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 $\mathrm{LS}$ 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.