Local Response Theory of Electrified Interfaces from Screened Effective Charges

Abstract

First-principles, electronic-structure simulations provide direct access to ground-state, global system properties. In the context of computational electrochemistry these are, e.g., bias-dependent energies, free energies, work functions, and capacitances. However, a comparably systematic local description of how these quantities respond to biasing via interfacial charging is still missing. Here, we introduce the screened electrochemical Born effective charge (SEBEC), a mixed total-energy derivative that measures the force response of an atomic degree of freedom to interfacial charging under electrochemical boundary conditions. SEBECs play the role for electrochemistry that Born effective charges play in the modern theory of polarization: they provide an unambiguous decomposition of global response and generate the same formal structures for structural relaxation, capacitance, and electrochemical Stark tuning that are familiar from solid-state response theory. The broader implication is a local response framework that brings electrochemical interfaces closer to the conceptual rigor long established for insulating solids.