Gap Structure Effects on Surface-Enhanced Raman Scattering Intensities for Gold Gapped Rods

Gapped rods provide a unique platform for elucidating structure/function relationships, both for single-molecule electrochemical techniques and for surface-enhanced Raman scattering (SERS). This paper attempts to elucidate the dependence of SERS intensities on gap topography and gap distance for gold gapped rods with segment lengths varying over a wide range (40-2000 nm). Significantly, we have determined that rough gaps lead to a smaller SERS enhancement than smooth gaps for these structures even though the rough gaps have a larger total surface area. Both theory and experiment show periodic variation of SERS intensity with segment length as determined by odd-symmetry plasmon multipoles. Excitation of even-symmetry modes is dipole forbidden (for polarization along the rod axis), but this selection rule can be relaxed by roughness or, for smooth gaps, by near-field coupling between the rod segments.