Continuum Embedding Models for Electrolyte Solutions in First‐Principles Simulations of Electrochemistry

Classical polarizable continuum models of liquid solutions are well-assessed tools in quantum- chemistry simulations, allowing the inexpensive characterization of solvent effects in a wide variety of electronic and molecular properties of solutes. Recent developments in continuum embedding models have extended their applicability to condensed matter electronic-structure simulations, allowing the inexpensive study of two-dimensional solvated interfaces. In particular, extensions to the continuum modelling of electrolyte solutions allow for the first time to include important environment effects into the first-principle simulation of electrochemical processes. Thanks to a detailed derivation and analysis of the energetics of electrochemical systems, these methods allow to relate the widely used approach of the computational hydrogen electrode (CHE) to a general grand canonical description of electrified interfaces. Here we will review the main derivation of these recent continuum models, underlining their specific features and advantages with respect to previous approaches in the literature. Initial applications of these models to electro-chemistry and electro-catalysis are presented.