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The Journal of Chemical Physics

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

Siwei Wang, Gregory D. Scholes, Liang‐Yan Hsu

Published Jul 2, 2019• 54 citations
Publisher

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)].

DOI
10.1063/1.5100014

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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)].
Quantum emitters near the surface of silver nanoparticles undergo Rabi oscillations in electronic population dynamics due to strong coupling with near-field multipole modes that are not radiative. Low-frequency nanoparticle dipole modes are radiative but do not couple strong enough to quantum emitters. These features limit the observation of strong coupling. Using macroscopic quantum electrodynamics theory within a Lorentzian pseudo-mode approximation for the non-Markovian interaction kernel, we demonstrate that by coating spherical silver nanoparticles with a thin molecular J-aggregate layer, the resulting core-shell plexciton resonance restructures the local electromagnetic vacuum at dipole-mode frequencies to enable Rabi oscillations for quantum emitters that otherwise would only undergo exponential population decay. Specifically, we show for quantum dot emitters in the near field of silver nanospheres of 20 nm radius, that weak-to-strong coupling crossovers can be induced using 2 nm J-aggregate shells. Our work demonstrates the potential of molecular aggregates to enable deep sub-wavelength structuring of the vacuum field for the observation of coherent quantum dynamics in optical nanocavities.
In this study, we present the superradiance effects of N identical molecular emitters inside Fabry–Pérot (FP) cavity systems in the framework of macroscopic quantum electrodynamics. The proposed theory can estimate the enhancement of spontaneous emission rates, including the effects of cavity geometry and material dielectric properties. Moreover, our study connects the multichromophoric excitation energy transfer theory and the Tavis–Cummings model via identical cooperative decay rates and dipole–dipole shifts. For molecules resonant with the cavity photon mode, we find that the enhancement is not exactly proportional to N even in a perfect FP cavity due to the effects of electrostatic dipole–dipole interactions. Moreover, in a silver FP cavity, our simulation shows that the enhancement saturates for a large N, indicating that the cavity photon mode can lead to only the collective emission of a limited number of molecules. For molecules in the proximity of the silver mirror, we demonstrate that under specific conditions, the subradiance of molecular emitters can occur through surface plasmon polaritons. Our study not only provides new insights into the mechanism of superradiance effects but also demonstrates that collective effects such as superradiance and subradiance can be controlled by manipulating the dielectric environments.
We develop a microscopic quantum theory of surface plasmon polaritons valid for arbitrary metal-dielectric geometries. Our framework is based on the Power-Zienau-Woolley representation of quantum electrodynamics, which provides an optimal separation between electronic and photonic degrees of freedom and is therefore particularly well suited for constructing quantum descriptions of polaritonic excitations in strongly dispersive media. Within this formulation, the fundamental electronic oscillator is identified as the bulk plasmon mode, which is nonperturbatively coupled to the radiative continuum of free photon modes. This coupling induces a geometry-dependent renormalization of the bulk plasma frequency, giving rise to confined plasmonic resonances. As specific applications, we recover the localized surface plasmon modes of metallic nanoparticles, including radiative frequency shifts and decay, as well as the exact dispersion relation of propagating surface plasmon polaritons at planar interfaces. Our quantum treatment further reveals that light-matter interactions at metal-dielectric interfaces are inherently in the ultrastrong coupling regime. As a result, in the quasistatic limit, the system exhibits unconventional ground-state quantum fluctuations that can be controlled through the refractive index. These results open new intriguing perspectives in the field of quantum plasmonics.
Simulating the dynamics of molecular excitons in complex nanophotonic environments requires integrating rigorous electromagnetic simulations with accurate treatments of open quantum system dynamics. In this work, we develop MQED-QD (Macroscopic Quantum Electrodynamics for Quantum Dynamics), a robust computational package for simulating exciton dynamics in arbitrary dielectric and plasmonic environments. Based on the MQED framework, the package offers a unified workflow for constructing the dyadic Green's functions from classical electromagnetic solvers, parametrizing quantum master equations, and propagating the time evolution to determine the molecular subsystem's dynamical properties. To demonstrate the package's capabilities, we simulate exciton transport within a one-dimensional molecular chain near a silver nanostructure, including benchmarking against planar surfaces and exploring the influence of silver nanorods. Our results reveal that surface plasmon polaritons on nanorods dramatically enhance long-range dipole-dipole interactions, accelerating exciton delocalization and yielding higher participation ratios compared to planar geometries. By elucidating accurate molecular exciton dynamics in conjunction with nanophotonics and plasmonics, MQED-QD provides a powerful, open-source package that facilitates the rational design of nanoscale architectures.
Enabling the confinement of light to a scale far below the one of conventional optics, surface plasmon polaritons (SPPs) induced by an electromagnetic field in a metal-dielectric interface supply an ideal system to explore strong quantized light-matter coupling. The fast matter-SPP population exchange reported in previous works makes it a candidate for spin manipulation, but such reversible dynamics asymptotically vanishes accompanying the quantum matter relaxing completely to its ground state. Here, we study the exact dissipative dynamics of a quantum emitter (QE) coupled to SPPs. It is interesting to find that, qualitatively different from conventional findings, the QE can be partially stabilized in its excited state even in the presence of the lossy metal. Our analysis reveals that it is the formation of a QE-SPP bound state which results in such suppressed dissipation. Enriching the decoherence dynamics of the QE in the lossy medium, our result is helpful to understand QE-SPP interactions and apply plasmonic nanostructures in quantum devices.
In this article, we address fluorescence of single molecule inside a plasmonic picocavity by proposing a semi-classical theory via combining the macroscopic quantum electrodynamics theory and the open quantum system theory. To gain insights into the experimental results [Nat. Photonics, 14, 693 (2020)], we have further equipped this theory with the classical electromagnetic simulation of the pico-cavity, formed by single atom decorated silver STM tip and a silver substrate, and the time-dependent density functional theory calculation of zinc phthalocyanine molecule. Our simulations not only reproduce the fluorescence spectrum as measured in the experiment, confirming the influence of extreme field confinement afforded by the picocavity, but also reveal Rabi oscillation dynamics and Mollow triplets spectrum for moderate laser excitation. Thus, our study highlights the possibility of coherently manipulating the molecular state and exploring non-linear optical phenomena with the plasmonic picocavity.