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DFT calculations to compute Mössbauer parameters of the 1-X complexes were also undertaken. Our initial success in closely matching the calculated Mössbauer parameters for the parent 1-NCMe complex with those obtained by experiment (ref 18, as well as the success of others refs 79 and 80, led us to anticipate that the corresponding parameters of the 1-X series could be also correctly predicted. For reasons not currently well understood, this expectation has not been borne out for 1-X complexes independent of the basis sets or functionals used for the calculations. Since DFT-calculated ΔEQ values typically have an error of 0.5 mm/s and most of the complexes listed in Table 1 have small ΔEQ values, the DFT calculations yield ΔEQ and η values that are in poor agreement with the experimental values
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Q and η values that are in poor agreement with the experimental values.
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We performed similar computations using the pure BP86 functional, and the results are collected in Table S12. The major trends are virtually identical to those discussed for computations using the PBE0 functional, with the exception that the MO compositions are more covalent when the BP86 functional is used.
-
We performed similar computations using the pure BP86 functional, and the results are collected in Table S12. The major trends are virtually identical to those discussed for computations using the PBE0 functional, with the exception that the MO compositions are more covalent when the BP86 functional is used.
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86
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51949100829
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yz MOs are nondegenerate. However, for most 1-X complexes, these orbitals have very similar energies and thus will be referred to together unless otherwise noted.
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yz MOs are nondegenerate. However, for most 1-X complexes, these orbitals have very similar energies and thus will be referred to together unless otherwise noted.
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