Accurate Redox Potentials of Mononuclear Iron, Manganese, and Nickel Model Complexes
Accurate Redox Potentials of Mononuclear Iron, Manganese, and Nickel Model Complexes
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DOI：
10.1002/jcc.21029
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发表时间：
2009-01-30
影响因子：
3
通讯作者：
Knapp, Ernst-Walter
中科院分区：
文献类型：
--
作者：
Galstyan, Artur;Knapp, Ernst-Walter
将密度泛函理论（DFT）与连续介质中泊松方程的求解相结合，计算了铁、锰、镍等过渡金属单核配合物的氧化还原电位.通过改变B3 LYP DFT泛函（B4（XQ 3）LYP方法）并使用具有三个额外可调参数的经验修正项G（x）对其进行补充，取得了进展，该修正项在量子化学DFT计算后应用。该方法被用来计算58氧化还原电位的48个不同的TMC涉及不同的氧化还原状态溶剂化在质子和非质子溶剂。对于59个氧化还原电位，与实验值的均方根偏差（RMSD）为65 mV。本方法的可靠性也支持的观察，满足所有研究的TMC的电子基态的自旋多重性的能量顺序，如果从溶剂的影响。也被认为是。(C)2008 Wiley Periodicals，Inc. J Comput Chem 30：203-211，2009
Density functional theory (DFT) was combined with solution of the Poisson equation for continuum dielectric media to compute accurate redox potentials for several mononuclear transition metal complexes (TMCs) involving iron, manganese, and nickel. Progress was achieved by altering the B3LYP DFT functional (B4(XQ3)LYP-approach) and Supplementing it with an empirical correction term G(x) having three additional adjustable parameters, which is applied after the quantum-chemical DFT Computations. This method was used to compute 58 redox potentials of 48 different TMCs involving different pairs of redox states solvated in both protic and aprotic solvents. For the 59 redox potentials the root mean square deviation (RMSD) from experimental values is 65 mV. The reliability of the present approach is also supported by the observation that the energetic order of the spin multiplicities of the electronic ground states is fulfilled for all Studied TMCs, if the influence from the solvent. is considered as well. (C) 2008 Wiley Periodicals, Inc. J Comput Chem 30: 203-211, 2009