Water interactions with mixed alkane thiol monolayers of tuned hydrophobic and hydrophilic character

COLL 286

Ronald L. Grimm, grimm@uci.edu, Nicole M. Barrentine, and John C. Hemminger, jchemmin@uci.edu. Department of Chemistry and AirUCI, University of California, Irvine, Department of Chemistry, Univeristy of California, Chemistry Dept, Irvine, CA 92697-2025
Temperature programmed desorption (TPD) experiments characterize the interaction between water and self assembled monolayers (SAM) of mixed hydrophobic and hydrophilic thiols on Au(111). Two-component SAM surfaces form by exposing gold samples to mixed millimolar solutions of methyl-terminated and carboxylic acid-terminated thiols. Water desorption spectra from the pure hydrophobic surface exhibit first order desorption at low coverage with narrow peaks at ~145 K. Conversely, desorption of water from a pure acid-terminated surface exhibits broad peaks shifted to higher temperatures. Interestingly, water TPD spectra from a 50% / 50% methyl- and acid-terminated surface closely resemble desorption from the purely hydrophobic SAM. Increasing the surface acid fraction beyond 50% shifts desorption profiles to higher temperatures with long, high-temperature tails approaching the behavior of water desorbing from the pure acid-terminated surface. We discuss the implications for water interaction with "textured" organic surfaces as well as with atmospherically-relevant organic aerosol. In particular, results suggest that significant surface oxidation is necessary to impact water interactions with organic aerosol surfaces.