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Main Authors: Gallego-Valencia, Daniela, Mewes, Lars, Feist, Johannes, Sanz-Vicario, José Luis
Format: Preprint
Published: 2024
Subjects:
Online Access:https://arxiv.org/abs/2403.04734
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author Gallego-Valencia, Daniela
Mewes, Lars
Feist, Johannes
Sanz-Vicario, José Luis
author_facet Gallego-Valencia, Daniela
Mewes, Lars
Feist, Johannes
Sanz-Vicario, José Luis
contents The fast dynamics of molecular polaritonics is scrutinized theoretically through the implementation of two-dimensional spectroscopy protocols. We derive conceptually simple and computationally efficient formulas to calculate two-dimensional spectra for molecules, each of them modeled as a system of two electronic states including vibrational relaxation, immersed in an optical cavity, thus coupled to quantized radiation. Cavity photon losses and molecular relaxation are incorporated into the Hamiltonian dynamics to form an open quantum system that is solved through a master equation. In the collective case, the relaxation dynamics into dark states reveals to be the crucial factor to explain the asymmetries in both the diagonal and cross peaks of two-dimensional spectra for long waiting times between excitation and detection, a feature shown by recent experiments. Our theoretical method provides a deeper insight in those processes that yield relevant signals in multidimensional molecular spectroscopy.
format Preprint
id arxiv_https___arxiv_org_abs_2403_04734
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Coherent multidimensional spectroscopy in polariton systems
Gallego-Valencia, Daniela
Mewes, Lars
Feist, Johannes
Sanz-Vicario, José Luis
Quantum Physics
The fast dynamics of molecular polaritonics is scrutinized theoretically through the implementation of two-dimensional spectroscopy protocols. We derive conceptually simple and computationally efficient formulas to calculate two-dimensional spectra for molecules, each of them modeled as a system of two electronic states including vibrational relaxation, immersed in an optical cavity, thus coupled to quantized radiation. Cavity photon losses and molecular relaxation are incorporated into the Hamiltonian dynamics to form an open quantum system that is solved through a master equation. In the collective case, the relaxation dynamics into dark states reveals to be the crucial factor to explain the asymmetries in both the diagonal and cross peaks of two-dimensional spectra for long waiting times between excitation and detection, a feature shown by recent experiments. Our theoretical method provides a deeper insight in those processes that yield relevant signals in multidimensional molecular spectroscopy.
title Coherent multidimensional spectroscopy in polariton systems
topic Quantum Physics
url https://arxiv.org/abs/2403.04734