Galstyan Artur, Knapp Ernst-Walter
Department of Biology, Chemistry, and Pharmacy, Institute of Chemistry and Biochemistry, Free University of Berlin, Fabeckstr. 36a, D-14195 Berlin, Germany.
J Comput Chem. 2009 Jan 30;30(2):203-11. doi: 10.1002/jcc.21029.
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 58 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.
密度泛函理论（DFT）与连续介质电介质的泊松方程解相结合，以计算几种涉及铁、锰和镍的单核过渡金属配合物（TMC）的精确氧化还原电位。通过改变B3LYP DFT泛函（B4(XQ3)LYP方法）并补充一个具有三个额外可调参数的经验校正项G(X)取得了进展，该经验校正项在量子化学DFT计算之后应用。该方法用于计算48种不同TMC的58个氧化还原电位，这些TMC涉及在质子溶剂和非质子溶剂中溶剂化的不同氧化还原态对。对于这58个氧化还原电位，与实验值的均方根偏差（RMSD）为65 mV。如果也考虑溶剂的影响，所有研究的TMC的电子基态自旋多重性的能量顺序都得到满足，这一观察结果也支持了本方法的可靠性。
