Structural effects on trends in the deposition and dissolution of metal-supported metal adstructures.

Description/Abstract

A simple thermodynamic formalism is combined with Density Functional Theory calculations to determine periodic trends in the reversible deposition/dissolution potentials of admetals on a variety of transition metal substrates. For each admetal/substrate combination (81 in total), the deposition/dissolution potential shift (referenced to the corresponding potential of the admetal in its bulk, elemental form) is calculated for isolated adatoms, for dimers, and for more extended kink structures. Clear periodic trends are found for the potential shifts across the space of different admetals and substrates. In addition, for the significant majority of these admetal/substrate systems, the structural effects are found to be a strong function of the local coordination number of the metal atoms, thereby verifying an important assumption that has been widely used in semiempirical models of deposition and dissolution.