The electrochemical interface in first-principles calculations

Abstract First-principles predictions play an important role in understanding chemistry at the electrochemical interface. Electronic structure calculations are straightforward for vacuum interfaces, but do not easily account for the interfacial fields and solvation that fundamentally change the nature of electrochemical reactions. Prevalent techniques for first-principles prediction of electrochemical processes range from expensive explicit solvation using ab initio molecular dynamics, through a hierarchy of continuum solvation techniques, to neglecting solvation and interfacial field effects entirely. Currently, no single approach reliably captures all relevant effects of the electrochemical double layer in first-principles calculations. This review systematically lays out the relation between all major approaches to first-principles electrochemistry, including the key approximations and their consequences for accuracy and computational cost. Focusing on ab initio methods for thermodynamic properties of aqueous interfaces, we first outline general considerations for modeling electrochemical interfaces, including solvent and electrolyte dynamics and electrification. We then present the specifics of various explicit and implicit models of the solvent and electrolyte. Finally, we discuss the compromise between computational efficiency and accuracy, and identify key outstanding challenges and future opportunities in the wide range of techniques for first-principles electrochemistry.