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The performance of nonhybrid density functionals for calculating the structures and spin states of Fe(II) and Fe(III) complexes
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UNSPECIFIED (2004) The performance of nonhybrid density functionals for calculating the structures and spin states of Fe(II) and Fe(III) complexes. JOURNAL OF COMPUTATIONAL CHEMISTRY, 25 (15). pp. 1840-1848. doi:10.1002/jcc.20101 ISSN 0192-8651.
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Official URL: http://dx.doi.org/10.1002/jcc.20101
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)L-6 and Fe(III)L-6 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 substituted analogs, which are high spin at room temperature but cross over to low spin at low temperature, suggest the RPBE/COSMO combination generates low spin states which are too stable by approximately 13 kcal mol(-1). (C) 2004 Wiley Periodicals, Inc.
Item Type: | Journal Article | ||||
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Subjects: | Q Science > QD Chemistry | ||||
Journal or Publication Title: | JOURNAL OF COMPUTATIONAL CHEMISTRY | ||||
Publisher: | JOHN WILEY & SONS INC | ||||
ISSN: | 0192-8651 | ||||
Official Date: | 30 November 2004 | ||||
Dates: |
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Volume: | 25 | ||||
Number: | 15 | ||||
Number of Pages: | 9 | ||||
Page Range: | pp. 1840-1848 | ||||
DOI: | 10.1002/jcc.20101 | ||||
Publication Status: | Published |
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