Characterizing Anion Adsorption to Aqueous Interfaces: Toluene-Water versus Air-Water

We continue our investigation of the behavior of simple ions at aqueous interfaces, employing the combination of two surface-sensitive nonlinear spectroscopy tools, broadband deep UV electronic sum-frequency generation and UV second harmonic generation, to characterize the adsorption of thiocyanate to the interface of water with toluene─a prototypical hydrophobe. We find that both the interfacial spectrum and the Gibbs free energy of adsorption closely match results previously reported for the air-water interface. We observe no relative spectral shift in the higher-energy CTTS transition of thiocyanate, implying similar solvation environments for the two interfaces. Similarly, the Gibbs free energies of adsorption agree within error; however, we expect the respective enthalpic and entropic contributions to differ between the two interfaces, similar to our earlier findings for the air-water versus graphene-water interfaces. Further experiments and theoretical modeling are necessary to quantify the mechanistic differences.