Structure and Energetics of Li+–(BF4 –) n , Li+–(FSI–) n , and Li+–(TFSI–) n : Ab Initio and Polarizable Force Field Approaches

The Li+–BF4 – and BF4 ––BF4 – interactions are studied using second order perturbation theory (MP2) and coupled cluster singles and doubles approach, including the effect of connected triples, CCSD(T). The MP2 and CCSD(T) results are in excellent agreement. Using only the MP2 approach, the interactions of Li+ with bis(trifluoromethane)sulfonimide anion (TFSI) and Li+ with bis(fluorosulfonyl)imide anion (FSI) are studied. The results of these high level calculations are compared with density functional theory (DFT) calculations for a variety of functionals and with the APPLE&P force field. The B3LYP approach well reproduces the accurate calculations using both a small and large basis set. The M06 and M06L functionals in the larger basis set are in good agreement with the high level calculations. While the APPLE&P force field does not outperform the best functionals, the APPLE&P results agree better with the accurate results than do some of the functionals tested.