Wavepacket and reduced-density approaches for high-dimensional quantum dynamics: Application to the nonlinear spectroscopy of asymmetrical light-harvesting building blocks.

Galiana, Joachim; Desouter, Michèle; Lasorne, Benjamin

doi:10.1063/5.0270440

Article (Scientific journals)

Wavepacket and reduced-density approaches for high-dimensional quantum dynamics: Application to the nonlinear spectroscopy of asymmetrical light-harvesting building blocks.

Galiana, Joachim; Desouter, Michèle; Lasorne, Benjamin

2025 • In Journal of Chemical Physics, 162 (24)

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https://hdl.handle.net/2268/334159

DOI
10.1063/5.0270440

PubMed
40548660

arXiV
2412.03412v3

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Keywords :

Excitation energy transfer; Hamiltonian models; Poly(phenylene ethynylenes); Poly(phenyleneethynylene); Vibronic coupling; 2D spectroscopy; Time-resolved spectra; HEOM; ML-MCTDH

Abstract :

[en] Excitation-energy transfer (EET) and relaxation in an optically excited building block of poly(phenylene ethynylene) (PPE) dendrimers are simulated using wavepackets with the multilayer multiconfiguration time-dependent Hartree (ML-MCTDH) method and reduced-density matrices with the hierarchical equations of motion (HEOM) approach. The dynamics of the ultrafast electronic funneling between the first two excited electronic states in the asymmetrically meta-substituted PPE oligomer with two rings on one branch and three rings on the other side, with a shared ring in between, is treated with 93-dimensional ab initio vibronic-coupling Hamiltonian (VCH) models, either linear or with bilinear and quadratic terms. The linear VCH model is also used to calibrate an open quantum system that falls in a computationally demanding non-perturbative non-Markovian regime. The linear-response absorption and emission spectra are simulated with both the ML-MCTDH and HEOM methods. The latter is further used to explore the nonlinear regime toward two-dimensional spectroscopy. We illustrate how a minimal VCH model with the two main active bright states and the impulsive-pulse limit in third-order response theory may provide at lower cost polarization-sensitive time-resolved signals that monitor the early EET dynamics. We also confirm the essential role played by the high-frequency acetylenic and quinoidal vibrational modes.

Disciplines :

Chemistry

Author, co-author :

Galiana, Joachim ; ICGM, Univ Montpellier, CNRS, ENSCM, Montpellier, France

Desouter, Michèle ; Université de Liège - ULiège > Département de chimie (sciences) ; Institut de Chimie Physique, Université Paris-Saclay-CNRS, UMR8000, F-91400 Orsay, France

Lasorne, Benjamin ; ICGM, Univ Montpellier, CNRS, ENSCM, Montpellier, France

Language :

English

Title :

Wavepacket and reduced-density approaches for high-dimensional quantum dynamics: Application to the nonlinear spectroscopy of asymmetrical light-harvesting building blocks.

Publication date :

28 June 2025

Journal title :

Journal of Chemical Physics

ISSN :

0021-9606

eISSN :

1089-7690

Publisher :

American Institute of Physics (AIP), United States

Volume :

162

Issue :

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/5.0270440/20566205/244102_1_5.0270440.pdf

Funders :

ENSL - Ecole Normale Supérieure de Lyon
MESR - France. Ministère de l'Enseignement supérieur et de la Recherche

Funding text :

J.G. acknowledges the French MESR (Minist\u00E8re charg\u00E9 de l\u2019Enseignement Sup\u00E9rieur et de la Recherche) and the ENS (Ecole Normale Sup\u00E9rieure) of Lyon for funding his Ph.D. grant, hosted at the University of Montpellier. We thank J.M. Teuler of the University Paris-Saclay for the upgrade of his JMFFT-7.2 library (CNRS-IDRIS France).

Commentary :

19 pages of manuscript, 32 pages of supplementary materials

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since 07 July 2025

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