论文标题
评估最新的远程校正双杂交密度函数的TAMM-DANCOFF近似，单线和单线刺激
Assessing the Tamm-Dancoff Approximation, singlet-singlet, and singlet-triplet excitations with the latest long-range corrected double-hybrid density functionals
论文作者
论文摘要
我们继续在我们在时间依赖性（TD）密度功能理论（DFT）的背景下开发的远程校正后校正后的双杂交密度函数（LC-DHDFS）ωb2plyp和ωb2GP-PLYP，以启用对单线刺激的可靠描述[J. J. J.化学理论计算。 15，4735（2019）]。在我们的初步研究中，我们仅评估了远程校正（LC）对基于BLYP的DHDF的影响，在此，我们通过在既定的TD-DHDF方案中提供了基于PBE的LC-DHDF的首次测试来扩展我们的理解。此外，这项研究是少数提供TD-DHDF与它们更快的TAMM-DAMCOFF-APPROXIMATION变体（TDA-DHDFS）之间直接比较的研究之一。最重要的是，这是自Grimme和Neese的TDA-B2PlyP以来的第一项TDA-DHDF研究[J.化学物理。 127，154116（2007）]和TD-DHDF上的第一批工作，该作品涉及Singlet-Triplet激发。我们展示了TD-DHDF和TDA-DHDF之间的差异通常可以忽略不计，而对于单链弹性激发，但如何将TDA-DHDFS应用于三重态激发。对于这两种激发类型，LC都对基于BLYP的DHDF有益，但对基于PBE的DHDF有害。对于局部价值和Rydberg激发，可以建议使用ωb2plyp和ωb2gp-Plyp以及全局DHDF PBE-QIDH。如果过渡表现出电荷转移特征，则应应用ωb2plyp和ωb2gp-plyp。对我们系统的第一个单元和三重态激发态之间的差距的分析表明，还有进一步改进的空间以达到更好的鲁棒性。在实现该目标之前，我们建议ωb2plyp和ωb2gp-plyp作为当前最佳的TDA-DFT方法。
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 [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, 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.
