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Transferable, Polarizable Force Field for Electrolytes, Protic Ionic Liquids and Deep Eutectic Solvents

preprint
revised on 25.09.2020 and posted on 25.09.2020 by Agilio Padua, Kateryna Goloviznina, Margarida Costa Gomes, Zheng Gong
The transferable, polarizable CL&Pol force field for aprotic ionic liquids presented in our previous study (J. Chem. Theory Comput. 2019, 15, 5858, DOI: 10.1021/acs.jctc.9b00689) is extended to electrolytes, protic ionic liquids, deep eutectic solvents, and glycols. These systems are problematic in polarizable simulations because they contain either small, highly charged ions or strong hydrogen bonds, which cause trajectory instabilities due to the pull exerted on the induced dipoles. We use a Tang-Toennies function to dampen, or smear, the interactions between charges and induced dipole at short range involving small, highly charged atoms (such as hydrogen or lithium), thus preventing the "polarization catastrophe". The new force field gives stable trajectories and is validated through comparison with experimental data on density, viscosity, and ion diffusion coefficients of liquid systems of the above-mentioned classes. The results also shed light on the hydrogen-bonding pattern in ethylammonium nitrate, a protic ionic liquid, for which the literature contains conflicting views. We describe the implementation of the Tang-Toennies damping function, of the temperature-grouped Nosé-Hoover thermostat for polarizable molecular dynamics and of the periodic perturbation method for viscosity evaluation from non-equilibrium trajectories in the LAMMPS molecular dynamics code. The main result of this work is the wider applicability of the CL&Pol polarizable force field to new, important classes of fluids, achieving robust trajectories and a good description of equilibrium and transport properties in challenging systems. The transferability and fragment-based approach of CL&Pol will allow ready extension to a wide variety of protic ionic liquids, deep eutectic solvents and electrolytes.

Funding

ANR-16-IDEX-005

Liquid Interfaces of 2D Materials for Nanoelectronic Devices – LIQUI2D

Agence Nationale de la Recherche

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History

Email Address of Submitting Author

agilio.padua@ens-lyon.fr

Institution

École Normale Supérieure de Lyon

Country

France

ORCID For Submitting Author

0000-0002-7641-6526

Declaration of Conflict of Interest

No conflict of interest

Version Notes

v1.0, preprint

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