Assessing OPLS-based force fields for investigating the characteristics of imidazolium-based dicationic ionic liquids: A comparative study with AIMD simulations and experimental findings

Abstract

In this study, we extended the optimized potentials for liquid simulation-ionic-liquid virtual site (OPLS-VSIL) force field (FF) to imidazolium-based dicationic ionic liquids (DILs) and evaluated the ability of different OPLS-based FFs (i.e., OPLS-2009IL, 0.8*OPLS-2009IL, and OPLS-VSIL) in predicting different properties of the studied DIL by comparing their results with ab initio molecular dynamics (AIMD) simulation and experimental results. To achieve this purpose, MD simulations with three different OPLS-based FFs as well as AIMD simulation were performed for [C3(mim)2][NTF2]2 DIL and its structural, dynamical, vibrational, and volumetric properties were analyzed. Structural properties of the studied DIL, i.e., radial distribution functions (RDFs), structure factor, and hydrogen-bond network, showed that compared to 0.8*OPLS-2009IL FF, there is a much better agreement between the results of both OPLS-2009IL and OPLS-VSIL FFs with the AIMD simulation. On the other hand, the results of dynamical properties, such as mean square displacements, van Hove correlation functions as well as hydrogen bond, ion pair, and ion cage dynamics, depicted that in both 0.8*OPLS-2009IL and OPLS-VSIL FFs, the dynamics of the system is almost similar, and compared to OPLS-2009IL FF, they have better agreements with experimental results where they exist. So, it can be seen that although reducing the total charge of studied DIL by 20% leads to an increase in the dynamics of the system, the type distribution of partial charges on each atom does not significantly affect the system’s dynamics. The calculated infrared (IR) and power spectra showed that the vibrational features of studied DIL in three OPLS-based FFs are mostly the same and reducing total charge and different type distribution of partial charges have no significant effect on the studied system. Furthermore, in volumetric properties, OPLS-VSIL FF shows somehow better agreement with experimental results. Overall, the evaluation of different structural, dynamical, vibrational, and volumetric properties of [C3(mim)2][NTF2]2 DIL shows that the OPLS-VSIL FF may be the best choice among the different studied OPLS FFs.