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.
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.
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)].
A major challenge in light-matter simulations is bridging the disparate time and length scales of electrodynamics and molecular dynamics. Current computational approaches often rely on heuristic approximations of either the electromagnetic (EM) or the material component, hindering the exploration of complex light-matter systems. Herein, MaxwellLink -- a modular, open-source Python framework -- is developed for the massively parallel, self-consistent propagation of classical EM fields interacting with a large heterogeneous molecular ensemble. The package utilizes a robust TCP/UNIX socket interface to couple EM solvers with a wide range of molecular drivers. In this initial release, MaxwellLink supports EM solvers spanning from single-mode cavities to full-feature three-dimensional finite-difference time-domain (FDTD) engines, and molecules described by multilevel open quantum systems, force-field and first-principles molecular dynamics, and nonadiabatic real-time Ehrenfest dynamics. With the socket-based architecture, users can seamlessly switch between levels of theory of either the EM solver or molecules without modifying the counterpart. Moreover, the EM engine and molecular drivers scale independently across multiple high-performance computing (HPC) nodes, facilitating large-scale simulations previously inaccessible to existing numerical schemes. The versatility and accuracy of this code are further demonstrated through applications including superradiance, radiative energy transfer, vibrational strong coupling in Bragg resonators, and plasmonic heating of molecular gases. By providing a unified, extensible engine, MaxwellLink potentially offers a powerful platform for exploring emerging phenomena across the research fronts of spectroscopy, quantum optics, plasmonics, and polaritonics.
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.
The unprecedented pace of evolution in nanoscale architectures for cavity quantum electrodynamics (cQED) has posed crucial challenges for theory, where the quantum dynamics arising from the non-perturbative dressing of matter by cavity electric and magnetic fields as well as the fundamentally non-Hermitian character of the system are to be treated without significant approximation. The lossy electromagnetic resonances of photonic, plasmonic, or magnonic nanostructures are described as quasinormal modes (QNMs), whose properties and interactions with quantum emitters and spin qubits are central to the understanding of dissipative nano-optics and magnetodielectric cQED. Despite recent advancements toward a fully quantum framework for QNMs, a general and universally accepted approach to QNM quantization for arbitrary linear media remains elusive. In this work, we introduce a unified theoretical framework, based on macroscopic QED and complex coordinate transformations, which achieves QNM quantization for a wide class of spatially inhomogeneous, dissipative and dispersive, linear, magnetodielectric resonators. The complex coordinate transformations equivalently convert the radiative losses into non-radiative material dissipation, and via a suitable transformation that reflects all the losses of the resonator, we define creation and annihilation operators that allow the construction of modal Fock states for the joint excitations of field-dressed matter. By directly addressing the intricacies of modal loss in a fully quantum theory of magnetodielectric cQED, our approach enables the exploration of modern, quantum nano-optical experiments utilizing dielectric, plasmonic, magnetic, or hybrid cQED architectures and paves the way toward a rigorous assessment of room-temperature, quantum nanophotonic technologies without recourse to ad hoc quantization schemes.
Open optical or plasmonic resonators are placed on and connected through surfaces or via waveguides, forming complex lightguiding nanostructures, e.g. for integrated photonic quantum devices. We derive general boundary conditions for quasinormal modes that account for the structure's specific geometry. We then present a general quantization scheme for multiple, interacting quasinormal-mode cavities coupled to quantum emitters and to a non-bosonic bath of propagating photons on waveguides or a surface. We derive a system-bath Hamiltonian with rigorously defined coupling elements that can be computed using Maxwell solvers, including light-matter coupling between the electromagnetic field and quantum emitters. We define system-bath correlation functions for an effective, bath-mediated, and time-delayed interaction between the quasinormal modes and quantum emitters, which is a main ingredient commonly used to simulate open quantum system dynamics.
Light-matter coupling strength and optical loss are two key physical quantities in cavity quantum electrodynamics (CQED), and their interplay determines whether light-matter hybrid states can be formed or not in chemical systems. In this study, by using macroscopic quantum electrodynamics (MQED) combined with a pseudomode approach, we present a simple but accurate method, which allows us to quickly estimate the light-matter coupling strength and optical loss without free parameters. Moreover, for a molecular emitter coupled with photonic modes (including cavity modes and plasmon polariton modes), we analytically and numerically prove that the dynamics derived from the MQED-based wavefunction approach is mathematically equivalent to the dynamics governed by the CQED-based Lindblad master equation when the Purcell factor behaves like Lorentzian functions.