Relevance of the Quadratic Diamagnetic and Self-Polarization Terms in Cavity Quantum Electrodynamics

• Published in: ACS photonics Vol. 7; no. 4; pp. 975 - 990
• Main Authors: Schäfer, Christian, Ruggenthaler, Michael, Rokaj, Vasil, Rubio, Angel
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 15-04-2020
• Subjects: polaritonic chemistry; ab initio quantum electrodynamics; strong light−matter coupling; electronic structure; quantum optics
• ISSN: 2330-4022; 2330-4022
• DOI: 10.1021/acsphotonics.9b01649

Experiments at the interface of quantum optics and chemistry have revealed that strong coupling between light and matter can substantially modify the chemical and physical properties of molecules and solids. While the theoretical description of such situations is usually based on nonrelativistic quantum electrodynamics, which contains quadratic light–matter coupling terms, it is commonplace to disregard these terms and restrict the treatment to purely bilinear couplings. In this work, we clarify the physical origin and the substantial impact of the most common quadratic terms, the diamagnetic and self-polarization terms, and highlight why neglecting them can lead to rather unphysical results. Specifically, we demonstrate their relevance by showing that neglecting these terms leads to the loss of gauge invariance, basis set dependence, disintegration (loss of bound states) of any system in the basis set limit, unphysical radiation of the ground state, and an artificial dependence on the static dipole. Besides providing important guidance for modeling of strongly coupled light–matter systems, the presented results also indicate conditions under which those effects might become accessible.