Comparison of pure and hybrid DFT functionals for geometry optimization and calculation of redox potentials for iron nitrosyl complexes with “μ-SCN” bridging ligands
作者： Nina Emel’yanova , Nataliya Sanina , Alexander Krivenko , Roman Manzhos , Konstantin Bozhenko
DOI: 10.1007/S00214-012-1316-6
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摘要: The geometry and electronic structure of neutral molecules mono-anions iron nitrosyl complexes with “µ-SCN” bridging ligands [(¼-SC7H4SN)Fe(NO)2]2 (I) [(µ-SC2H3N4)Fe(NO)2]2 (II) were studied using the density functional theory: pure functionals BP86, OLYP, OPBE, TPSS, PW91 hybrid B3LYP, B1B95, B3PW91 along 6-311++G**//6-31G*. For optimization, are more appropriate than functionals. mono-anions, favor doublet over quartet state by 8.0–13.9 kcal/ mol, whereas yield spin these anions to be stable. redox potentials I II have been computed DFT compared experimental results obtained from cyclic voltammetry method. calculated for (especially BP86) close values, those significantly deviate experiment.
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