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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Chapter 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 [(¼-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

97-104

Book

TITLE

8th Congress on Electronic Structure: Principles and Applications (ESPA 2012)

ISBN

978-3-642-41271-4
978-3-642-41272-1

Identifiers

URI

http://scigraph.springernature.com/pub.10.1007/978-3-642-41272-1_12

DOI

http://dx.doi.org/10.1007/978-3-642-41272-1_12

DIMENSIONS

https://app.dimensions.ai/details/publication/pub.1019835924


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