Capturing Electrode Potential Dynamics in Ab Initio Electrochemical Simulations

Learn advanced computational electrochemistry techniques in this 45-minute conference talk that addresses the critical challenge of electrode potential treatment in atomistic simulations of electrochemical interfaces. Explore how conventional constant-charge and constant-voltage boundary conditions fail to capture complete potential dynamics, reproducing electrode potential behavior in only limited regions of the supercell while suppressing dynamics elsewhere. Discover the revolutionary thermopotentiostat approach that introduces dynamic boundary conditions, enabling ab initio molecular dynamics simulations to accurately reproduce potential distribution dynamics throughout microscopic simulation volumes. Examine the practical application of this technique to solve the 150-year-old mystery of anomalous anodic hydrogen evolution during magnesium corrosion, where simulations reveal a transiently stable Mg²⁺(OH)⁻ ion complex behaving as a unipositive Mg species. Understand how these findings reconcile the long-standing controversy between coulometric measurements indicating unipositive Mg and spectroelectrochemical techniques that never detected it. Gain insights into how dynamic boundary conditions unlock mechanistic understanding hidden under static control conditions and recognize their essential role in enabling predictive ab initio electrochemistry for complex electrochemical systems.