Adsorption potentials for nonplanar geometries

We present a method to compute, assuming a continuous distribution of sources, the elementary potential created by a differential element of volume of matter, whose integral generates a known adsorption field V(z) for a planar surface. We show that this elementary potential is univocally determined by the original field and can be used to generate adsorption potentials for other nontrivial geometries. We illustrate the method for the Chizmeshya-Cole-Zaremba physisorption potential and discuss several examples and applications.

Adsorption energy and spin state of first-row transition metals adsorbed on MgO(100)

Slab and cluster model spin-polarized calculations have been carried out to study various properties of isolated first-row transition metal atoms adsorbed on the anionic sites of the regular MgO(100) surface. The calculated adsorption energies follow the trend of the metal cohesive energies, indicating that the changes in the metal-support and metal-metal interactions along the series are dominated by atomic properties. In all cases, except for Ni at the generalized gradient approximation level, the number of unpaired electron is maintained as in the isolated metal atom. The energy required to change the atomic state from high to low spin has been computed using the PW91 and B3LYP density-functional-theory-based methods. PW91 fails to predict the proper ground state of V and Ni, but the results for the isolated and adsorbed atom are consistent within the method. B3LYP properly predicts the ground state of all first-row transition atom the high- to low-spin transition considered is comparable to experiment. In all cases, the interaction with the surface results in a reduced high- to low-spin transition energy.