The adsorption of ions to water-hydrophobe interfaces influences a wide range of phenomena, including chemical reaction rates, ion transport across biological membranes, and electrochemical and many catalytic processes; hence, developing a detailed understanding of the behavior of ions at water-hydrophobe interfaces is of central interest. Here, we characterize the adsorption of the chaotropic thiocyanate anion (SCN^-) to two prototypical liquid hydrophobic surfaces, water-toluene and water-decane, by surface-sensitive nonlinear spectroscopy and compare the results against our previous studies of SCN^- adsorption to the air-water interface. For these systems, we observe no spectral shift in the charge transfer to solvent spectrum of SCN^-, and the Gibb's free energies of adsorption for these three different interfaces all agree within error. We employed molecular dynamics simulations to develop a molecular-level understanding of the adsorption mechanism and found that the adsorption for SCN^- to both water-toluene and water-decane interfaces is driven by an increase in entropy, with very little enthalpic contribution. This is a qualitatively different mechanism than reported for SCN^- adsorption to the air-water and graphene-water interfaces, wherein a favorable enthalpy change was the main driving force, against an unfavorable entropy change.

Ultrafast time-resolved extreme ultraviolet (EUV) reflectivity measurements of optically pumped amorphous carbon (a-C) have been performed with the FERMI free electron laser (FEL). This work extends the energy range used in previous reflectivity studies and adds polarization dependence. The EUV probe is known to be sensitive to lattice dynamics, since in this range the reflectivity is essentially unaffected by the photo-excited surface plasma. The exploitation of both s-and p-polarized EUV radiation permits variation of the penetration depth of the probe; a significant increase in the characteristic time is observed upon increasing the probing depth (1 vs. 5 ps) due to hydrodynamic expansion and consequent destruction of the excited region, implying that there is only a short window during which the probed region is in the isochoric regime. A weak wavelength dependence of the reflectivity is found, consistent with previous measurements and implying a maximum electronic temperature of 0.8 eV ± 0.4.