Excited states computation of models of phenylalanine protein chains: TD-DFT and composite CC2/TD-DFT protocols - Archive ouverte HAL Access content directly
Journal Articles International Journal of Molecular Sciences Year : 2022

Excited states computation of models of phenylalanine protein chains: TD-DFT and composite CC2/TD-DFT protocols

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1
Eric Gloaguen
Michel Mons
Valérie Brenner

Abstract

The present benchmark calculations testify to the validity of time-dependent density functional theory (TD-DFT) when exploring the low-lying excited states potential energy surfaces of models of phenylalanine protein chains. Among three functionals suitable for systems exhibiting charge-transfer excited states, LC-ωPBE, CAM-B3LYP, and ωB97X-D, which were tested on a reference peptide system, we selected the ωB97X-D functional, which gave the best results compared to the approximate coupled-cluster singles and doubles (CC2) method. A quantitative agreement for both the geometrical parameters and the vibrational frequencies was obtained for the lowest singlet excited state (a ππ* state) of the series of capped peptides. In contrast, only a qualitative agreement was met for the corresponding adiabatic zero-point vibrational energy (ZPVE)-corrected excitation energies. Two composite protocols combining CC2 and DFT/TD-DFT methods were then developed to improve these calculations. Both protocols substantially reduced the error compared to CC2 and experiment, and the best of both even led to results of CC2 quality at a lower cost, thus providing a reliable alternative to this method for very large systems.
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Dates and versions

cea-03524523 , version 1 (13-01-2022)

Licence

Attribution - CC BY 4.0

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Marine Lebel, Thibaut Very, Eric Gloaguen, Benjamin Tardivel, Michel Mons, et al.. Excited states computation of models of phenylalanine protein chains: TD-DFT and composite CC2/TD-DFT protocols. International Journal of Molecular Sciences, 2022, 23 (2), pp.621. ⟨10.3390/ijms23020621⟩. ⟨cea-03524523⟩
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