Semiclassical Truncated-Wigner-Approximation Theory of Molecular Exciton-Polariton Dynamics in Optical Cavities

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Autor principal: Phuc, Nguyen Thanh
Formato: Preprint
Publicado: 2024
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author Phuc, Nguyen Thanh
author_facet Phuc, Nguyen Thanh
contents Molecular exciton polaritons are hybrid states resulting from the strong coupling of molecular electronic excitations with an optical cavity mode, presenting a promising approach for controlling photophysical and photochemical properties in molecular systems. In this study, we develop a semiclassical theory for molecular exciton-polariton dynamics using the truncated Wigner approximation (TWA) to explore the collective behavior of molecular electronic excited states under strong light-matter coupling. Our approach expands the previously developed TWA theory for molecular vibration-polariton dynamics (J. Chem. Theory Comput. 2024, 20, 3019--3027) by incorporating semiclassical treatment of quantum coherence between ground and excited molecular states. We initially apply the TWA theory to a simplified system of molecules modeled as two-level (spin-1/2) systems, omitting vibronic coupling. The semiclassical results derived from applying the TWA to single-spin operators demonstrate excellent agreement with full quantum dynamic simulations in systems with a sufficiently large number of molecules. Lastly, the TWA theory is extended to incorporate molecular vibronic coupling, revealing the dynamic polaron decoupling effect, where quantum coherence between molecular excitations is preserved under strong light-matter coupling.
format Preprint
id arxiv_https___arxiv_org_abs_2409_18460
institution arXiv
publishDate 2024
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spellingShingle Semiclassical Truncated-Wigner-Approximation Theory of Molecular Exciton-Polariton Dynamics in Optical Cavities
Phuc, Nguyen Thanh
Chemical Physics
Mesoscale and Nanoscale Physics
Quantum Physics
Molecular exciton polaritons are hybrid states resulting from the strong coupling of molecular electronic excitations with an optical cavity mode, presenting a promising approach for controlling photophysical and photochemical properties in molecular systems. In this study, we develop a semiclassical theory for molecular exciton-polariton dynamics using the truncated Wigner approximation (TWA) to explore the collective behavior of molecular electronic excited states under strong light-matter coupling. Our approach expands the previously developed TWA theory for molecular vibration-polariton dynamics (J. Chem. Theory Comput. 2024, 20, 3019--3027) by incorporating semiclassical treatment of quantum coherence between ground and excited molecular states. We initially apply the TWA theory to a simplified system of molecules modeled as two-level (spin-1/2) systems, omitting vibronic coupling. The semiclassical results derived from applying the TWA to single-spin operators demonstrate excellent agreement with full quantum dynamic simulations in systems with a sufficiently large number of molecules. Lastly, the TWA theory is extended to incorporate molecular vibronic coupling, revealing the dynamic polaron decoupling effect, where quantum coherence between molecular excitations is preserved under strong light-matter coupling.
title Semiclassical Truncated-Wigner-Approximation Theory of Molecular Exciton-Polariton Dynamics in Optical Cavities
topic Chemical Physics
Mesoscale and Nanoscale Physics
Quantum Physics
url https://arxiv.org/abs/2409.18460