Theory of strong coupling between molecules and surface plasmons on a grating

TL;DR

This paper develops a detailed theoretical model for the strong coupling between molecules and surface plasmons on a grating, revealing complex multi-band dispersion relations and the importance of grating design in tuning the interaction.

Contribution

It introduces a multi-band dispersion relation model treating molecules as independent oscillators, including dark states, and highlights the grating's role in coupling and system tuning.

Findings

Five-band dispersion relation near molecular resonance crossing

Dark states are included in the dispersion analysis

Grating design influences molecule-plasmon coupling strength

Abstract

The strong coupling of molecules with surface plasmons results in hybrid states which are part molecule, part surface-bound light. Since molecular resonances may acquire the spatial coherence of plasmons, which have mm-scale propagation lengths, strong-coupling with molecular resonances potentially enables long-range molecular energy transfer. Gratings are often used to couple incident light to surface plasmons, by scattering the otherwise non-radiative surface plasmon inside the light-line. We calculate the dispersion relation for surface plasmons strongly coupled to molecular resonances when grating scattering is involved. By treating the molecules as independent oscillators rather than the more typically-considered single collective dipole, we find the full multi-band dispersion relation. This approach offers a natural way to include the dark states in the dispersion. We demonstrate that for a molecular resonance tuned near the crossing point of forward and backward grating-scattered plasmon modes, the interaction between plasmons and molecules gives a five-band dispersion relation, including a bright state not captured in calculations using a single collective dipole. We also show that the role of the grating in breaking the translational invariance of the system appears in the position-dependent coupling between the molecules and the surface plasmon. The presence of the grating is thus not only important for the experimental observation of molecule-surface-plasmon coupling, but also provides an additional design parameter that tunes the system.