Molecular orbital theory of octahedral complexes
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Self‐consistent charge and configuration (SCCC) molecular orbital calculations are reported for 32 selected octahedral and tetrahedral first‐row transition‐metal complexes containing halide and chalcogenide ligands. It is found that for the range of metal oxidation states II through IV, Fσ, chosen to fit the experimental Δ, is a function of only the metal atomic number for constant Fπ. In the range of formal metal oxidation numbers V through VII, Fσ is also a function of oxidation number.
Calculated and observed trends in covalency, Δ values, and first L→M charge‐transfer energies are compared. The conclusion is drawn that the molecular orbital method, in its present formulation, gives a reasonable account of the ground states and low excited states in simple metal complexes.
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