Ab Initio Calculations of Quantum Light–Matter Interactions in General Electromagnetic Environments

The emerging field of strongly coupled light–matter systems has drawn significant attention in recent years because of the prospect of altering both the physical and chemical properties of molecules and materials. Because this emerging field draws on ideas from both condensed-matter physics and quantum optics, it has attracted the attention of theoreticians from both fields. While the former often employ accurate descriptions of the electronic structure of the matter, the description of the electromagnetic environment is often oversimplified. In contrast, the latter often employs sophisticated descriptions of the electromagnetic environment while using oversimplified few-level approximations of the electronic structure. Both approaches are problematic because the oversimplified descriptions of the electronic system are incapable of describing effects such as light-induced structural changes in the electronic system, while the oversimplified descriptions of the electromagnetic environments can lead to unphysical predictions because the light–matter interactions strengths are misrepresented. In this work, we overcome these shortcomings and present the first method which can quantitatively describe both the electronic system and general electromagnetic environments from first principles. We realize this by combining macroscopic QED (MQED) with Quantum Electrodynamical Density-Functional Theory. To exemplify this approach, we consider the example of an absorbing spherical cavity and study the impact of different parameters of both the environment and the electronic system on the transition from weak-to-strong coupling for different aromatic molecules. As part of this work, we also provide an easy-to-use tool to calculate the cavity coupling strengths for simple cavity setups. Our work is a significant step toward parameter-free ab initio calculations for strongly coupled quantum light–matter systems and will help bridge the gap between theoretical methods and experiments in the field.