Constant Chemical Potential-Quantum Mechanical-Molecular Dynamics simulations of the Graphene-electrolyte double layer

TL;DR

This paper introduces a novel coupling of constant potential molecular dynamics with quantum mechanics to accurately simulate graphene-electrolyte interfaces, capturing detailed electrochemical properties across various ion concentrations.

Contribution

The study develops a new simulation protocol combining CμMD and QMMD to model polarizable electrodes and electrolyte solutions, enabling detailed analysis of double layer properties.

Findings

Accurate modeling of electrolyte screening and potential profiles.

Calculation of electrochemical double layer capacitance across concentrations.

Observation of ion adsorption and clustering phenomena at the interface.

Abstract

We present the coupling of two frameworks -- the pseudo-open boundary simulation method known as constant potential Molecular Dynamics simulations (C$\mu$MD), combined with QMMD calculations -- to describe the properties of graphene electrodes in contact with electrolytes. The resulting C$\mu$QMMD model was then applied to three ionic solutions (LiCl, NaCl and KCl in water) at bulk solution concentrations ranging from 0.5 M up to 6 M in contact with a charged graphene electrode. The new approach we are describing here provides a simulation protocol to control the concentration of the electrolyte solutions while including the effects of a fully polarizable electrode surface. Thanks to this coupling, we are able to accurately model both the electrode and solution side of the double layer and provide a thorough analysis of the properties of electrolytes at charged interfaces, such as the screening ability of the electrolyte and the electrostatic potential profile. We also report the calculation of the integral electrochemical double layer capacitance in the whole range of concentrations analysed for each ionic species, while the QM simulations provide access to the differential and integral quantum capacitance. We highlight how subtle features, such as the adsorption of potassium at the interface or the tendency of the ions to form clusters, emerge from our simulations, contribute to explaining the ability of graphene to store charge and suggest implications for desalination.