The computational modeling of chemical reactions at electrode interfaces presents extraordinary challenges from the perspective of electronic structure theory.  Target applications include electrolyte reduction in formation of the solid-electrolyte interphase (SEI) and the nucleation and growth of metal dendrites.  These problems combine large system sizes with subtle interactions, multiple dynamical timescales, and electronically non-adiabatic effects.  The development of new methods to perform reliable, on-the-fly electronic structure calculations at a computational cost that makes feasible the simulation of long-timescale dynamics in large systems remains a central theoretical challenge. We describe progress towards the development of accurate, scalable treatments for describing the electronic structure of electrode-electrolyte interfaces in molecular simulations.  Specifically, we introduce the recently developed Exact Embedding method for exactly calculating the non-additive kinetic potential (NAKP) in embedded density functional theory (e-DFT) [1], and we demonstrate the accuracy and the scalability of this approach for condensed-phase systems [2].  Finally, we describe recent progress towards a new, multi-scale e-DFT approach that allows for the seamless electronic structure description of the electrode/electrolyte interface.[1] J. D. Goodpaster, N. Ananth, F. R. Manby, and T. F. Miller, III, �Exact non-additive kinetic potentials for embedded density functional theory,� J. Chem. Phys. 133 (2010) 084103.[2] J. D. Goodpaster, T. A. Barnes, and T. F. Miller, III, �Embedded density functional theory for covalently bonded and strongly interacting subsystems,� J. Chem. Phys., 134 (2011) 164108.

Exactly embedded density functional theory methods for the multi-scale simulation of electrode interfaces

243rd National Meeting (2012)

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