A model for the electrochemical interface appropriate to the simulation of metal atom deposition and dissolution processes using electronic structure methods has been constructed and analyzed to observe the key steps governing the movement of a metal atom across the electrochemical double layer. A transition from metal-metal bonding to metal-solvent bonding occurs at a distance of 1 angstrom. Shortcomings in this model are assessed and related to the difficulty of dynamical sampling in ab initio treatments. The model is shown to provide a flexible basis for understanding the effect of system perturbations to the structure of the dissolution potential energy surface. (C) 2008 Elsevier B.V. All rights reserved.