There has been considerable interest in microscopic aspects of material removal processes in fields such as corrosion, erosion, evaporation, battery technology, electropolishing, and semiconductor etching. Reports of theoretical work related to many of these problems can be found in the literature although metal dissolution is a noticeable exception. Critical issues common to all dissolution reactions include the relationship between the surface morphology and the driving term (e.g. potential, concentration, temperature); the role of surface active sites, dislocations, and other heterogeneities to the dissolution kinetics; and the influence of surface diffusion We have shown that microscopic analysis of electrochemically dissolving metal surfaces via computer simulations can lead to a fundamental understanding of the relationship between surface morphology and dissolution kinetics. Microscopic information on surface processes is not contained in phenomenological equations such as the Butler-Volmer equation, which is commonly used to describe electrode dissolution. In particular, we find that the surface roughness and, consequently, the number of surface active sites, are determined by thermodynamic parameters such as the applied electrode potential. The morphology of surfaces has been shown to be an essential aspect of kinetic processes such as crystal growth and mineral dissolution. Electrochemical processes, however, are fundamentally different in that they feature the presence of very high electrical fields at the interface, which directly affect the surface reactions. To date, treatments of the kinetics of electrochemically dissolving metal surfaces have ignored surface morphology. Over the next few years, results from theoretical modeling of dissolution processes, in conjunction with new experimental techniques such as STM, are expected to provide a new insight into the processes controlling metal dissolution and corrosion.
