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It is commonly observed that the calculated Löwdin charges do not reflect the oxidation or reduction events with nearly integer changes in the calculated charges. This is partly due to the large electronic relaxation effects accompanying ionization events and also to the problem of properly dividing the charge in the bond region and the 4s population between the metal and ligand atoms. The 4s orbital has a probability density maximum roughly at the position of the ligands. Assigning its contribution to the iron is therefore problematic. The spin densities on the other hand are dominated by the compact 3d shell and reflect the actual events more closely. Due to these difficulties one should not equate the changes in Löwdin charges with shifts in edge energies. A proper calculation of edge energies and preedge intensities is beyond the scope of this paper.
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Experimental magnetic susceptibility data are adiabatic measurements and the fairest comparison between theory and experiment would therefore involve comparison of fully relaxed structures for all spin states. However, such a geometry dependence is already beyond the scope of the Heisenberg Hamiltonian and would lead to deviations from the regular spin ladder. In addition, there are the technical difficulties of obtaining the geometry of the low-spin state as opposed to the BS state and problems of numerical precision because the energy differences involved are very small. These effects may be ignored if the geometric relaxation effects are very small. However, in the present work, we have observed some uncomfortably large variations of geometry with spin state (HS or BS). Because geometrical parameters are only known for one of the spin states from the EXAFS and X-ray crystallographic experiments, we prefer to estimate the exchange couplings using the standard approach of fixed geometry calculations.
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(a) Brown, C. A.; Remar, G. J.; Musselman, R. L.; Solomon, E. I. Inorg. Chem. 1995, 34, 688
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Brown, C.A.1
Remar, G.J.2
Musselman, R.L.3
Solomon, E.I.4
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84
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0000208617
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(b) Solomon, E. I. Brunold, T. C.; Davis, M. I.; Kemsely, J. N.; Lee, S.-K., Lehnert, N.; Neese, F.; Skulan, A. J.; Yang, Y.-S., Zhou, J. Chem. Rev. 2000, 100, 235.
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(2000)
Chem. Rev.
, vol.100
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Solomon, E.I.1
Brunold, T.C.2
Davis, M.I.3
Kemsely, J.N.4
Lee, S.-K.5
Lehnert, N.6
Neese, F.7
Skulan, A.J.8
Yang, Y.-S.9
Zhou, J.10
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87
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0347545244
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note
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A + 1) + S(S + 1)/2S(S + 1). In the limit of large |J| only the first two terms contribute to the observed g tensor, and the single-site zfs contribution can be neglected in the prediction of the g-values.
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