Revisiting crossed-correlated baths in open quantum systems simulated by HEOM or T-TEDOPA.

[en] Excited-state dynamics of open quantum systems is analyzed by the hierarchical equations of motion (HEOM) or the thermalized time-evolving density operator with orthogonal polynomials algorithm (T-TEDOPA) method when a discrete ab initio linear vibronic model is parameterized by continuous temperature-dependent spectral densities leading to crossed correlation functions, i.e., correlated fluctuations of the energy gap collective modes. We focus on a conical intersection involving two collective modes tuning the energy of each excited state, and we revisit the transformation of the initial correlated tuning baths to de-correlated shared baths in order to reduce the computational resources. While a completely frequency-dependent transformation poses problems for HEOM, we find that in some particular cases, an optimal approximate frequency-independent transformation may be derived. On the contrary, T-TEDOPA is very efficient and allows us to use this frequency-dependent transformation at the price of managing long-range couplings in the tensor chain. An illustrative application is shown by using the linear vibronic coupling model of a planar symmetrical (phenylethynyl)benzene dimer.

Disciplines :

Chemistry

Author, co-author :

Le Dé, Brieuc ; Institut des Nanosciences de Paris, Sorbonne Université, CNRS, F-75005 Paris, France ; Department of Chemistry and Biochemistry, University of California, Merced, California 95343, USA

Mangaud, Etienne ; MSME, Université Gustave Eiffel, UPEC, CNRS, F-77454 Marne-La-Vallée, France

Chin, Alex W ; Institut des Nanosciences de Paris, Sorbonne Université, CNRS, F-75005 Paris, France

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

Language :

English

Title :

Revisiting crossed-correlated baths in open quantum systems simulated by HEOM or T-TEDOPA.

Publication date :

07 July 2026

Journal title :

Journal of Chemical Physics

ISSN :

0021-9606

eISSN :

1089-7690

Publisher :

AIP Publishing, United States

Volume :

165

Issue :

Peer reviewed :

Peer Reviewed verified by ORBi

Additional URL :

https://pubs.aip.org/aip/jcp/article-pdf/doi/10.1063/5.0340260/21060238/014101_1_5.0340260.pdf

Funders :

ANR - Agence Nationale de la Recherche

Available on ORBi :

since 02 July 2026

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