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Title: Influence of Charge Scaling on the Solvation Properties of Ionic Liquid Solutions

Journal Article · · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
 [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Wisconsin−Madison, Madison, WI (United States)
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Scaled-charge force fields (FFs) are widely employed in the simulation of neat ionic liquids (ILs), where the charges on the ions are empirically scaled to approximately account for electronic polarization and/or charge transfer. Such charge scaling has been found to yield significant improvement in liquid-state thermodynamic and dynamic properties (when compared to experiment). However, the mean field approximation inherent in charge scaling becomes suspect when applied to IL mixtures or solutions. In this work, we simulate solutions of IL with various nonpolar and polar gas solutes and compare results of charge-scaled and polarizable FFs to experiment. Our results demonstrate that scaling of the Coulomb interaction inherent in scaled-charge FFs leads to an underestimation of the solute–solvent electrostatic interaction and thus also the enthalpy and free energy of solvation; this effect is particularly pronounced for polar solutes. In some cases, we find that this artificial reduction in the solute–solvent interaction can also alter the apparent phase behavior of the resulting solution. Altogether, the totality of our results suggests that explicit polarization (rather than charge scaling) is likely necessary to provide high transferability to both neat IL and IL mixtures and solutions.

Research Organization:
Univ. of Wisconsin, Madison, WI (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0014059; SC0017877
OSTI ID:
1576980
Journal Information:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 123, Issue 43; ISSN 1520-6106
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 23 works
Citation information provided by
Web of Science

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Cited By (3)

Molecular dynamics simulation of imidazolium C n MIM-BF 4 ionic liquids using a coarse grained force-field journal January 2020
Molecular Dynamics Simulation of Imidazolium CnMIM-BF4 Ionic Liquids using a Coarse Grained Force-Field text January 2019
Harnessing Structural and Dynamic Heterogeneity to Direct Ion Transport in Plastic Crystal-Polymer Composite Solid-Ion Conductors preprint January 2020

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY