Title:Open Thermodynamic Boundary Conditions for First-Principles Electrochemistry

Speaker:Prof.Stefan Wippermann, Philipps-Universität Marburg, Germany

Time:2026-07-17 15: 30

Venue:Room W260, Physics Building

Abstract:Ab initio techniques have revolutionized the way in which theory can help practitioners to explore critical mechanisms and to develop new strategies for materials discovery and design. Yet, their application to electrochemical systems remains limited: Electrified interfaces are inherently open thermodynamic systems. Consequently, the electrode potential and the chemical potentials of the participating species are determined by external reservoirs. Capturing reaction mechanisms and free-energy barriers requires molecular dynamics simulations, where the electrode potential ceases to be a static boundary condition and instead becomes a thermodynamic degree of freedom. In real electrochemical systems, the electrode potential continuously evolves in response to charge transfer, ion adsorption and solvent reorganization. Reproducing this evolution of the electrode potential within a finite ab initio simulation cell constitutes one of the central challenges of first-principles electrochemistry.

Here we present a framework that realizes open thermodynamic boundary conditions in ab initio molecular dynamics by introducing dynamic control of the electrode potential. The resulting framework provides a physically consistent description of dynamically evolving electrochemical interfaces in finite simulation cells. In order to demonstrate its performance, we reveal the precise mechanistic origin of the anomalous anodic hydrogen evolution on magnesium - a problem that has remained unexplained for more than 150 years. More generally, the framework enables predictive first-principles simulations of electrochemical systems under realistic operating conditions.

Bio：Stefan Wippermann is Professor of Theoretical Physics at Philipps-Universität Marburg, Germany, where he leads the Ab Initio Energy Materials Group. His research combines first-principles electronic structure theory, molecular dynamics and multiscale modelling to understand electrochemical interfaces, energy materials and low-dimensional quantum materials. His work focuses on the development of predictive simulation methods for electrochemical systems, including constant-potential ab initio molecular dynamics and open thermodynamic boundary conditions for electrified interfaces. Beyond electrochemistry, his research addresses charge and exciton dynamics in quantum materials, solid-state phase transitions and light-matter interactions. His current research aims to bridge the gap between atomistic simulations and experimentally relevant operating conditions.

Short CV:

2011-2013: Postdoc at Giulia Galli Group, University of California, Davis

since 2013: Groupleader at Max-Planck-Institute for Sustainable Materials, Düsseldorf, Germany

since 2022: Professor of Theoretical Physics, Philipps-Universität Marburg, Germany