Molecular Force Field for Ionic Liquids Composed of Triflate or Bistriflylimide Anions

Abstract

A set of force field parameters is proposed for the molecular simulation of ionic liquids containing the anions trifluoromethylsufate and bis(trifluoromethylsulfonyl)imide, also known as triflate and bistriflylimide, respectively. The new set can be combined with existing force fields for cations in order to simulate common room-temperature ionic liquids, such as those of the dialkylimidazolium family, and can be integrated with the OPLS-AA or similar force fields. Ab initio quantum chemical calculations were employed to obtain molecular geometry, torsional energy profiles, and partial charge distribution in the triflate and bistriflylimide anions. One of the torsions in bistriflylimide, corresponding to the dihedral angle S−N−S−C, has a complex energy profile which is precisely reproduced by the present parameter set. A new set of partial electrostatic charges is also proposed for the pyrrolidinium and tri- and tetra-alkylammonium cations. Again, these parameters can be combined with the OPLS-AA specification for amines in order to simulate alkylammonium salts. The force-field models were validated against crystal structures and liquid-state densities.