Toffoli Daniele, Quarin Matteo, Fronzoni Giovanna, Stener Mauro
Dipartimento di Scienze Chimiche e Farmaceutiche, Università degli Studi di Trieste, via L. Giorgieri 1, I-34127 Trieste, Italy.
CNR-IOM, Istituto Officina dei Materiali, I-34149, Trieste, Italy.
J Phys Chem A. 2022 Oct 13;126(40):7137-7146. doi: 10.1021/acs.jpca.2c04473. Epub 2022 Sep 29.
We report a benchmark study of vertical excitation energies and oscillator strengths for the HOMO → LUMO transitions of 17 boron-dipyrromethene (BODIPY) structures, showing a large variety of ring sizes and substituents. Results obtained at the time-dependent density functional theory (TDDFT) and at the delta-self-consistent-field (ΔSCF) by using 13 different exchange correlation kernels (within LDA, GGA, hybrid, and range-separated approximations) are benchmarked against the experimental excitation energies when available. It is found that the time-independent ΔSCF DFT method, when used in combination with hybrid PBE0 and B3LYP functionals, largely outperforms TDDFT and can be quite competitive, in terms of accuracy, with computationally more costly wave function based methods such as CC2 and CASPT2.
我们报告了一项针对17种硼二吡咯亚甲基（BODIPY）结构的HOMO→LUMO跃迁的垂直激发能和振子强度的基准研究，这些结构展现出了多种多样的环大小和取代基。利用13种不同的交换相关核（在局域密度近似、广义梯度近似、杂化近似和范围分离近似范围内），通过含时密度泛函理论（TDDFT）和δ-自洽场（ΔSCF）获得的结果，在有可用实验激发能的情况下，与实验值进行了基准比较。研究发现，与混合PBE0和B3LYP泛函结合使用时，与时间无关的ΔSCF DFT方法在很大程度上优于TDDFT，并且在准确性方面，与计算成本更高的基于波函数的方法（如CC2和CASPT2）相比具有相当的竞争力。
