Grand-canonical approaches to understand structures and processes at electrochemical interfaces from an atomistic perspective

Electrochemical interfaces between an electrode and an electrolyte are often covered by ions from the solution. These adsorbed ions can strongly modify the properties of the interfaces. Furthermore, in electrocatalysis, the reacting species typically have to get into contact with the surface of the electrocatalyst, where the reaction then proceeds. Hence the understanding of the interaction of solvated species with electrode surfaces and the determination of the resulting adsorbate structures as a function of electrochemical control parameters such as electrode potential and electrolyte concentrations are crucial in electrochemistry. Here, grand-canonical theoretical approaches to derive adsorbate structures at electrochemical interfaces from an atomistic perspective will be reviewed. Special emphasis will be put on the distinction between the validity of the approach and the approximations that are typically made when using this approach.

Automated summary

In electrochemistry, the interface between an electrode and an electrolyte is often influenced by ions from the solution, which can alter the properties of the interface significantly. For electrocatalysis to occur, the reacting species need to come into contact with the surface of the catalyst, highlighting the importance of understanding the interaction between solvated species and electrode surfaces. The determination of resulting adsorbate structures based on electrochemical control parameters is crucial, and theoretical approaches to derive these structures are reviewed with emphasis on the validity of the approach and typical approximations made.