基于密度泛函理论的吖啶衍生物基态和激发态还原电位的快速准确估算

IF 1.9 4区 化学 Q2 CHEMISTRY, ORGANIC
Jiyoon Choi, Kyungtae Kang, Ji Hun Park, Hyungjun Kim
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引用次数: 0

摘要

我们设计了一种量子化学模拟方案,可以快速准确地预测吖啶鎓光氧化催化剂(PCs)的基态和激发态还原电位(分别为 E0 和 E*)。为了绕过耗时的激发态几何优化,我们使用基态平衡几何来计算激发态的电子能量,从而提供合理的 E0 和 E* 估计值。为了估算 E0 和 E*,我们系统地改变了密度函数中哈特里-福克交换(HFX)的贡献。除了再现实验结果之外,物理上合理的模型(如对激子行为的正确描述)也是非常必要的。根据激子相关值,我们确定 B3LYP 函数中 HFX 的适当含量为 30%,以便为小型有机分子生成物理上合理的结合电子-空穴对。我们还研究了基集对 E0 和 E* 可预测性的影响。用 B3LYP-D2(HFX 20 %)/6-31G 进行几何优化,用 (TD-)B3LYP-D2(HFX 30 %)/6-311++G(d,p) 进行单点能量细化,得到了最佳结果。由八个吖啶鎓衍生物组成的测试集证实了建议方案的可移植性。这项研究可以利用相对较少的计算资源提供相当准确的结果,因此有望极大地促进新型吖啶鎓 PCs 的开发。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Density functional theory-based rapid and accurate estimation of reduction potentials of acridinium derivatives in ground and excited state

We devised a quantum chemical simulation protocol that can rapidly and accurately predict ground and excited state reduction potentials (E0 and E*, respectively) of acridinium photoredox catalysts (PCs). To bypass time-consuming excited state geometry optimizations, we used ground state equilibrium geometries to compute the electronic energy of excited states, which provides reasonable E0 and E* estimates. The contribution of Hartree-Fock exchange (HFX) in density functionals was systematically varied to estimate E0 and E*. In addition to reproducing experimental results, physically sensible models, such as correct descriptions of exciton behavior, are highly necessary. Based on the exciton correlation values, the appropriate amount of HFX in the B3LYP functional was determined to be 30 % to yield physically sensible bound electron-hole pairs for small organic molecules. We also investigated the impact of basis sets on the predictability of E0 and E*. Geometry optimizations with B3LYP-D2(HFX 20 %)/6-31G and single point energy refinement with (TD-)B3LYP-D2(HFX 30%)/6-311++G(d,p) yielded the best results. The transferability of the suggested protocol was confirmed with a test set consisting of eight acridinium derivatives. This study can provide reasonably accurate results with relatively small amounts of computational resources, and it is therefore expected to greatly contribute to the development of new acridinium PCs.

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来源期刊
CiteScore
3.60
自引率
11.10%
发文量
161
审稿时长
2.3 months
期刊介绍: The Journal of Physical Organic Chemistry is the foremost international journal devoted to the relationship between molecular structure and chemical reactivity in organic systems. It publishes Research Articles, Reviews and Mini Reviews based on research striving to understand the principles governing chemical structures in relation to activity and transformation with physical and mathematical rigor, using results derived from experimental and computational methods. Physical Organic Chemistry is a central and fundamental field with multiple applications in fields such as molecular recognition, supramolecular chemistry, catalysis, photochemistry, biological and material sciences, nanotechnology and surface science.
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