Abstract
We have performed an Auger-photoelectron coincidence spectroscopy (APECS) study of the Pd ${M}_{45}\mathrm{VV}$ Auger transition to ascertain the intrinsic line shapes of the ${M}_{4}\mathrm{VV}$ and ${M}_{5}\mathrm{VV}$ transitions at high-energy resolution (0.72 eV considering electrons and photons). The line shapes cannot be described by a simple self-convolution of the valence-band density of states, but are well described by the Cini-Sawatzky (CS) theory when it is applied separately to each component of the multiplet structure of the ${d}^{8}$ Auger final state. A fit to the APECS data using the sum of a CS distortion of the final-state multiplet splittings for the ${M}_{4}\mathrm{VV}$ and ${M}_{5}\mathrm{VV}$ Auger transitions indicates that the correlation energy of the most intense ${}^{1}{G}_{4}$ multiplet is $3.2\ifmmode\pm\else\textpm\fi{}0.1\mathrm{eV}.$ In addition, we find evidence that $(12\ifmmode\pm\else\textpm\fi{}3)%$ of the intrinsic ${M}_{4}\mathrm{VV}$ intensity is associated with Coster-Kronig-preceded Auger decays of ${3d}_{3/2}$ core holes.
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