Absorption cross-section spectroscopy of single strong coupling system between plasmon and molecular exciton resonance using single silver nanoparticle dimer generating surface enhanced resonant Raman scattering

TL;DR

This paper examines spectral changes in absorption cross-sections of single plasmon-molecular exciton systems during SERRS quenching, revealing how coupling energy variations affect optical properties, aiding in system optimization.

Contribution

It introduces a classical hybridization model including molecular multi-level properties to analyze spectral changes in strong coupling systems during SERRS quenching.

Findings

Blue-shifts observed in peak energies during quenching

Increased peak intensities in extinction cross-sections

Model reproduces spectral changes by decreasing coupling energy

Abstract

This study investigated spectral changes in the absorption cross-sections of single strong coupling systems composed of single silver nanoparticle dimers and a few dye molecules during the quenching of surface-enhanced resonant Raman scattering (SERRS). The absorption cross-section was obtained by subtracting the scattering cross-section from an extinction cross-section. The spectral changes in these cross-sections were evaluated using a classical hybridization model composed of a plasmon and a molecular exciton including a molecular multi-level property. The changes in the scattering and extinction cross-sections exhibit blue-shifts in their peak energy and increased peak intensities, respectively, during SERRS quenching. These properties are effectively reproduced in the model by decreasing the coupling energy. In particular, the peaks in the scattering and extinction cross-sections appear as peaks or dips in the absorption cross-sections depending on the degree of scattering loss, which reflects the dimer sizes. These results are useful for optimizing photophysical and photochemical effects mediated by the electronic excited states of strong coupling systems.