First principles approaches and concepts for electrochemical systems

Abstract

Ab initio techniques have revolutionised the way in which theory can help practitioners to explore critical mechanisms that govern reactions or properties, and to develop new strategies for materials discovery and design. Yet, their application to electrochemical systems is still limited, due to the challenges electronic structure calculations face in achieving a realistic description of electrified solid/liquid interfaces including, e.g., potential and pH control or free energies of barrier configurations. A well-known example of how novel concepts can extend the scope of simulations is the development of thermostats, which introduced temperature control to electronic structure Density Functional Theory (DFT) calculations. The analogous technique for modelling electrochemical systems - potential control, inherent to most electrochemical experiments - is just emerging. In this review, we critically discuss state-of-the-art approaches to describe electrified interfaces between a solid electrode and a liquid electrolyte in realistic environments. By exchanging energy, electronic charge and ions with their environment, electrochemical interfaces are thermodynamically open systems. In addition, large fluctuations of the electrostatic potential and field occur on the time and length scales relevant to chemical reactions. We systematically discuss the key challenges in incorporating these features into realistic ab initio simulations, as well as the available techniques and approaches to overcome them, in order to facilitate the development and use of these novel techniques by the wider community. These methodological developments provide researchers with a new level of realism to explore fundamental electrochemical mechanisms and reactions from first principles.