Is surface layering of aqueous alkali halides determined by ion pairing in the bulk solution?

This contribution aims to elucidate the connection between ion-ion-solvent interactions in the bulk of aqueous electrolyte solutions and the properties of their liquid-air interface. In particular, we were interested in the conditions under which ion pairs form at the surface and whether this is linked to ion pairing in the bulk. For this reason different combinations of hard (Cl(-), Li(+)) and soft ions (I(-), Cs(+)) were investigated. Ion hydration and possible ion association in the bulk was probed with dielectric relaxation spectroscopy. This technique monitors the cooperative reorientation of the dipolar solvent molecules and detects all ion-pair species possibly present in the solution. At the interface, the formation of contact ion pairs was investigated by infrared-visible-sum frequency spectroscopy (SFG). This nonlinear optical technique possesses an inherent surface specificity and can be used for the characterization of interfacial water. The intensity of the SFG-active vibrational stretching modes depends on the number of oriented water molecules. The electric field at the surface of a charged aqueous interface aligns the water dipoles, which in turn increases the SFG response. Hence, the enhancement of the oscillator strengths of the water vibrational modes can be used to draw some conclusions on the strengths and geometrical extension of the electric field. The formation of ion pairs at the interface reduces the intensity of the band associated with hydrogen-bonded water. The underlying theory is presented. The combined data show that there are no contact ion pairs in the bulk of the fluid and--at best--only small amounts of solvent shared ion pairs. On the other hand, the combination of hard/hard or soft/soft ions leads to the formation of ion pairs at the liquid-air interface.