ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
In contrast to former ligand field predictions, the standard energetic order of the metal 3d orbitals, δ〈π〈σ, is not reproduced here. Throughout, the 3dσ molecular orbital (MO) level is found rather low lying because of σ-donating ligand induced 3d-4s hybridization in these linear dicoordinated compounds, while the 3dπ is rather high due to the pronounced π-donor character of the halogen ligands at the short distances of the digonal halides. This results in an unexpected electron distribution for the ground state and in an unusual order of electronic states. The calculations are in general consistent with recent experimental findings. The approach yields semiquantitatively correct geometric parameters and vibrational frequencies, and qualitatively correct trends for the dissociation energies. Those properties show a secondary periodicity, similar to the one known for octahedral high-spin complexes, though for different electronic reasons. Unknown structures, vibrational frequencies, and dissociation energies are predicted. © 1998 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.477359
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