Time-Dependent Long-Range-Corrected Double-Hybrid Density Functionals with Spin-Component and Spin-Opposite Scaling: A Comprehensive Analysis of Singlet–Singlet and Singlet–Triplet Excitation Energies

Posted on 22.07.2021 - 11:34
Following the work on spin-component and spin-opposite scaled (SCS/SOS) global double hybrids for singlet–singlet excitations by Schwabe and Goerigk [J. Chem. Theory Comput. 2017, 13, 4307−4323] and our own works on new long-range corrected (LC) double hybrids for singlet–singlet and singlet–triplet excitations [J. Chem. Theory Comput. 2019, 15, 4735−4744 and J. Chem. Phys. 2020, 153, 064106], we present new LC double hybrids with SCS/SOS that demonstrate further improvement over previously published results and methods. We introduce new unscaled and scaled versions of different global and LC double hybrids based on Becke88 or PBE exchange combined with LYP, PBE, or P86 correlation. For singlet–singlet excitations, we cross-validate them on six benchmark sets that cover small to medium-sized chromophores with different excitation types (local-valence, Rydberg, and charge transfer). For singlet–triplet excitations, we perform the cross-validation on three different benchmark sets following the same analysis as in our previous work in 2020. In total, 203 excitations are analyzed. Our results confirm and extend those of Schwabe and Goerigk regarding the superior performance of SCS and SOS variants compared to their unscaled parents by decreasing mean absolute deviations, root-mean-square deviations, or error spans by more than half and bringing absolute mean deviations closer to zero. Our SCS/SOS variants are shown to be highly efficient and robust for the computation of vertical excitation energies, which even outperform specialized double hybrids that also contain an LC in their perturbative part. In particular, our new SCS/SOS-ωPBEPP86 and SCS/SOS-ωB88PP86 functionals are four of the most accurate and robust methods tested in this work, and we fully recommend them for future applications. However, if the relevant SCS and SOS algorithms are not available to the user, we suggest ωPBEPP86 as the best unscaled method in this work.

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Casanova-Páez, Marcos; Goerigk, Lars (2021): Time-Dependent Long-Range-Corrected Double-Hybrid Density Functionals with Spin-Component and Spin-Opposite Scaling: A Comprehensive Analysis of Singlet–Singlet and Singlet–Triplet Excitation Energies. ACS Publications. Collection. https://doi.org/10.1021/acs.jctc.1c00535
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