Comparison of pure and hybrid DFT functionals for geometry optimization and calculation of redox potentials for iron nitrosyl complexes with ... View Full Text


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Article Info

DATE

2012-12-19

AUTHORS

Nina Emel’yanova, Nataliya Sanina, Alexander Krivenko, Roman Manzhos, Konstantin Bozhenko, Sergey Aldoshin

ABSTRACT

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

PAGES

1316

Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/s00214-012-1316-6

DOI

http://dx.doi.org/10.1007/s00214-012-1316-6

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1019748967


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