Vibrational Spectroscopic Observation of Atomic-Scale Local Surface Sites Using Site-Selective Signal Enhancement.

Molecule-substrate interactions are sensitively affected by atomic-scale surface structures. Unique activity in heterogeneous catalysts or electrocatalysts is often related with local surface sites with specific structures. We demonstrate that adsorption geometry of a model molecule with an isocyanide anchor is drastically varied among one-fold atop, two-fold bridge, and three-fold hollow configurations with increasing the size of atomic-scale local surface sites of Pd islands on an Au(111) model surface. The vibrational spectroscopic observation of such local information is realized by site-selective and self-assembled formation of hotspots, where Raman scattering intensity is significantly enhanced via excitation of localized surface plasmons.