstrate that these variations can be recaptured by a slight modification of the descriptor.