Impact of dipole self-energy on cavity-induced nonadiabatic dynamics

Fuente: arXiv
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Autores principales: Fábri, Csaba, Halász, Gábor J., Hofierka, Jaroslav, Cederbaum, Lorenz S., Vibók, Ágnes
Formato: Preprint
Publicado: 2024
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author Fábri, Csaba
Halász, Gábor J.
Hofierka, Jaroslav
Cederbaum, Lorenz S.
Vibók, Ágnes
author_facet Fábri, Csaba
Halász, Gábor J.
Hofierka, Jaroslav
Cederbaum, Lorenz S.
Vibók, Ágnes
contents The coupling of matter to the quantized electromagnetic field of a plasmonic or optical cavity can be harnessed to modify and control chemical and physical properties of molecules. In optical cavities, a term known as the dipole self-energy (DSE) appears in the Hamiltonian to assure gauge invariance. The aim of this work is twofold. First, we introduce a method, which has its own merits and complements existing methods, to compute the DSE. Second, we study the impact of the DSE on cavity-induced nonadiabatic dynamics in a realistic system. For that purpose, various matrix elements of the DSE are computed as functions of the nuclear coordinates and the dynamics of the system after laser excitation is investigated. The cavity is known to induce conical intersections between polaritons, which gives rise to substantial nonadiabatic effects. The DSE is shown to slightly affect these light-induced conical intersections and, in particular, break their symmetry.
format Preprint
id arxiv_https___arxiv_org_abs_2411_07831
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Impact of dipole self-energy on cavity-induced nonadiabatic dynamics
Fábri, Csaba
Halász, Gábor J.
Hofierka, Jaroslav
Cederbaum, Lorenz S.
Vibók, Ágnes
Chemical Physics
The coupling of matter to the quantized electromagnetic field of a plasmonic or optical cavity can be harnessed to modify and control chemical and physical properties of molecules. In optical cavities, a term known as the dipole self-energy (DSE) appears in the Hamiltonian to assure gauge invariance. The aim of this work is twofold. First, we introduce a method, which has its own merits and complements existing methods, to compute the DSE. Second, we study the impact of the DSE on cavity-induced nonadiabatic dynamics in a realistic system. For that purpose, various matrix elements of the DSE are computed as functions of the nuclear coordinates and the dynamics of the system after laser excitation is investigated. The cavity is known to induce conical intersections between polaritons, which gives rise to substantial nonadiabatic effects. The DSE is shown to slightly affect these light-induced conical intersections and, in particular, break their symmetry.
title Impact of dipole self-energy on cavity-induced nonadiabatic dynamics
topic Chemical Physics
url https://arxiv.org/abs/2411.07831