Abstract
Photoelectron spectra of [Ni(PF
3
)
4
] have been measured using synchrotron radiation. Relative partial photoionization cross-sections and photoelectron branching ratios of the valence bands (binding energy 9-21 eV) of [Ni(PF
3
)
4
] are reported over the photon-energy range 21-100 eV. The cross-sections of the
d
bands show both a shape resonance between 30 and 50 eV and a
p
-
d
resonance between 70 and 100 eV. Intensity variations are interpreted in terms of the atomic orbital contributions to the molecular orbital from which ionization is taking place. The occurrence of the
p
-
d
resonance for a
d
10
compound is attributed to covalent mixing of
d
character into unoccupied molecular orbitals.