ISSN:
1572-8862
Schlagwort(e):
Metal-metal multiple bonds
;
valence-bond theory
;
electronictransitions
;
theoretical methods
Quelle:
Springer Online Journal Archives 1860-2000
Thema:
Maschinenbau
,
Physik
Notizen:
Abstract The energetics of the δ → δ* transition in quadruply bonded complexes are investigated using a very simple valence-bond formalism, called the isolated δ → δ* manifold (IDDM) model. In this model all electrons except for those that occupy the δ or δ* molecular orbitals are ignored, as are explicit metal-ligand interactions. The resulting equations allow the calculation of transition energies very inexpensively, albeit with poor quantitative agreement: the δ → δ* transition in prototypical quadruple-bond systems is predicted to occur at energies greater than 70,000 cm1. The model incorporates configuration interaction between the two1 A 1g configurations (|δδ| and |δ*δ*|) to roughly the same extent as do correlated all-electron calculations. The application of the method to systems that involve relative changes in δ → δ* transition energies, such as the torsional twisting of quadruple bonds, is more successful quantitatively.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1007/BF01165497
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