Pd M45VV Auger spectrum determined by Auger-photoelectron coincidence spectroscopy:: Intrinsic line shape and Coster-Kronig transitions -: art. no. 115115

We have performed an Auger-photoelectron coincidence spectroscopy (APECS) study of the Pd M45VV Auger transition to ascertain the intrinsic line shapes of the M4VV and M5VV 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 M4VV and M5VV Auger transitions indicates that the correlation energy of the most intense (1)G(4) multiplet is 3.2+/-0.1 eV. In addition, we find evidence that (12+/-3)% of the intrinsic M4VV intensity is associated with Coster-Kronig-preceded Auger decays of 3d(3/2) core holes.