Challenges in the first-principles description of electrochemical interfaces

Electrochemical interfaces play a crucial role in many technologically relevant and scientificaly interesting processes related to electrochemical energy conversion and storage. Still, it is fair to say that our atomistic understanding of the structure of such interfaces is still limited, in particular as far as the electric double layer (EDL) at such interfaces is concerned. In this contribution, I will in particular address the challenges associated with an appropriate quantum modeling of the EDL, both from a conceptual and from a computational point of view. I will show how the liquid nature of the electrolyte can be considered in ab initio molecular dynamics calculations [1], also taking the electrode potential into account. On the other hand, I will present examples in which the structure of the electrode surface has been faithfully reproduced as a function of the electrochemical control parameters within a grand-canonical approach [3], but without explicitly considering the electrolyte.

[1] A. Groß and S. Sakong, Chem. Rev. 122, 10746 (2022).

[2] A. Groß, Curr. Opin. Electrochem. 40, 101345 (2023),

[3] A. Groß, J. Phys. Chem. C 126, 11439 (2023).