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Updated: Mar 14, 2026

Determination of the Excitation and Coupling Rates Between Light Emitters and Surface Plasmon Polaritons
Published on: July 21, 2018
Novel photochemistry of molecular polaritons in optical cavities
Kochise Bennett1, Markus Kowalewski1, Shaul Mukamel1
1Chemistry Department, University of California, Irvine, California 92697-2025, USA. kcbennet@uci.edu.
Abstract:
Violations of the Born-Oppenheimer approximation (BOA) and the consequent nonadiabatic dynamics have long been an object of intense study. Recently, such dynamics have been induced via strong coupling of the molecule to a high-amplitude (spatially confined) mode of the electromagnetic field in optical cavities. However, the effects of a cavity on a pre-existing avoided crossing or conical intersection are relatively unexplored. The dynamics of molecules dressed by cavity modes are usually calculated by invoking the rotating wave approximation (RWA), which greatly simplifies the calculation but breaks down when the cavity mode frequency is higher than the relevant material frequencies. We develop a protocol for computing curve crossing dynamics in an optical cavity by exploiting a recently-developed method of solving the quantum Rabi model without invoking the RWA. The method is demonstrated for sodium iodide.
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