Equilibrium structures of water at well-defined organic surfaces

COLL 429

David L. Allara, dla3@psu.edu1, Thomas Boland, tboland@clemson.edu2, Matthew Dixon3, and Maria Fortunato, mef191@psu.edu3. (1) Department of Chemistry and The Materials Research Institute, The Pennsylvania State University, 104 Chemistry Building, University Park, PA 16802, (2) Department of Bioengineering, Clemson University, 520 Rhodes, Clemson, SC 29634, (3) Department of Chemistry, Pennsylvania State University, 104 Chemistry, Pennsylvania State University, University Park, PA 16802
We report combined in-situ infrared vibrational spectroscopic and coverage measurements, from submonolayer to near condensation, of equilibrium water adsorption at well-defined organic surfaces synthesized by molecular self-assembly. The adsorption isotherm data were used to develop thermodyamic parameters of the adsorbed films while the IR data give information on the water structures. The IR spectra were interpreted quantitatively by using modeling based on electromagnetic theory and the known optical function spectra of various phases of water. The results reveal a range of water structures from ice-like to clathrate-like and liquid-like depending on the water chemical potential, the chemical functionality of the surface and on the presence of dilute inorganic salts dissolved in the near water films. In the case of hydrophobic methyl-terminated surfaces, the water adopts a liquid-like structure from submonolayer to near-condensation coverages, contradicting views in which water is ordered at hydrophobic surfaces. In contrast, for polar surfaces such as CO2H, the water adopts a strongly H-bonded structure up to the condensation point. The incorporation of dissolved salts at the interfaces serves to broaden the range of water structures observed.