The breakdown of the one-electron picture in the ligand XPES of Mo2 (O2CH)4, Mo2 (O2CCH3)4, and Cr2 (O2CCH3)4

Abstract
The C1s and O1s photoelectron spectra of gaseous Mo2(O2CH)4, Mo2(O2CCH3)4, and Cr2(O2CCH3)4 are reported. An intense satellite peak is associated with C1s ionization in Mo2(O2CH)4 and Mo2(O2CCH3)4, but is absent in the other spectra. These observations are interpreted using ab initio MO calculations, together with initial and final state correlation effects. The intense satellite is associated with the transition δ→Lpπ, where δ is a metal–metal bonding orbital and Lpπ is an orbital of the same symmetry localized on the ligand from which ionization has occurred.

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