Unified evaluation of surface-enhanced resonance Raman scattering and fluorescence under strong coupling regime

TL;DR

This paper investigates how multiple excitons and higher-order plasmons influence the enhancement and quenching of resonance Raman scattering and fluorescence in single molecules under strong coupling, revealing complex spectral behaviors.

Contribution

It introduces a coupled oscillator model incorporating multiple excitons and higher-order plasmons to explain spectral changes and quenching phenomena in surface-enhanced resonance Raman and fluorescence.

Findings

Multiple excitons cause complex spectral shifts.

Higher-order plasmons lead to significant quenching.

The coupled oscillator model accurately reproduces experimental observations.

Abstract

We demonstrate importance of molecular multiple excitons and higher-order plasmons for both enhancement and quenching of resonance Raman and fluorescence of single dye molecule located at plasmonic hotspot under strong coupling regime. The multiple excitons induce complicated spectral changes in plasmon resonance and higher-order plasmons yield drastic quenching for both resonant Raman and fluorescence. A coupled oscillator model composed of plasmon and multiple excitons reproduces the complicated spectral changes. Purcell factors derived from higher-order plasmons reproduce the drastic quenching with considering ultra-fast surface enhanced fluorescence.