Metal dissolution from first principles: Potential-dependent kinetics and charge transfer

Metal dissolution and its inverse process are integral to both corrosion and electrodeposition; however, many mechanistic details regarding the dissolution process are challenging to decipher. These include how ion dissolution kinetics and charge transfer are influenced by the competition between metal and solvent interactions under an electrode potential. In this work, we introduce a computational framework based on density functional theory with grand-canonical treatment of electrons to directly predict the potential energy landscape for metal dissolution at a constant potential. Using aluminum as an example, we demonstrate that dissolution kinetics is governed by competing kinetics between two physical processes associated with metal–metal bond breaking and ion-migration within the electrical double layer, respectively. We identify a kinetic transition between regimes dominated by each of these processes and show that this transition depends on the operating electrode potential, among other key factors. It is further found that kinetics and thermodynamics of these processes can be described with a simple, one-parameter Marcus-theory-type model. Beyond offering new understanding of charge transfer during dissolution, our simulation protocol provides a recipe for directly predicting other important quantities in electrochemical reactions from first principles that are difficult to measure, such as the symmetry factor.