Quantum Dynamics of Fluorescence Coupled with Surface Plasmon Polaritons and Intramolecular Vibrations

We study quantum dynamics of molecular fluorescence on a metal surface based on macroscopic quantum electrodynamics and explore the Purcell factor including non-Markovian effect (beyond Fermi's golden rule). The method we present is general for molecular fluorescence in a variety of plasmonic nanostructures (not limited to metal surfaces). Furthermore, the proposed method allows us to express memory kernels in terms of the parts of surface plasmon polaritons and molecular vibrations and enables us to calculate the kernels via classical electrodynamics, e.g., finite-difference time domain method. We find that, under different strengths of exciton-polariton couplings, the interplay of surface plasmon polaritons and molecular vibrations can lead to distinct characteristics in dynamics. Our study also provides a direction for exploring the effect of vibrational coherence on plasmon-enhanced molecular fluorescence.

The authors acknowledge financial support by the National Science Foundation, MRI No. DMR-1229217, and by Princeton University through the Innovation Fund for New Ideas in the Natural Sciences.