Molecular Electrodynamic Relaxation in Dielectric and Plasmonic Cavities
Abstract
Molecular radiative emission is a fundamental relaxation process that governs excited-state lifetimes and significantly influences photophysical dynamics, but direct self-consistent Maxwell--Schrödinger simulations of molecular radiation suffer from numerical instabilities in evaluating radiative self-interaction. Herein, this issue is resolved within the self-consistent propagation of classical Maxwell's equations coupled to real-time density-functional electronic dynamics and their tight-binding approximation. By carefully removing the longitudinal components of radiative self-reaction, this framework quantitatively reproduces radiative lifetimes of atomic and molecular emitters in vacuum and further captures cavity-modified emission at weak and strong coupling regimes beyond perturbation theory. For molecules weakly coupled to an optical microcavity, the cavity Purcell effect is shown to reach maximum using a modestly red-detuned cavity due to nuclear thermal motion. Moreover, for a single methylene blue molecule strongly coupled to a realistic nanoparticle-on-mirror plasmonic cavity, the predicted molecular electrodynamical relaxation is accelerated to approximately 11 femtoseconds, directly competing with nonadiabatic nuclear dynamics. This work establishes a route to first-principles design of material radiative properties in a wide range of dielectric environments.
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BibTeX
@misc{meng2026molecular,
title = {{Molecular Electrodynamic Relaxation in Dielectric and Plasmonic Cavities}},
author = {Gang Meng and Tao E. Li},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.38992},
eprint = {2610.38992},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.38992},
}
RIS
TY - UNPB
TI - Molecular Electrodynamic Relaxation in Dielectric and Plasmonic Cavities
AU - Gang Meng
AU - Tao E. Li
PY - 2026
DA - 2026/10/28
PB - arXiv
DO - 10.48550/arxiv.2610.38992
UR - https://arxiv.org/abs/2610.38992
AB - Molecular radiative emission is a fundamental relaxation process that governs excited-state lifetimes and significantly influences photophysical dynamics, but direct self-consistent Maxwell--Schrödinger simulations of molecular radiation suffer from numerical instabilities in evaluating radiative self-interaction. Herein, this issue is resolved within the self-consistent propagation of classical Maxwell's equations coupled to real-time density-functional electronic dynamics and their tight-binding approximation. By carefully removing the longitudinal components of radiative self-reaction, this framework quantitatively reproduces radiative lifetimes of atomic and molecular emitters in vacuum and further captures cavity-modified emission at weak and strong coupling regimes beyond perturbation theory. For molecules weakly coupled to an optical microcavity, the cavity Purcell effect is shown to reach maximum using a modestly red-detuned cavity due to nuclear thermal motion. Moreover, for a single methylene blue molecule strongly coupled to a realistic nanoparticle-on-mirror plasmonic cavity, the predicted molecular electrodynamical relaxation is accelerated to approximately 11 femtoseconds, directly competing with nonadiabatic nuclear dynamics. This work establishes a route to first-principles design of material radiative properties in a wide range of dielectric environments.
ER -