期刊
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
卷 25, 期 12, 页码 8376-8385出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/d3cp00474k
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The study investigates the mixing between charge transfer (CT) and local excited (LE) characters upon twisting of N-phenylpyrrole (N-PP) geometry using theoretical calculations of six low-lying singlet excited states (ES). Results show that the Bethe-Salpeter equation (BSE) formalism is more reliable than Time-Dependent Density Functional Theory (TD-DFT) for close-lying ES with mixed CT/LE nature. BSE/GW provides a more accurate evolution of the excited state potential energy surfaces (PES) with negligible exchange-correlation functional starting point dependency.
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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