Voltage equilibration for reactive atomistic simulations of electrochemical processes

Abstract

We introduce EChemDID, a model to describe electrochemical driving force in reactive molecular dynamics simulations. The method describes the equilibration of external electrochemical potentials (voltage) within metallic structures and their effect on the self consistent partial atomic charges used in reactive molecular dynamics. An additional variable assigned to each atom denotes the local potential in its vicinity and we use fictitious, but computationally convenient, dynamics to describe its equilibration within not-simply connected metallic structures on-the-fly during the molecular dynamics simulation. This local electrostatic potential is used to dynamically modify the atomic electronegativities used to compute partial atomic changes via charge equilibration. Validation tests show that the method provides an accurate description of the electric fields generated by the applied voltage and the driving force for electrochemical reactions. We demonstrate EChemDID via simulations of the operation of electrochemical metallization cells. The simulations predict the switching of the device between a high-resistance to a low-resistance state as a conductive metallic bridge is formed and resistive currents that can be compared with experimental measurements. In addition to applications in nanoelectronics, EChemDID could be useful to model electrochemical energy conversion devices.

19 pages, 5 figures

References in corpus (3)

• Voltage equilibration for reactive atomistic simulations of electrochemical processes
• Redox reactions with empirical potentials: Atomistic battery discharge simulations
• Mesodynamics with implicit degrees for freedom

Cited by in corpus (6)

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• Molecular Simulation of Electrode-Solution Interfaces
• Charge fluctuations from molecular simulations in the constant-potential ensemble
• Voltage equilibration for reactive atomistic simulations of electrochemical processes
• Effect of the metallicity on the capacitance of gold - aqueous sodium chloride interfaces
• A molecular perspective on induced charges on a metallic surface