Work

Non-equilibrium rate theory for polariton relaxation dynamics

Year: 2024

Type: article

Abstract: We derive an analytic expression of the non-equilibrium Fermi's golden rule (NE-FGR) expression for a Holstein-Tavis-Cumming Hamiltonian, a universal model for many molecules collectively coupled to the optical cavity. These NE-FGR expressions capture the full-time-dependent behavior of the rate constant for transitions from polariton states to dark states. The rate is shown to be reduced to the well-known frequency domain-based equilibrium Fermi's golden rule (E-FGR) expression in the equilibrium and collective limit and is shown to retain the same scaling with the number of sites in non-equilibrium and non-collective cases. We use these NE-FGR to perform population dynamics with a time-non-local and time-local quantum master equation and obtain accurate population dynamics from the initially occupied upper or lower polariton states. Furthermore, NE-FGR significantly improves the accuracy of the population dynamics when starting from the lower polariton compared to the E-FGR theory, highlighting the importance of the non-Markovian behavior and the short-time transient behavior in the transition rate constant.

Source: The Journal of Chemical Physics

DOI: 10.1063/5.0231396

Authors: Yifan Lai, Wenxiang Ying, Pengfei Huo

Institution: University of Rochester

Language: English

Topic: Strong Light-Matter Interactions

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: green

Funders: National Science Foundation, U.S. Department of Energy

Awards: Quantum Dynamics Approaches to Simulate Polariton Photochemistry, UNLOQ: UNDERSTANDING COHERENCE IN LIGHT-MATTER INTERFACES FOR QUANTUM SCIENCE