Suppression of the low-spin multiplet components in the 3p photoelectron spectra of atomic and solid 3d metals

The 3p photoelectron spectra of Cr, Mn, Fe, and Co atoms have been studied experimentally and theoretically. The 3p-3d interaction in the final ionic state gives rise to an LS multiplet structure spanning a binding-energy range of around 20 eV. The prominent high-spin components at low binding energies contrast with the broad and weak low-spin components at high binding energies. Term-dependent lifetime broadening by super-Coster-Kronig decays is the main cause of the almost complete suppression of the latter lines. The corresponding 3p photoelectron spectra of the metals display only a single broad asymmetric line. The influence of correlation on the 3p photoelectron spectra is shown to be less dramatic than in the case of the better known 3s photoelectron spectra. We show that, while the peculiarities in the 3s spectrum are caused by configuration interaction, the single-configuration approximation already provides the clue to the interpretation of the 3p spectrum.