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Article Dans Une Revue Physical Chemistry Chemical Physics Année : 2023

Excited state potential energy surfaces of N -phenylpyrrole upon twisting: reference values and comparison between BSE/GW and TD-DFT

Résumé

The puzzling case of the mixing between the charge transfer (CT) and local excited (LE) characters upon twisting of the geometry of N-phenylpyrrole (N-PP) is investigated considering the six low-lying singlet excited states (ES). The theoretical calculations of the potential energy surfaces (PES) have been performed for these states using a Coupled Cluster method accounting for the impact of the contributions from the triples, many-body Green's function GW and Bethe–Salpeter equation (BSE) formalisms, as well as Time-Dependent Density Functional Theory (TD-DFT) using various exchange–correlation functionals. Our findings confirm that the BSE formalism is more reliable than TD-DFT for close-lying ES with mixed CT/LE nature. More specifically, BSE/GW yields a more accurate evolution of the excited state PES than TD-DFT when compared to the reference coupled cluster values. BSE/GW PES curves also show negligible exchange–correlation functional starting point dependency in sharp contrast with their TD-DFT counterparts.
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Dates et versions

hal-04087277 , version 1 (03-05-2023)

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Iryna Knysh, Kelvine Letellier, Ivan Duchemin, Xavier Blase, Denis Jacquemin. Excited state potential energy surfaces of N -phenylpyrrole upon twisting: reference values and comparison between BSE/GW and TD-DFT. Physical Chemistry Chemical Physics, 2023, 25 (12), pp.8376-8385. ⟨10.1039/D3CP00474K⟩. ⟨hal-04087277⟩
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