Assessing the Tamm-Dancoff approximation, singlet-singlet, and singlet-triplet excitations with the latest long-range corrected double-hybrid density functionals

Abstract

We continue our work on the long-range corrected double-hybrid density functionals (LC-DHDFs) ωB2PLYP and ωB2GP-PLYP that we developed in the context of time-dependent (TD) Density Functional Theory (DFT) to enable the robust description of singlet-singlet excitations [M. Casanova-Páez, M. B. Dardis, and L. Goerigk, J. Chem. Theory Comput. 15, 4735 (2019)]. In our initial study, we only assessed the impact of a LC on BLYP-based DHDFs, and herein, we extend our understanding by providing the first test of PBE-based LC-DHDFs within the established TD-DHDF scheme. Moreover, this study is one of few that provides a direct comparison between TD-DHDFs and their faster Tamm-Dancoff-approximation variants (TDA-DHDFs). Most importantly, this is the first TDA-DHDF study since Grimme and Neese's TDA-B2PLYP [J. Chem. Phys. 127, 154116 (2007)] and the first work on TD-DHDFs that addresses singlet-triplet excitations. We show how the difference between TD-DHDFs and TDA-DHDFs is often negligible for singlet-singlet excitations, but how one has to apply TDA-DHDFs for triplet excitations. For both excitation types, the LC is beneficial to the BLYP-based DHDFs, but detrimental to the PBE-based ones. For local-valence and Rydberg excitations, ωB2PLYP and ωB2GP-PLYP as well as the global DHDF PBE-QIDH can be recommended. If a transition exhibits charge-transfer character, ωB2PLYP and ωB2GP-PLYP should be applied. An analysis of the gaps between the first singlet and triplet excited states of our systems revealed that there is room for further improvements to reach better robustness. Until that goal has been achieved, we recommend ωB2PLYP and ωB2GP-PLYP as some of the currently best TDA-DFT methods.