Systematic refinement of Canongia Lopes-Pádua force field for pyrrolidinium-based ionic liquids.

Reliable force field (FF) is a central issue in successful prediction of physical chemical properties via computer simulations. While Canongia Lopes-Pádua (CL&P) FF provides good to excellent thermodynamics and structure of pure room-temperature ionic liquids (RTILs), it suffers from drastically and systematically underestimated ionic motion. This occurs due to neglected partial electron transfer from the anion to the cation, resulting in unphysically small simulated self-diffusion and conductivity and high shear viscosities. We report a systematic refinement of the CL&P FF for six pyrrolidinium-based RTILs (1-N-butyl-1-methylpyrrolidinium dicyanamide, triflate, bis(fluorosulfonyl)imide, bis(trifluoromethanesulfonyl)imide, tetrafluoroborate, chloride). The elaborated procedure accounts for specific cation-anion interactions in the liquid phase. Once these interactions are described effectively, experimentally determined transport properties can be reproduced with an acceptable accuracy. Together with the original CL&P parameters, our force field fosters computational investigation of ionic liquids. In addition, the reported results shed more light on the chemical nature of cation-anion binding in various families of RTILs.