Comparison between Ab Initio Molecular Dynamics and OPLS-Based Force Fields for Ionic Liquid Solvent Organization

OPLS-based force fields (FFs) have been shown to provide accurate bulk-phase properties for a wide variety of imidazolium-based ionic liquids (ILs). However, the ability of OPLS to reproduce an IL solvent structure is not as well-validated given the relative lack of high-level theoretical or experimental data available for comparison. In this study, ab initio molecular dynamics (AIMD) simulations were performed for three widely used ILs: the 1-butyl-3-methylimidazolium cation with chloride, tetrafluoroborate, or hexafluorophosphate anions, that is, [BMIM][Cl], [BMIM][BF₄], and [BMIM][PF₆], respectively, as a basis for further assessment of two unique IL FFs: the ±0.8 charge-scaled OPLS-2009IL FF and the OPLS-VSIL FF. The OPLS-2009IL FF employs a traditional all-atom functional form, whereas the OPLS-VSIL FF was developed using a virtual site that offloads negative charge to inside the plane of the ring with careful attention given to reproducing hydrogen bonding. Detailed comparisons between AIMD and the OPLS FFs were made based on radial distribution functions (RDFs), combined distribution functions (CDFs), and spatial distribution functions (SDFs) to examine cation-anion interactions and π⁺-π⁺ stacking between the imidazolium rings. While both FFs were able to correctly capture the general solvent structure of these popular ILs, the OPLS-VSIL FF quantitatively reproduced interaction distances more accurately. In addition, this work provides further insights into the different short- and long-range structure patterns of these popular ILs.