Constant inner potential DFT for modelling electrochemical systems under constant potential and bias

Electrocatalytic systems are crucial in various renewable energy conversion and storage technologies, forming a foundational basis for our sustainable future. Realizing their full potential requires advancements in catalytic materials to achieve better catalytic efficiencies, higher stability, and lower costs. This necessitates an atomic-level understanding of electrocatalytic systems, particularly the complex electrocatalyst-electrolyte interface, which involves numerous components and processes. Moreover, the interface properties can vary substantially depending on solvent and electrode potential and the variations can, in turn, have direct impact on electrocatalytic behaviour.

The grand-canonical ensemble (GCE) DFT calculations provide a powerful framework for modeling electrochemical interfaces and reactions at the atomic level under fixed electrode potentials. In my presentation, I will introduce the constant inner potential approach, our recent advancement in GCE-DFT, which extends the applicability of the method to systems previously beyond the scope of standard GCE-DFT. The examples will showcase our latest applications of GCE-DFT methods.