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Article Dans Une Revue Journal of Physical Chemistry Letters Année : 2023

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

Résumé

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.
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Dates et versions

hal-04137107 , version 1 (22-06-2023)

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Citer

Iryna Knysh, Jose Villalobos-Castro, Ivan Duchemin, Xavier Blase, Denis Jacquemin. Exploring Bethe–Salpeter Excited-State Dipoles: The Challenging Case of Increasingly Long Push–Pull Oligomers. Journal of Physical Chemistry Letters, 2023, 14 (15), pp.3727-3734. ⟨10.1021/acs.jpclett.3c00699⟩. ⟨hal-04137107⟩
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