Insights into electrochemical solid/liquid interfaces under potential control from first principles and atomistic calculations

Many of the challenges we face today in relation to electro-catalysis, fuel cells, corrosion, battery materials, and others, centre on our understanding of processes occurring at electrochemical solid/liquid interfaces. Targeted design and optimisation of desired functionalities critically rely on the understanding, quantifying and ultimately controlling such processes already at the scale of atoms and molecules. Attaining the required insights is, however, challenging to both theoretical modelling and experimental characterisation. In the past few years, we have developed and implemented key methodological approaches and algorithms that allow an unprecedentedly realistic and fully ab initio description of phenomena taking place at the electrified solid-liquid interface. Our recent advances in developing a novel potentiostat design [1] and a canonical thermopotentiostat [2] enable us to control the electrode potential of the system by tuning the excess charge of the working electrode and use ab initio and atomistic molecular dynamics simulations to study solid/liquid interfaces under realistic conditions of applied bias. Opportunities opened by the availability of these new approaches will be showcased by discussing the properties of water and the adsorption and desorption behaviour of ions at electrified solid/liquid interfaces. Furthermore, the impact of water on the properties of these interfaces will be discussed using the example of an H/Pt/H₂O interface [3; Surendralal et al., submitted].