G4 accuracy at DFT cost: unlocking accurate redox potentials for organic molecules using systematic error cancellation
G4 accuracy at DFT cost: unlocking accurate redox potentials for organic molecules using systematic error cancellation
复制标题
DFT 成本下的 G4 精度：使用系统误差消除解锁有机分子的精确氧化还原电位
DOI：
10.1039/c9cp06622e
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发表时间：
2020
影响因子：
3.3
通讯作者：
Raghavachari, Krishnan
中科院分区：
文献类型：
--
作者：
Maier, Sarah;Thapa, Bishnu;Raghavachari, Krishnan
氧化还原电位是一个强大的热力学和动力学工具，用于预测许多化学和生化机制。然而，尽管密度泛函理论（DFT）的预测能力有所提高，但DFT通常难以实现化学精确的理论氧化还原电位。例如，计算出的氧化还原电位对密度函数的选择很敏感，往往达不到期望的精度。因此，不同密度泛函之间计算氧化还原电位的误差范围可能变得相当大。目前的研究提出了一种具有成本效益的方案，利用有效的误差抵消方案来准确预测各种有机分子的氧化还原电位。这种计算协议被称为CBH- redox，是基于连接的层次（CBH）方法的扩展，可以产生接近g4精度的热化学数据。在此，我们针对实验和G4参考值测试了cbh -氧化还原方案，并将这些结果与单独的DFT进行了比较。考虑46个含C、O、N、F、Cl和S原子的分子，当使用CBH-Redox校正方案时，与实验和G4相比，所有8个密度函数的MAEs都在0.09 V的目标精度范围内。此外，CBH-Redox达到了令人印象深刻的准确性，与G4相比，在测试的8种密度函数中，有6种的MAE为0.05 V或更低。此外，当应用CBH校正时，测试的所有功能的误差范围与G4相比从0.12 V减小到约0.05 V，与实验相比从0.13 V减小到0.04 V。
The redox potential is a powerful thermodynamic and kinetic tool used to predict numerous chemical and biochemical mechanisms. However, despite the improving predictive power of density functional theory (DFT), chemically accurate theoretical redox potentials are often difficult to achieve with DFT. For example, calculated redox potentials are sensitive to density functional choice and often fall short of the desired accuracy. Thus, ranges of errors for computed redox potentials between different density functionals can become quite large. The current study presents a cost-effective protocol that utilizes effective error cancellation schemes in order to accurately predict the redox potentials of a wide range of organic molecules. This computational protocol, called CBH-Redox, is an extension of the connectivity-based hierarchy (CBH) method, and produces thermochemical data with near-G4 accuracy. Herein, we test the CBH-Redox protocol against both experimental and G4 reference values and compare these results to DFT alone. Considering 46 C, O, N, F, Cl, and S atom-containing molecules, when using the CBH-Redox correction scheme, the MAEs for all eight density functionals tested are within the 0.09 V target accuracy versus both experiment and G4. Moreover, CBH-Redox achieves an impressive accuracy, with a MAE of 0.05 V or below when compared to G4 for six of the eight density functionals tested. In addition, when the CBH correction is applied, the error range across all functionals tested decreases from 0.12 V to about 0.05 V versus G4, and from 0.13 V to 0.04 V versus experiment.