GAFF-Based Polarizable Force Field Development and Validation for Ionic Liquids.

Abstract

Ionic liquids (ILs) have been used in many applications, including gas separations, electrochemistry, lubrication, and catalysis. Understanding how the different properties of ILs are related to their chemical structure and composition is crucial for these applications. Experimental investigations often provide limited insights and can be tedious in exploring a range of state points. Therefore, molecular simulations have emerged as a powerful tool that not only offers a microscopic perspective but also enables rapid screening and prediction of physical properties. The accuracy of these predictions, however, depends on the quality of the intermolecular potentials (force fields) used. The widely used classical fixed charge models, such as GAFF, OPLS, and CL&P, are popular due to their simplicity and computational efficiency. However, it has been shown that the use of integer charges with these classical models leads to sluggish dynamics. The use of scaled charge models can improve the dynamics, but these mean-field approaches are unable to account for polarization effects explicitly. Several different approaches have been proposed to include polarizability in IL force fields. In this work, we follow the protocol of the CL&Pol model to develop a Drude oscillator model based on the GAFF force field (Goloviznina, K., et al. J. Chem. Theory Comput. 2019, 15, 5858). We compare the performance of the model for eight imidazolium- and pyrrolidinium-based ILs against that of other models. We find that the new model provides reasonable estimations of density, self-diffusivity, and structural properties for these ILs and suggests a relatively simple way of extending the general GAFF model to more ILs.