A New Solid State Table for Predicting Coverage Dependent Adsorption Energies On Transition Metal Surfaces

We have previously shown substantial correlations in the coverage dependent adsorption energies of atomic adsorbates on close-packed transition metal surfaces. The correlations are related to a common adsorbate-induced change to the metal surface electronic structure. The surface d-band is broadened by overlap of the surface d-orbitals with the adsorbate orbitals. The broadening causes a reduction in the average energy of the d-band, which results in a weakening of the adsorbate bonds with increasing coverage. We show here how the d-band broadening, and corresponding coverage dependence can be interpreted in terms of matrix elements that describe the bonding. We present a set of parameters derived from DFT calculations that can be used to predict the adsorbate-induced surface electronic structure changes and the coverage dependence of C, N, O and S adsorption on the late transition metal (111) surfaces.