A theoretical investigation of the interactions between water molecules and ionic liquids.

Quantum chemical calculations have been used to investigate the interaction between water molecules and ionic liquids based on the imidazolium cation with the anions [Cl(-)], [Br(-)], [BF(4)(-)], and [PF(6)(-)]. The predicted geometries and interaction energies implied that the water molecules interact with the Cl(-), Br(-), and BF(4)(-0 anions to form X(-)...W (X = Cl or Br, W = H(2)O), 2X-...2W, BF(4)(-)...W, and W...BF(4)(-)...W complexes. The hydrophobic PF(6)(-) anion could not form a stable complex with the water molecules at the density functional theory (DFT) level. Further studies indicate that the cation could also form a strong interaction with the water molecules. The 1-ethyl-3-methylimidazolium cation (Emim(+)) has been used as a model cation to investigate the interaction between a water molecule and a cation. In addition, the interaction between the ion pairs and the water was studied by using 1-ethyl-3-methylimidazolium chloride (Emim x Cl) as a model ionic liquid. The strengths of the interactions in these categories follow the trend anion-W > cation-W > ion pair-W.