Modeling magnesium surfaces and their dissolution in an aqueous environment using an implicit solvent model

Abstract

Magnesium has attracted growing interest for its use in various applications, primarily due to its abundance, lightweight properties, and relatively low cost. However, one major drawback to its widespread use remains to be its reactivity in aqueous environments, which is poorly understood at the atomistic level. Ab initio density functional theory methods are particularly well suited to bridge this knowledge gap, but the explicit simulation of electrified water/metal interfaces is often too costly from a computational viewpoint. Here, we investigate water/Mg interfaces using the computationally efficient implicit solvent model VASPsol. We show that the Mg (0001), (101̄0), and (101̄1) surfaces each form different electrochemical double layers due to the anisotropic smoothing of the electron density at their surfaces, following Smoluchowski rules. We highlight the dependence that the position of the diffuse cavity surrounding the interface has on the potential of zero charge and the electron double layer capacitance, and how these parameters are also affected by the addition of explicit water and adsorbed OH molecules. Finally, we calculate the equilibrium potential of Mg2+/Mg0 in an aqueous environment to be -2.46 V vs a standard hydrogen electrode, in excellent agreement with the experiment.