Static Electric Dipole Polarizability and Hyperpolarizability Tensors from Mean-Field Cavity Quantum Electrodynamics Approaches
A. Eugene DePrince, Stephen H. Yuwono
Abstract
First-order electric dipole response functions are implemented for cavity quantum electrodynamics (QED) generalizations of Hartree–Fock (HF) and Kohn–Sham density functional theory (DFT) in order to assess the degree to which static molecular response properties are impacted by interactions between electronic degrees of freedom and an optical cavity mode. Isotropically averaged static electric dipole polarizability tensors from QED-HF and QED-DFT are found to be somewhat insensitive to the presence of the cavity under realistic single-molecule coupling strengths. In contrast, the first hyperpolarizability tensor computed using QED-HF can be significantly modified by the cavity, depending on the relative orientation of the molecule and the cavity mode polarization axis. For example, compared to the isolated molecule case, the isotropically averaged hyperpolarizability for p -nitroaniline decreases by more than 20% when the molecule is coupled to a single-mode optical cavity with a coupling strength of | λ | = 0.05 au and when the cavity mode is polarized along the principal molecular axis. On the other hand, with this coupling strength and polarization, the isotropically averaged static dipole polarizability from QED-HF or QED-DFT decreases by only ≈2–5%, depending on the choice of the DFT functional.