Assessment of the performance of commonly used DFT functionals vs. MP2 in the study of IL-Water, IL-Ethanol and IL-(H2O)3 clusters

Abstract

We present a comparative study of the accuracy of different DFT approaches vs. MP2 for evaluating ionic liquids (ILs) + cosolvent. Namely, we are interested in [XBmim] + cosolvent (X being Cl−, BF4−, PF6−, and CH3SO3− anions and cosolvent being water or ethanol) and [XBmim] + (H2O)3 clusters. In this study the B3LYP, B3LYP-D3, M06, M06-2X and M06-HF functionals with Pople and Dunning basis sets are considered. We find that the influence of the basis sets is a factor to take into consideration. As already seen for weakly bonded systems when the basis set quality is low the uncorrected counterpoise (unCP) or averaging counterpoise (averCP) energies must be used due to cancellation errors. Besides, the inclusion of extra diffuse functions and polarization is also required specially in the case of ILs interacting with water clusters. The B3LYP functional does not reproduce either the structure or the interaction energies for ILs + H2O and ILs + EtOH aggregates, the energetic discrepancies being more significant than the structural ones. Among the dispersive corrected functionals, M06-2X results resemble to a great extent the reference data when the unCP interaction energies are considered for both water and ethanol. In turn, M06 and B3LYP-D3 functionals are the best option for ILs containing polar and non-polar anions, respectively, whether the averCP interactions energies are taking into consideration. From the structural point of view, B3LYP and M06 functionals describe more open structures whereas B3LYP-D3, M06-2X and M06-HF structures resemble quite well MP2 results. When the number of water molecules increases the H bonding motif gains importance and the effect depends on the underlying functional. Only M06-2X and M06-HF behaviour is similar to that observed for one water molecule. This is important because to describe ILs-cosolvent solutions is not only necessary to take into account the ILs-cosolvent interactions but also the cosolvent-cosolvent ones in the ensemble of the system.