Exploring Bethe–Salpeter Excited-State Dipoles: The Challenging Case of Increasingly Long Push–Pull Oligomers

Autor:	Iryna Knysh, Jose D. J. Villalobos-Castro, Ivan Duchemin, Xavier Blase, Denis Jacquemin
Přispěvatelé:	Chimie Et Interdisciplinarité : Synthèse, Analyse, Modélisation (CEISAM), Institut de Chimie du CNRS (INC)-Centre National de la Recherche Scientifique (CNRS)-Nantes université - UFR des Sciences et des Techniques (Nantes univ - UFR ST), Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ)-Nantes Université - pôle Sciences et technologie, Nantes Université (Nantes Univ)-Nantes Université (Nantes Univ), Théorie de la Matière Condensée (NEEL - TMC), Institut Néel (NEEL), Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes (UGA)-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP ), Université Grenoble Alpes (UGA), Laboratory of Atomistic Simulation (LSIM), Modélisation et Exploration des Matériaux (MEM), Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Direction de Recherche Fondamentale (CEA) (DRF (CEA)), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA)-Institut de Recherche Interdisciplinaire de Grenoble (IRIG), Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Commissariat à l'énergie atomique et aux énergies alternatives (CEA)-Université Grenoble Alpes (UGA), ANR-20-CE29-0005,BSE-forces,Géométries dans l'état excité dans le formalisme de Bethe-Salpeter(2020), ANR-18-EURE-0012,LumoMat-E,Molecular Materials for Organic Electronics/Photonics(2018)
Jazyk:	angličtina
Rok vydání:	2023
Předmět:	[CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Excited states methodology General Materials Science Condensed Matter Physical and Theoretical Chemistry Ab initio quantum chemical calculations
Zdroj:	Journal of Physical Chemistry Letters Journal of Physical Chemistry Letters, 2023, 14 (15), pp.3727-3734. ⟨10.1021/acs.jpclett.3c00699⟩
ISSN:	1948-7185
DOI:	10.1021/acs.jpclett.3c00699⟩
Popis:	International audience; The change of molecular dipole moment induced by photon absorption is key to interpret the measured optical spectra. Except for compact molecules, time-dependent density functional theory (TD-DFT) remains the only theory allowing to quickly predict µ ES , albeit with a strong dependency on the selected exchange-correlation functional. This Letter presents the first assessment of the performances of the many-body Green's function Bethe-Salpeter equation (BSE) formalism for the evaluation of the µ ES. We explore increasingly long push-pull oligomers as they present an excited-state nature evolving with system size. This work shows that BSE's µ ES do present the same evolution with oligomeric length as their CC2 and CCSD counterparts, with a dependency on the starting exchange-correlation functional that is strongly decreased as compared to TD-DFT. This Letter demonstrates that BSE is a valuable alternative to TD-DFT for properties related to the excited-state density, and not only for transition energies and oscillator strengths.
Databáze:	OpenAIRE
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