Ab initio nonrelativistic quantum electrodynamics: Bridging quantum chemistry and quantum optics from weak to strong coupling

Abstract

By applying the Born-Huang expansion, originally developed for coupled nucleus-electron systems, to the full nucleus-electron-photon Hamiltonian of nonrelativistic quantum electrodynamics (QED) in the long-wavelength approximation, we deduce an exact set of coupled equations for electrons on photonic energy surfaces and the nuclei on the resulting polaritonic energy surfaces. This theory describes seamlessly many-body interactions among nuclei, electrons, and photons including the quantum fluctuation of the electromagnetic field and provides a proper first-principle framework to describe QED-chemistry phenomena, namely polaritonic and cavity chemistry effects. Since the photonic surfaces and the corresponding nonadiabatic coupling elements can be solved analytically, the resulting expansion can be brought into a compact form, which allows us to analyze aspects of coupled nucleus-electron-photon systems in a simple and intuitive manner. Furthermore, we discuss structural differences between the exact quantum treatment and Floquet theory, show how existing implementations of Floquet theory can be adjusted to adhere to QED, and highlight how standard drawbacks of Floquet theory can be overcome. We then highlight, by assuming that the relevant photonic frequencies of a prototypical cavity QED experiment are in the energy range of the electrons, how from this generalized Born-Huang expansion an adapted Born-Oppenheimer approximation for nuclei on polaritonic surfaces can be deduced. This form allows a direct application of first-principle methods of quantum chemistry such as coupled-cluster or configuration interaction approaches to QED chemistry. By restricting the basis set of this generalized Born-Oppenheimer approximation, we furthermore bridge quantum chemistry and quantum optics by recovering simple models of coupled matter-photon systems employed in quantum optics and polaritonic chemistry. We finally highlight numerically that simple few-level models can lead to physically wrong predictions, even in weak-coupling regimes, and show how the presented derivations from first principles help to check and derive physically reliable simplified models.