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

TL;DR

This paper investigates the unique features of SERS spectra of 4,4-bipyridine in single molecule detection, highlighting the dominant role of quadrupole interactions and the influence of experimental geometry on spectral features.

Contribution

It provides new insights into the mechanisms of SERS enhancement, emphasizing the significance of quadrupole interactions and the impact of experimental setup on spectral observations.

Findings

Quadrupole light-molecule interaction causes prominent spectral lines.

Weak forbidden lines indicate dipole interactions are still present.

Spectral features depend on the experimental geometry used.

Abstract

The paper briefly describes main statements of the theory of the SERS spectra with regards to the single molecule regime, when the enhancement achieves the values . 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 and 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 plays a leading 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 .