Park Woojin, Komarov Konstantin, Lee Seunghoon, Choi Cheol Ho
Department of Chemistry, Kyungpook National University, Daegu 41566, South Korea.
Center for Quantum Dynamics, Pohang University of Science and Technology, Pohang 37673, South Korea.
J Phys Chem Lett. 2023 Oct 5;14(39):8896-8908. doi: 10.1021/acs.jpclett.3c02296. Epub 2023 Sep 28.
The density functional theory (DFT) and linear response (LR) time-dependent (TD)-DFT are of the utmost importance for routine computations. However, the single reference formulation of DFT suffers in the description of open-shell singlet systems such as diradicals and bond-breaking. LR-TDDFT, on the other hand, finds difficulties in the modeling of conical intersections, doubly excited states, and core-level excitations. In this Perspective, we demonstrate that many of these limitations can be overcome by recently developed mixed-reference (MR) spin-flip (SF)-TDDFT, providing an alternative yet accurate route for such challenging situations. Empowered by the practicality of the LR formalism, it is anticipated that MRSF-TDDFT can become one of the major workhorses for general routine tasks.
密度泛函理论（DFT）和线性响应（LR）含时（TD）-DFT对于常规计算至关重要。然而，DFT的单参考公式在描述诸如双自由基和键断裂等开壳单重态体系时存在不足。另一方面，LR-TDDFT在锥形交叉、双激发态和芯能级激发的建模方面存在困难。在本展望中，我们证明最近发展的混合参考（MR）自旋翻转（SF）-TDDFT可以克服这些局限性中的许多问题，为这类具有挑战性的情况提供了一条替代但准确的途径。受LR形式的实用性的推动，预计MRSF-TDDFT能够成为一般常规任务的主要工具之一。
