Comparative study of the interaction of pyridine with polycrystalline Ag and amorphous solid water

The interaction of pyridine (C5H5N) with polycrystalline Ag and amorphous solid water (D2O) is compared. Metastable impact electron spectroscopy (MIES) and reflection-absorption infrared spectroscopy (RAIRS) were utilized to obtain information on the structure of the pyridine-Ag and pyridine-water interfaces. On polycrystalline Ag, C5H5N adsorbs with its molecular axis perpendicular to the surface whereby a work function decrease of 1.5 eV takes place during the build up of the first layer. In the second layer the molecular axis is tilted with respect to the surface normal. On amorphous solid water, C5H5N is initially adsorbed on top with its ring plane oriented preferentially near parallel with respect to the surface, reflecting the contribution of two different interactions to the bonding, the formation of a pi-hydrogen bond, and competitive bonding via the nitrogen lone pair. Coverage-driven reorientation takes place during the completion of the first monolayer and increases the average tilt angle. We have followed the growth of pyridine films up to the third layer which, according to RAIRS, shows clear signs of condensation. No embedding of pyridine species into the underlying water film can be noticed when heating up to desorption. The exposure of a pyridine film at 124 K to D2O molecules does not lead to on top adsorption. Instead, D2O becomes initially embedded into the pyridine film, and RAIRS indicates solvation of the pyridine species.