Grand-Canonical First Principles-Based Calculations of Electrochemical Reactions

Abstract

This article introduces the first principles-based grand-canonical formalisms of several representative electronic structure calculation methods in electrochemistry, which are essential for elucidating the atomic-scale mechanisms of electrochemical reactions and discovering the guiding principles for designing advanced materials. While most applications still rely on approximate structures obtained by static calculations at absolute zero, the foundational theories of more rigorous molecular dynamics simulations are also developing. I discuss methods that combine these theories with emerging machine-learning interatomic potentials, suggesting that this approach could pave the way to predict the thermodynamics and kinetics of electrochemical reactions at finite temperatures purely from first principles.