Effects of symmetry-restricted covalence on the electronic spectra of tetragonal copper(II)-ammine compounds

✍ Scribed by Derek W. Smith

• Publisher: Elsevier Science
• Year: 1972
• Tongue: English
• Weight: 290 KB
• Volume: 16
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(72)80307-5

✦ Synopsis

The relative energies of the ZB2g and 'Eg states in tetragonal copper(Iammine complexes are discussed in terms of n model which txka account of symmet-y-restricted covalence. The two-elcct~on terms which arise in expressions for the d-d transition energies are calculnted in the INDO approximation, win, 0 eigenvectors obtained from esperimental ESR data and a simple approximation based on pzrturbation theory. These lead to the prediction that for scjuare coplanar Cu(NH3)$' the *Bz, state should Be higher in energy than 'Eg if the bzg and % orbitals are accidentally degenerate, as indicated by the-angular overlap model. However, it is shown thn! the approach of asial ligmds having ndonor orbital:; leads to the ordering *Eg > 2B2,, notwithstanding the destabilization of the eg orbit& by x-interaction with the axial tigonds. These results are in .:&ordance with the available experimental data.