Ab Initio Simulations of Water/Metal Interfaces

Structures and processes at water/metal interfaces play an important technological role in electrochemical energy conversion and storage, photoconversion, sensors, and corrosion, just to name a few. However, they are also of fundamental significance as a model system for the study of solid–liquid interfaces, which requires combining concepts from the chemistry and physics of crystalline materials and liquids. Particularly interesting is the fact that the water–water and water–metal interactions are of similar strength so that the structures at water/metal interfaces result from a competition between these comparable interactions. Because water is a polar molecule and water and metal surfaces are both polarizable, explicit consideration of the electronic degrees of freedom at water/metal interfaces is mandatory. In principle, ab initio molecular dynamics simulations are thus the method of choice to model water/metal interfaces, but they are computationally still rather demanding. Here, ab initio simulations of water/metal interfaces will be reviewed, starting from static systems such as the adsorption of single water molecules, water clusters, and icelike layers, followed by the properties of liquid water layers at metal surfaces. Technical issues such as the appropriate first-principles description of the water–water and water–metal interactions will be discussed, and electrochemical aspects will be addressed. Finally, more approximate but numerically less demanding approaches to treat water at metal surfaces from first-principles will be briefly discussed.