混合功能
电离能
密度泛函理论
还原(数学)
二茂铁
电离
水准点(测量)
基准集
计算化学
化学
溶剂化
隐溶剂化
热力学
材料科学
物理化学
数学
物理
分子
有机化学
电化学
大地测量学
地理
离子
几何学
电极
作者
Mateja Toma,Tea Kuvek,Valerije Vrček
标识
DOI:10.1021/acs.jpca.0c06663
摘要
Hybrid density functionals have been regularly applied in state-of-the-art computational models for predicting reduction potentials. Benchmark calculations of the absolute reduction potential of ferricenium/ferrocene couple, the IUPAC-proposed reference in nonaqueous solution, include the B3LYP/6-31G(d)/LanL2TZf protocol. We used this procedure to calculate ionization energies and reduction potentials for a comprehensive set of ferrocene derivatives. The protocol works very well for a number of derivatives. However, a significant discrepancy (>1 V) between experimental and calculated data was detected for selected cases. Three variables were assessed to detect an origin of the observed failure: density functional, basis set, and solvation model. It comes out that the Hartree-Fock exchange fraction in hybrid-DFT methods is the main source of the error. The accidental errors were observed for other hybrid models like PBE0, BHandHLYP, and M06-2X. Therefore, hybrid DFT methods should be used with caution, or pure functionals (BLYP or M06L) may be used instead.
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