Ab initio modeling of electrochemical interfaces and determination of electrode potentials

The choice for representation of the electrolyte phase can vary from continuum models, molecular mechanics to ab initio molecular dynamics (AIMD) method. Increase of computational power has encouraged applications of AIMD to electrochemical interfaces, for example calculating interfacial structures, potentials of zero charge of metal/water interfaces, surface acidities, and band alignment of semiconductor/water interfaces, thermochemistry of surface reactions, etc. This chapter begins by introducing related theoretical background of electrochemistry, including the concept of the electrode potential and reference electrode. It summarizes the computational methods for modeling electrochemical interfaces. The chapter reviews the two main methods for computing the electrode potentials of the solid/liquid interfaces, i.e. work function based and reference electrode based methods. Finally, some applications of these methods for simulations of interfaces and determination of electrode potentials are mentioned.