Unraveling the Ag+ ion coordination and solvation thermodynamics in the 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid

The solvation of the Ag+ ion in the 1-butyl-3-methylimidazolium tetrafluoroborate ([C4mim][BF4]) ionic liquid (IL) has been studied by means of experimental and theoretical methods with the aim of elucidating the cation coordination structure and thermodynamic properties. Car-Parrinello molecular dynamics (CPMD) simulations showed that the Ag+ ion is coordinated by an average number of four [BF4]- anions in a pseudo-tetrahedral geometry. A high configurational disorder of the first solvation sphere is found, where the anions can be found both in mono-and bidentate coordination mode around the Ag+ ion. Also, a solvational equilibrium is observed as due to [BF4]- anion dissociation along the trajectory. The analysis of X-ray absorption spectroscopy data confirmed the picture provided by the CPMD simulation. Classical molecular dynamics simulations were carried out to obtain the single-ion solvation thermodynamic parameters. The negative water -> IL free energy of transfer suggests that the Ag+ ion is more favorably solvated in the [C4mim][BF4] IL than in water. This behavior is due to a balance between the enthalpic and entropic contributions, which allows to find a rationale to the strong solvation capabilities of BF4-based ILs towards Ag+.