Peculiarities of the SERS Spectra of 4,4′-Bipyridine Molecule in a Single Molecule Detection Regime

Abstract

The paper describes briefly main statements of the theory of the SERS spectra with regards to the single molecule regime, when the enhancement achieves the values ~10¹⁴−10¹⁵. Analysis of the spectra of 4,4′-bypyridine, obtained on the dimer lattice of sharp nanoparticles points out that the observed enhancement is caused exclusively by a strong quadrupole light-molecule interaction, which manifests in the presence of lines, caused by vibrations with the unit irreducible representations of the D₂ and D_2h symmetry groups, which apparently describe the symmetry properties of the molecule. The study of the spectra, obtained by tip enhanced spectroscopy demonstrates that the strong quadrupole light-molecule interaction still has a governing role, however the strong dipole interaction still manifests in the existence of very weak forbidden lines. This result apparently is associated with another experimental geometry.