Fine-Tuning the Polarizable CL&Pol Force Field for the Deep Eutectic Solvent Ethaline

TL;DR

This paper improves the CL&Pol polarizable force field for deep eutectic solvents by correcting atomic parameters and overpolarization issues, enhancing simulation accuracy and reliability.

Contribution

The authors identified and fixed specific problems in the original CL&Pol force field, making it more accurate for simulating DESs like ethaline.

Findings

Corrected chloride-hydroxyl interactions based on ab initio data.

Extended damping functions to reduce overpolarization effects.

Achieved more realistic structural and phase behavior in simulations.

Abstract

Polarizable force fields are gradually becoming a common choice for ionic soft matter, in particular for molecular dynamics (MD) simulations of ionic liquids (ILs) and deep eutectic solvents (DESs). The CL&Pol force field introduced in 2019 is the first general, transferable and polarizable force field for MD simulations of different types of DESs. The original formulation contains, however, some problems that appear in simulations of ethaline and may also have a broader impact. First, the originally proposed atomic diameter parameters are unbalanced, resulting in too weak interactions between the chlorides and the hydroxyl groups of the ethylene glycol molecules. This, in turn, causes an artificial phase separation in long simulations. Second, there is an overpolarization of chlorides due to strong induced dipoles that give rise to the presence of peaks and antipeaks at very low $q$-vector values (\SI{2.4}{\per\nano\meter}) in the partial components of the structure factors. In physical terms, this is equivalent to overestimated spatial nano-scale heterogeneity. To correct these problems, we adjusted the chloride-hydroxyl radial distribution functions against \textit{ab initio} data and then extended the use of the Tang-Toennis damping function for the chlorides' induced dipoles. These adjustments correct the problems without losing the robustness of the CL\&Pol force field. The results were also compared with the non-polarizable version, the CL&P force field. We expect that the corrections will facilitate reliable use of the CL&Pol force field for other types of DESs.