Generalized Born-Huang expansion under macroscopic quantum electrodynamics framework

Hung-Sheng Tsai; Chih-En Shen; Liang-Yan Hsu

doi:10.1063/5.0195087

Generalized Born-Huang expansion under macroscopic quantum electrodynamics framework

J Chem Phys. 2024 Apr 14;160(14):144112. doi: 10.1063/5.0195087.

Authors

Hung-Sheng Tsai^{1

2}, Chih-En Shen^{1

2}, Liang-Yan Hsu^{1

2

3}

Affiliations

¹ Department of Chemistry, National Taiwan University, Taipei 10617, Taiwan.
² Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan.
³ Physics Division, National Center for Theoretical Sciences, Taipei 10617, Taiwan.

PMID: 38597310
DOI: 10.1063/5.0195087

Abstract

Born-Huang expansion is the cornerstone for studying potential energy surfaces and non-adiabatic couplings (NACs) in molecular systems. However, the traditional approach is insufficient to describe the molecular system, which strongly interacts with quantum light. Inspired by the work by Schäfer et al., we develop the generalized Born-Huang expansion theory within a macroscopic quantum electrodynamics (QED) framework. The theory we present allows us to describe electromagnetic vacuum fluctuations in dielectric media and incorporate the effects of dressed photons (or polaritons) into NACs. With the help of the generalized Born-Huang expansion, we clearly classify electronic nuclear NACs, polaritonic nuclear NACs, and polaritonic electronic NACs. Furthermore, to demonstrate the advantage of the macroscopic QED framework, we estimate polaritonic electronic NACs without any free parameter, such as the effective mode volume, and demonstrate the distance dependence of the polaritonic electronic NACs in a silver planar system. In addition, we take a hydrogen atom in free space as an example and derive spontaneous emission rates from photonic electronic NACs (polaritonic electronic NACs are reduced to photonic electronic NACs). We believe that this work not only provides an avenue for the theoretical exploration of NACs in a nucleus-electron-polariton coupled system but also offers a more comprehensive understanding for molecules coupled with quantum light.