Spectral correlation between surface-enhanced resonant Raman and far field scattering destructed by dipole quadrupole coupled plasmon resonance

Abstract

The spectral relationships between surface enhanced resonant Raman scattering (SERRS) and plasmon resonance observed in far field scattering cross are investigated using single silver nanoparticle dimers with focusing on the lowest energy (superradiant) plasmon resonance. We find that these relationships can be classified into two types. The first is SERRS spectral envelopes with spectral shapes similar to those of plasmon resonance spectra. The second is SERRS envelopes exhibiting higher energy shifts from the plasmon resonance spectra. These results are examined as an effect of degree of morphological asymmetry in dimers based on an electromagnetic (EM) mechanism. The analysis of the first and second types reveals that dipole-dipole and dipole-quadrupole coupled plasmon resonance (subradiant Fano resonance) respectively determine the EM enhancement. This mechanism is commonly important for the development of plasmonic nanostructures for various surface enhanced spectroscopies.