Quantum dynamics of a molecular emitter strongly coupled with surface plasmon polaritons: A macroscopic quantum electrodynamics approach

Abstract

We study a molecular emitter above a silver surface in the framework of macroscopic quantum electrodynamics and explore the population dynamics including non-Markovian effects. The theory we present is general for molecular fluorescence in the presence of dielectrics with any space-dependent, frequency-dependent, or complex dielectric functions. Furthermore, the proposed theory allows us to calculate the memory kernel of polaritons using computational electrodynamics packages. In the limit of a high vibration frequency, the different strengths of exciton-polariton couplings lead to distinct characteristics in the population dynamics, e.g., Franck-Condon-Rabi oscillation. (The frequency of Rabi oscillation is dependent on the Franck-Condon factor.) Additionally, in a specific condition, we derive a parameter-free formula that can be used to estimate the exciton-polariton coupling between a molecular emitter and a nanocavity, and the coupling estimated by our theory is in good agreement with the reported experimental results [Chikkaraddy et al., Nature 535, 127–130 (2016)].

Simple but accurate estimation of light-matter coupling strength and optical loss for a molecular emitter coupled with photonic modes

“…where K pol (t,t ′ ) is the memory kernel of polariton which has been defined in our previous studies [34][35][36] ,…”

“…The mapping of the quantum dynamics from the mQED theory to the cQED model relies on two premises: one is the validity of the flat continuum approximation 34,77 , and the other is the Lorentz-shape Purcell factor,…”

“…Light-matter interaction plays a crucial role in various fields such as surface-enhanced Raman spectroscopy [1][2][3][4][5][6][7][8][9] , biosensing [10][11][12][13][14][15] , photosynthesis [16][17][18][19][20] , resonance energy transfer [21][22][23][24][25][26][27] , and molecular fluorescence [28][29][30][31][32][33][34][35][36] . Recently, due to advances in nanotechnology, the achievement of strong light-matter interaction [37][38][39][40][41] has motivated successive studies on the chemical properties of light-matter hybrid states, leading to the emergence of polariton chemistry [42][43][44][45][46] .…”

“…To incorporate the effect of dielectric environments, we developed a general theory of a molecular emitter strongly coupled with plasmon polaritons in the framework of macroscopic quantum electrodynamics (mQED) 34,35 . In addition, in the high-frequency limit, we derived a parameter-free formula which can be used to estimate light-molecule coupling a) Electronic mail: lyhsu@gate.sinica.edu.tw strengths, and the coupling strength given by this parameterfree formula is in agreement with the experimental results done by Cavendish Laboratory 38 .…”

Large-Scale Inhomogeneous Fluorescence Plasmonic Silver Chips: Origin and Mechanism

“…Here, we do not consider the processes of coherent quantum dynamics because the strong coupling condition is not satisfied. 49 In addition, for simplicity, we also neglect the mechanism of plasmon-coupled resonance energy transfer [50][51][52] and vibrational states. For the modeling of inhomogeneous gaps, we divide the inhomogeneous gaps into numerous intervals with equal spacing and assume that the gap distance is uniform within the interval, as shown in Figure 1B.…”