Density-Functional Tight Binding Meets Maxwell: Unraveling the Mysteries of (Strong) Light-Matter Coupling Efficiently

Abstract

Controlling chemical and material properties through strong light-matter coupling in optical cavities has gained considerable attention over the past decade. However, the underlying mechanisms remain insufficiently understood, and a significant gap persists between experimental observations and theoretical descriptions. This challenge arises from the intrinsically multi-scale nature of the problem, where non-perturbative feedback occurs across different spatial and temporal scales. Collective coupling between a macroscopic ensemble of molecules and a photonic environment, such as Fabry-Perot cavity, can strongly influence the microscopic properties of individual molecules, while microscopic details of the ensemble in turn affect the macroscopic coupling. To address this complexity, we present an efficient computational framework that combines density-functional tight binding (DFTB) with finite-difference time-domain (FDTD) simulations for Maxwell's equations (DFTB+Maxwell). This approach allows for a self-consistent treatment of both the cavity and microscopic details of the molecular ensemble. We demonstrate the potential for this method by tackling several open questions. First, we calculate non-perturbatively two-dimensional spectroscopic observable that directly connect to well-established experimental protocols. Second, we provide local, molecule-resolved information within collectively coupled ensembles, which is difficult to obtain experimentally. Third, we show how cavity designs can be optimized to target specific microscopic applications. Finally, we outline future directions to enhance the predictive power of this framework, including extension to finite temperature, condensed phases, and correlated quantum effects.