通过多态密度函数理论等级激发状态基准测试的山脉
Hong Zhu1,2, Ruoqi Zhao2, Yangyi Lu2
1School of Chemical Biology & Biotechnology, Peking University Shenzhen Graduate School, Shenzhen, Guangdong 518055, China.
The journal of physical chemistry. A
|September 28, 2023
概括
多态密度函数理论与非对角态相互作用 (MSDFT-NOSI) 准确地预测垂直激发能,优于依赖时间的DFT和一些波函数方法. 这一进步为电子结构计算提供了可靠的方法.
科学领域:
- 计算化学计算化学
- 量子化学 是一个量子化学.
- 理论化学 理论化学
背景情况:
- 准确预测垂直激发能量对于理解分子性质和电子转换至关重要.
- 像时间依赖密度函数理论 (TD-DFT) 和波函数理论 (WFT) 这样的现有方法在准确性和计算成本方面存在局限性.
- 多态密度函数理论 (MSDFT) 为描述激发状态提供了一个有希望的替代方案.
研究的目的:
- 评估MSDFT与非直角状态相互作用 (MSDFT-NOSI) 的性能,用于计算垂直激发能.
- 将MSDFT-NOSI与理论最佳估计和已建立的计算方法进行比较.
- 调查不同优化技术和过渡密度函数 (TDF) 估计对MSDFT-NOSI精度的影响.
主要方法:
- 这项研究使用Loos2018数据库上的MSDFT-NOSI评估了100个垂直激发能.
- 研究了两种优化技术 (区块局部激发和目标状态优化) 和两种TDF估计方法.
- 性能与完全配置交互 (FCI) 精度,TD-DFT和各种WFT方法 (CIS(D∞),LR-CC2,ADC(3),STEOM-CCSD,LR-CCSD) 相比进行了基准测试.
主要成果:
- 使用M06-2X功能和旋转倍数退化约束的MSDFT-NOSI实现了0.22 eV的根平均平方误差 (RMSE),明显优于TD-DFT (0.43 eV).
- MSDFT-NOSI的准确性与几种WFT方法相比相当或更好,误差小于CIS ((D∞),LR-CC2和ADC ((3) (0.28 eV),但大于STEOM-CCSD (0.14 eV) 和LR-CCSD (0.11 eV).
- MSDFT-NOSI的性能在价值,Rydberg,单元,三元和双激发状态中是一致的,使用PBE0功能导致系统偏差.
结论:
- MSDFT-NOSI提供了一种强大而准确的方法来计算垂直激发能量,其性能优于传统的TD-DFT.
- 为基态Kohn-Sham DFT开发的密度函数近似可以有效地应用于MSDFT计算,其中状态相互作用很重要.
- 这一基准验证了MSDFT-NOSI作为激发状态电子结构研究的有价值工具.
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