SERS as a probe for adsorbate orientation on silver nanoclusters

Surface‐enhanced Raman scattering (SERS) spectroscopy has been used to characterize multilayers of three isomeric aromatic compounds adsorbed on silver nanoclusters. The three structural isomers, all of which adsorb in the carboxylate form onto the silver nanoclusters, bind in two different geometries to the silver surface. Different molecular configurations correlate to differences in bonding strength of these molecules to the silver surface, which can be probed by SERS. For ortho‐hydroxybenzoic acid (salicylic acid), we observed red shifts of major SERS peaks in comparison to the normal Raman vibrations of nonadsorbed crystalline material. For this molecule the steric hindrance between the adjacent carboxylate and hydroxyl groups causes the carboxylate group to rotate from the common flat geometry of benzene substituents on surfaces and bond directly through one of the oxygen atoms to the surface. In this case, strong coordinative bonding between the carboxylate group and the metal surface causes the red shifts in the SERS peaks. For para‐, and meta‐hydroxybenzoic acid, the steric hindrance is less likely since the two functional groups are not at adjacent positions, and therefore these molecules adsorb on the silver surface in a totally flat geometry. For these molecules, in contrast to the ortho isomer, the CO₂ interacts with the surface through an extended π bond, and these molecules are physically adsorbed in the common flat position. Therefore, for the meta and para substituents, we do not observe significant red shifts in the SERS spectrum. Copyright © 2009 John Wiley & Sons, Ltd.