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

TL;DR

This study evaluates the performance of long-range corrected double-hybrid density functionals, comparing TD and TDA approaches for singlet and triplet excitations, and provides recommendations for their use in different excitation scenarios.

Contribution

First comprehensive comparison of TD-DHDFs and TDA-DHDFs for singlet-triplet excitations using the latest long-range corrected double-hybrid functionals.

Findings

TDA-DHDFs are nearly equivalent to TD-DHDFs for singlet-singlet excitations.

Applying TDA-DHDFs is necessary for accurate triplet excitation calculations.

Long-range correction benefits BLYP-based DHDFs but not PBE-based ones.

Abstract

We continue our work on the long-range corrected double-hybrid density functionals (LC-DHDFs) {\omega}B2PLYP and {\omega}B2GP-PLYP that we developed in the context of time-dependent (TD) Density Functional Theory (DFT) to enable the robust description of singlet-singlet excitations [J. Chem. Theory Comput. 15, 4735 (2019)]. In our initial study, we only assessed the impact of a long-range correction (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, {\omega}B2PLYP and {\omega}B2GP-PLYP as well as the global DHDF PBE-QIDH can be recommended. If a transition exhibits charge-transfer character, {\omega}B2PLYP and {\omega}B2GP-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 {\omega}B2PLYP and {\omega}B2GP-PLYP as some of the currently best TDA-DFT methods.