title: Probing the interfacial structure of aqueous electrolytes with femtosecond second harmonic generation spectroscopy.
abstract: The existence of polarizable anions at the outermost layer of electrolyte solutions has received much recent attention from both theory and experiment, but remains controversial. Anions can be probed directly in the UV via their strong charge-transfer-to-solvent (CTTS) transitions. We have recently described experimental characterizations of enhanced concentrations of several anions at the air-water interface, using the surface-specific technique of second harmonic generation. Here we present a detailed description of the experimental design and methodology used in these experiments, as well as a proof of principle experiment with the known surfactant tetrabutylammonium iodide (TBAI), yielding surface enhancements in excellent agreement with surface tension measurements. Furthermore, we analyze the observed increase in the nonresonant contribution to the SHG response from the water background of alkali halide solutions. The observed change in the water structure of alkali halide (except iodide) solutions is linear in concentration and correlates with the fractional saturation concentration of the salt and with the ionic volume fraction. Finally, the surface adsorption of iodide at high bulk concentrations is analyzed, but it is not possible to differentiate between a Gibbs free energy of adsorption of zero (surface concentration proportional to the bulk) or -0.8 kcal/mol, as predicted by recent molecular dynamics simulations.
authors.affiliation: Department of Chemistry, University of California, Berkeley, CA 94720, USA.
authors.forename: Poul B
authors.initials: PB
authors.lastname: Petersen
authors.forename: Richard J
authors.initials: RJ
authors.lastname: Saykally