(553d) Simulating the Electrochemical Double Layer Using Charge Dynamics

We have begun performing molecular dynamics (MD) simulations and quantum-chemistry calculations to study the effect of additive molecules at the electrolyte-metal interface for model systems characteristic of copper electrodeposition baths. The goal of the work is to improve understanding of the mechanisms by which additives enhance metal deposition, which will allow future optimization and tuning of additives for deposition problems. MD simulations are ideal for directly relating experimentally observed behavior to molecular structure and intermolecular interactions, because of the great amount of information available in the simulations. In order for the simulations to realistically model the molecular interactions of charged solution species with the metal, it is necessary for charges in the metal to be mobile. We describe a novel simulation algorithm to efficiently accomplish this. The method serves as a bridge between expensive ab initio calculations and large-scale MD simulations and should have application in other molecular systems to be simulated.