Improving the Accuracy of Atomistic Simulations of the Electrochemical Interface

Atomistic simulation of the electrochemical double layer is an ambitious undertaking, requiring quantum mechanical description of electrons, phase space sampling of liquid electrolytes, and equilibration of electrolytes over nanosecond time scales. All models of electrochemistry make different trade-offs in the approximation of electrons and atomic configurations, from the extremes of classical molecular dynamics of a complete interface with point-charge atoms to correlated electronic structure methods of a single electrode configuration with no dynamics or electrolyte. Here, we review the spectrum of simulation techniques suitable for electrochemistry, focusing on the key approximations and accuracy considerations for each technique. We discuss promising approaches, such as enhanced sampling techniques for atomic configurations and computationally efficient beyond density functional theory (DFT) electronic methods, that will push electrochemical simulations beyond the present frontier.

Automated summary

Atomistic simulation of the electrochemical double layer is a complex task that requires quantum mechanical description of electrons, phase space sampling of liquid electrolytes, and equilibration of electrolytes over nanosecond time scales. Different models of electrochemistry make different compromises in the approximation of electrons and atomic configurations. This review discusses various simulation techniques suitable for electrochemistry, emphasizing the key approximations and accuracy considerations for each technique. Promising approaches, such as enhanced sampling techniques for atomic configurations and computationally efficient electronic methods beyond density functional theory (DFT), are also explored, which will push the boundaries of electrochemical simulations.