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Efficient Parametrization of Force Field for the Quantitative Prediction of the Physical Properties of Ionic Liquid Electrolytes

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    Molecular Mechanics

    Efficient Parametrization of Force Field for the Quantitative Prediction of the Physical Properties of Ionic Liquid Electrolytes
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    Journal of Chemical Theory and Computation

    Cite this: J. Chem. Theory Comput. 2021, 17, 7, 4274–4290
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    https://doi.org/10.1021/acs.jctc.1c00268
    Published June 7, 2021
    Copyright © 2021 American Chemical Society
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    Abstract

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    The prediction of transport properties of room-temperature ionic liquids from nonpolarizable force field-based simulations has long been a challenge. The uniform charge scaling method has been widely used to improve the agreement with the experiment by incorporating the polarizability and charge transfer effects in an effective manner. While this method improves the performance of the force fields, this prescription is ad hoc in character; further, a quantitative prediction is still not guaranteed. In such cases, the nonbonded interaction parameters too need to be refined, which requires significant effort. In this work, we propose a three-step semiautomated refinement procedure based on (1) atomic site charges obtained from quantum calculations of the bulk condensed phase; (2) quenched Monte Carlo optimizer to shortlist suitable force field candidates, which are then tested using pilot simulations; and (3) manual refinement to further improve the accuracy of the force field. The strategy is designed in a sequential manner with each step improving the accuracy over the previous step, allowing the users to invest the effort commensurate with the desired accuracy of the refined force field. The refinement procedure is applied on N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammonium bis(trifluoromethanesulfonyl)imide (DEME-TFSI), a front-runner as an electrolyte for electric double-layer capacitors and single-molecule-based devices. The transferability of the refined force field is tested on N,N-dimethyl-N-ethyl-N-methoxyethoxyethylammonium bis(trifluoromethanesulfonyl)imide (N112,2O2O1-TFSI). The refined force field is found to be better at predicting both structural and transport properties compared to the uniform charge scaling procedure, which showed a discrepancy in the X-ray structure factor. The refined force field showed quantitative agreement with structural (density and X-ray structure factor) and transport properties—diffusion coefficients, ionic conductivity, and shear viscosity over a wide temperature range, building a case for the wide adoption of the procedure.

    Copyright © 2021 American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jctc.1c00268.

    • Force field nomenclature, atom-type nomenclature, simulation run details, atomic site charges, quantum mechanical potential energy surface (QM-PES), quenched Monte Carlo (QMC), density, liquid structure, self-diffusion coefficients, ionic conductivity, and shear viscosity (PDF)

    • DEME-TFSI and N112,2O2O1-TFSI systems’ GROMACS topology and gro files (ZIP)

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    Journal of Chemical Theory and Computation

    Cite this: J. Chem. Theory Comput. 2021, 17, 7, 4274–4290
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acs.jctc.1c00268
    Published June 7, 2021
    Copyright © 2021 American Chemical Society
    Request reuse permissions

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