Abstract
The amino-amido-thiol AT (HS-(CHZ)(10)-CO-NH-CHz-CHZ-NH2), adsorbed on Au(111), was studied by sum frequency generation (SFG) and infrared reflection absorption spectroscopy in the CHZ stretching vibration region. The SFG and infrared spectra are qualitatively similar; both show the symmetric stretching band and an intense and unusually broad antisymmetric stretching band. The infrared spectra show a reversible difference between a sample dried after rinsing in electrolyte and dried after rinsing in ethanol, thus exhibiting a `solvent memory' effect. SFG spectra demonstrate that the dried samples have a high density of conformational defects. The defects are located in the C-10 methylene chain. We ascribe them to intermolecular hydrogen-bonding. When the layer is studied by SFG spectroscopy in aqueous solution, even in the presence of coordinating Pd2+ ions no vibrational bands are observed in the CHZ stretching vibration region. This indicates a strongly reduced defect density with a straightened molecular backbone. We ascribe this to the solvation of the amine group; in this case intermolecular bonds play a minor role.
Bittner, A M