Observation of Charge Inversion of an Ionic Liquid at the Solid Salt-Liquid Interface by Sum Frequency Generation Spectroscopy.

Sum frequency generation (SFG) vibrational spectroscopy of the ionic liquid, 1-butyl-3-methylimidazolium dicyanamide [BMIM][DCA], in contact with two different solid salt surfaces, BaF2(111) single crystal and solid NaCl{100}, are discussed in this Letter. This investigation describes the nature of an ionic liquid-(solid) salt interface using SFG, contributing a new understanding to the molecular-level interactions involved in salts, which are conceptually similar compounds (of purely ionic character) but of different physical properties (liquid versus solid at room temperature). Results show the presence of [BMIM](+) at the NaCl{100} surface and [DCA](-) at the BaF2(111) surface. [BMIM](+) cations adhere closely via Coulombic interactions to the negatively charged NaCl{100} surface, while [DCA](-) anions subsequently have a strong electrostatic affinity to the positively charged BaF2(111) surface. Ions of the ionic liquid adsorb to the solid salt surface to form a Helmholtz-like electric double layer.