High-spin versus broken symmetry--Effect of DFT spin density representation on the geometries of three diiron (III) model compounds

Unrestricted density functional theory calculations have been conducted on three diiron(III) synthetic model compounds containing antiferromagnetically coupled high-spin (HS) irons for which crystallographic structures and Raman spectral data are available. Three density functionals have been employ...

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Veröffentlicht in:Journal of computational chemistry Jg. 29; H. 5; S. 716 - 723
Hauptverfasser: Binning, R.C. Jr, Bacelo, Daniel E
Format: Journal Article
Sprache:Englisch
Veröffentlicht: Hoboken Wiley Subscription Services, Inc., A Wiley Company 15.04.2008
Wiley Subscription Services, Inc
Schlagworte:
antiferromagnetic
broken symmetry
Chemical bonds
Chemical compounds
Chemistry
Computer Simulation
Crystal structure
Crystallography
density functional theory
diiron center
exchange coupling
Ferric Compounds - chemical synthesis
Ferric Compounds - chemistry
ferromagnetic
Iron
Models, Chemical
Models, Molecular
Molecular Structure
Quantum Theory
Spectrum Analysis, Raman - methods
Studies
Vibration
ISSN:0192-8651, 1096-987X, 1096-987X
Online-Zugang:Volltext
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Zusammenfassung:Unrestricted density functional theory calculations have been conducted on three diiron(III) synthetic model compounds containing antiferromagnetically coupled high-spin (HS) irons for which crystallographic structures and Raman spectral data are available. Three density functionals have been employed: BPW91, PWC, and BOP. The study compares the effects on optimized geometries and harmonic vibrational frequencies of spin-paired (SP) low-spin, HS, and broken symmetry antiferromagnetically coupled singlet representations of the spin density distribution. The geometries around the diiron centers in the HS and broken symmetry (BS) representations are found to be similar, both markedly different from those arising from the SP representation. Small differences between the HS and BS results are seen in bond lengths, angles, Raman frequencies, and spin densities associated with oxo and peroxo bridges between the irons.
Bibliographie:http://dx.doi.org/10.1002/jcc.20833
Consejo Nacional de Investigaciones Científicas y Técnicas de la República Argentina
ark:/67375/WNG-ZQCZ73SH-M
istex:9D26186B4E8F22285DF6A242E10727CC17EBB28D
National Science Foundation - No. MCB-0641269
ArticleID:JCC20833
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ISSN:0192-8651
1096-987X
1096-987X
DOI:10.1002/jcc.20833