Structure and Relative Spin-State Energetics of [Fe(H2O)6]3+: A Comparison of UHF, Møller−Plesset, Nonlocal DFT, and Semiempircal INDO/S Calculations
| Autor: | Andrew Komornicki, Daniel K. Harris, Gilda H. Loew |
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| Rok vydání: | 1997 |
| Předmět: | |
| Zdroj: | The Journal of Physical Chemistry A. 101:3959-3965 |
| ISSN: | 1520-5215 1089-5639 |
| Popis: | The optimized structure and spin-state energetics of the iron(ferric)−hexaaquo complex, [Fe(H2O)6]3+, in high (S = 5/2), intermediate (S = 3/2), and low (S = 1/2) spin states were determined from a common starting structure using unrestricted Hartree−Fock (UHF), Moller−Plesset (MP2), and nonlocal density functional theoretical (DFT) methods. All three methods indicate a high−spin ground state for the iron−water complex, consistent with experimental results. The optimized ground-state geometries were similar to each other and in quantitative agreement with known model-system crystal structures and experimental solution phase scattering data. The energy ordering of the spin states of the cluster was also found to be the same at all levels of calculation: E(5/2) < E(3/2) < E(1/2), in agreement with experiment. This same order of spin-state energies was found using the semiempirical INDO/S method. Optimized geometries for both the quartet and doublet excited states led to similar Fe−O(H2) bond distances from... |
| Databáze: | OpenAIRE |
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