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

作者：Di Meo F^*; Trouillas P; Adamo C; Sancho Garcia J C

来源：Journal of Chemical Physics, 2013, 139(16): 164104.

DOI：10.1063/1.4825359

The present work assesses some recently developed double-hybrid density functionals (B2 pi-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.

• 出版日期2013-10-28