Suppression of the low-spin multiplet components in the<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mn>3</mml:mn><mml:mi>p</mml:mi></mml:math>photoelectron spectra of atomic and solid<mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML" display="inline"><mml:mn>3</mml:mn><mml:mi>d</mml:mi></mml:math>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.

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