The performance of nonhybrid density functionals for calculating the structures and spin states of Fe(II) and Fe(III) complexes

Journal of Computational Chemistry
Robert J Deeth, Natalie Fey

Abstract

The local density approximation and a range of nonhybrid gradient corrected density functionals (PW91, BLYP, PBE, revPBE, RPBE) have been assessed with respect to the prediction of geometries and spin-state energy preferences for a range of homoleptic Fe(II)L6 and Fe(III)L6 complexes, where L = Cl-, CN-, NH3, pyridine, imidazole, H2O, O=CH2 and tetrahydrofuran. While the qualitative spin-state energies from in vacuo structure optimizations are reasonable the geometries are relatively poorly treated, especially for [FeCl6]3-/4-. Structural results for all the complexes are significantly improved by including environmental effects. The best compromise between structural and spin-state predictive accuracy was obtained for the RPBE functional in combination with the COSMO solvation approach. This approach systematically overestimates the energetic preference for a low spin state, which is partly due to the well-known effect of the lack of exact exchange in nonhybrid functionals and partly due to the larger solvation stabilization of low-spin complexes that have shorter bond lengths and thus smaller molecular volumes than their high-spin partners. Calculations on low spin [Fe(bipy)3]2+ and [Fe(phen)3]2+ and their ortho methyl substi...Continue Reading

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Citations

Jul 11, 2006·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Louis Noodleman, Wen-Ge Han
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