Kühn Michael, Weigend Florian
Institut für Physikalische Chemie, Karlsruher Institut für Technologie, Kaiserstraße 12, 76131 Karlsruhe, Germany.
J Chem Phys. 2015 Jan 21;142(3):034116. doi: 10.1063/1.4905829.
We report the implementation of a two-component variant of time-dependent density functional theory (TDDFT) for hybrid functionals that accounts for spin-orbit effects within the Tamm-Dancoff approximation (TDA) for closed-shell systems. The influence of the admixture of Hartree-Fock exchange on excitation energies is investigated for several atoms and diatomic molecules by comparison to numbers for pure density functionals obtained previously [M. Kühn and F. Weigend, J. Chem. Theory Comput. 9, 5341 (2013)]. It is further related to changes upon switching to the local density approximation or using the full TDDFT formalism instead of TDA. Efficiency is demonstrated for a comparably large system, Ir(ppy)3 (61 atoms, 1501 basis functions, lowest 10 excited states), which is a prototype molecule for organic light-emitting diodes, due to its "spin-forbidden" triplet-singlet transition.
我们报告了一种用于杂化泛函的含时密度泛函理论（TDDFT）的双组分变体的实现，该变体在闭壳层系统的塔姆 - 丹科夫近似（TDA）内考虑了自旋 - 轨道效应。通过与先前获得的纯密度泛函的数据[M. 库恩和F. 魏根德，《化学理论与计算杂志》9，5341（2013）]进行比较，研究了哈特里 - 福克交换混合对几个原子和双原子分子激发能的影响。它还与切换到局域密度近似或使用完整的TDDFT形式主义而非TDA时的变化相关。对于一个相对较大的系统Ir(ppy)3（61个原子，1501个基函数，最低的10个激发态）展示了其效率，由于其“自旋禁阻”的三重态 - 单重态跃迁，Ir(ppy)3是有机发光二极管的原型分子。
