Quantum dynamics of molecular ensembles coupled with quantum light: Counter-rotating interactions as an essential component
Yi-Ting Chuang, Liang‐Yan Hsu
Abstract
The rotating-wave approximation (discarded of counter-rotating interactions) to light-matter interactions is widely used in the quantum electrodynamics Hamiltonian; however, its validity has long been a matter of debate. In this article, we explore the importance of counter-rotating interactions in the quantum dynamics of multiple molecules in complex dielectric environments within the framework of macroscopic quantum electrodynamics. Through our analytical analysis, we find that, in the weak coupling regime, the lack of counter-rotating interactions results in the absence of the Casimir-Polder potentials (medium-assisted energy shifts) in the ground-state molecules and a significant deviation of the intermolecule dipole-dipole interactions. Notably, the deviation of intermolecule dipole-dipole interaction can reach up to 50 percent in the near-field zone (short intermolecule distance). We also conduct a case study on the population dynamics of a pair of identical molecules above a plasmonic surface. Through analytical and numerical analysis, it is revealed that the lack of counter-rotating interactions can profoundly affect the dynamics, especially the oscillatory pattern due to intermolecule dipole-dipole interactions, of the molecules in both strong and weak coupling regimes, emphasizing the need for careful consideration when making the rotating-wave approximation in a multiple-molecule system coupled with quantum light.