Polaritonic Huang-Rhys Factor: Basic Concepts and Quantifying Light-Matter Interactions in Media

J Phys Chem Lett. 2023 Mar 9;14(9):2395-2401. doi: 10.1021/acs.jpclett.3c00065. Epub 2023 Mar 1.

Abstract

The Huang-Rhys (HR) factor, a dimensionless factor that characterizes electron-phonon (vibronic) coupling, has been extensively employed to investigate a variety of material properties. In the same spirit, we propose a quantity called the polaritonic HR factor to quantitatively describe the effects of (i) light-matter coupling induced by permanent dipoles and (ii) dipole self-energy. The former leads to polaritonic displacements, while the latter is associated with the electronic coupling shift named reorganization dipole self-coupling. In the framework of macroscopic quantum electrodynamics, our theory can evaluate the polaritonic HR factor, reorganization dipole self-coupling, and modified light-matter coupling strength in an arbitrary dielectric environment without free parameters, whose magnitudes are in good agreement with the previous experimental results. We believe that this study provides a useful perspective on understanding and quantifying light-matter interactions in media.