Abstract: The development of electrochemistry theory dates back more than a century, from the Gouy-Chapman-Stern (GCS) double layer, phenomenological Tafel kinetics to the classical charge transfer Marcus theory and to the First-Principles simulations. The recent years have seen the rapid development in the application of first principles density functional theory (DFT) simulation on the solid/liquid interface. This article reviews the current theoretical methods for electrochemistry modelling, i.e simple thermodynamic method, periodic continuum solvation method (DFT/CM-MPB) and quantum mechanics molecular dynamics (QMMD). These methods have been applied to provide the atomic level insights into the nature of electrochemical double layer, charge transfer and the potential~current curve of electrocatalytic reaction. Despite these progresses, there is plenty of room for the new design and the improvement of theoretical methods for better describing the complex solid/liquid interface and the reaction therein.

Key words: electrochemistry, first principles calculations, solid/liquid interface, double layer, Tafel kinetics, charge transfer coefficient