Performance of DFT functionals for calculating the second-order nonlinear optical properties of dipolar merocyanines

Laurie Lescos, Sebastian P. Sitkiewicz, Pierre Beaujean, Mireille Blanchard-Desce, Benoît Champagne, Eduard Matito, Frédéric Castet

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Résumé

The second-order nonlinear optical responses of a series of recently designed dipolar merocyanines are investigated using the 2006 Minnesota family of hybrid exchange-correlation functionals (XCFs), as well as the LC-BLYP, ωB97XD and CAM-B3LYP long-range (LR) corrected XCFs. The performance of these different levels of approximation is discussed in regard to reference second-order Møller-Plesset calculations and experimental data obtained from Hyper-Rayleigh Scattering (HRS) measurements. Particular focus is given to the influence of the amount of exact Hartree-Fock exchange included in the XCF on the magnitude of the static HRS responses, as well as to the impact of tuning the range-separation parameter in LR-XCFs, according to a system-specific nonempirical procedure. Frequency dispersion effects are also investigated, as well as their crucial role in the comparison between theoretical and experimental data.

langue originaleAnglais
Pages (de - à)16579-16594
Nombre de pages16
journalPhysical Chemistry Chemical Physics
Volume22
Numéro de publication29
Date de mise en ligne précoce8 juil. 2020
Les DOIs
Etat de la publicationPublié - 7 août 2020

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