Integrating First-Principles Simulations with Electrochemical Experiments: Towards a Realistic Description of Aqueous Interfaces

Improved understanding of electrochemical interfaces is critical for a wide variety of emerging applications, such as hydrogen production, supercapacitors and water desalination. In this talk, we will discuss how first-principles simulations can be integrated with in-situ experiments to understand physicochemical properties of several representative electrochemical systems. We will present our studies of aqueous solutions at graphitic interfaces, where we show that structure and electrical response of the interfaces is governed by a complex interplay between bias potential, intrinsic electronic properties of the electrode, and specific ion effects-including ion hydration and charge transfer. In addition, we will discuss how a combination of first-principles molecular dynamics simulations, many-body perturbation theory, and X-ray photoelectron spectroscopy can provide insights into the relationship between interfacial structure, electronic properties of semiconductors and their reactivity in aqueous solutions.

This work was performed under the auspices of the U.S. DOE by LLNL under Contract DE-AC52-07NA27344, and is supported by the U.S. DOE, Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office via HydroGEN consortium