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American Institute of Physics, The Journal of Chemical Physics, 16(139), p. 164104

DOI: 10.1063/1.4825359

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Application of recent double-hybrid density functionals to low-lying singlet-singlet excitation energies of large organic compounds

Journal article published in 2013 by F. Di Meo ORCID, P. Trouillas, C. Adamo, J. C. Sancho García ORCID
This paper is available in a repository.
This paper is available in a repository.

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Abstract

The present work assesses some recently developed double-hybrid density functionals (B2π-PLYP, PBE0-DH, and PBE0-2) using linear-response Tamm-Dancoff Time-Dependent Density Functional Theory. This assessment is achieved against experimentally derived low-lying excitation energies of large organic dyes of recent interest, including some excitations dominated by charge-transfer transitions. Comparisons are made with some of the best-performing methods established from the literature, such as PBE0 or B3LYP hybrid or the recently proposed B2-PLYP and B2GP-PLYP double-hybrid models, to ascertain their quality and robustness on equal footing. The accuracy of parameter-free or empirical forms of double-hybrid functionals is also briefly discussed. Generally speaking, it turns out that double-hybrid expressions always provide more accurate estimates than corresponding hybrid methods. Double-hybrid functionals actually reach averaged accuracies of 0.2 eV, that can be admittedly considered close to any intended accuracy limit within the present theoretical framework.