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.