M4,5N4,5N4,5Auger-electron spectrum of free Pd atoms

The $M_{4,5}{N}_{4,5}{N}_{4,5}$ Auger-electron spectrum of free palladium atoms has been measured by means of a new high-temperature spectrometer using electron-beam excitation. The experimental spectrum has been compared with the theoretical profile calculated in a nonrelativistic mixed-coupling scheme applying $\mathrm{jj}$ coupling to the initial state and intermediate coupling to the final one. The energies have also been compared with the theoretical results obtained from relativistic intermediate-coupling calculations. Apart from the Auger energies, the free-atom $3d$ binding energies $E_B\left({3d}_{\frac{5}{2}}\right)=341.13\mathrm{}\left(15\right)\mathrm{}$ eV and $E_B\left({3d}_{\frac{3}{2}}\right)=346.45\mathrm{}\left(15\right)\mathrm{}$ eV have also been determined with the aid of optically known two-hole final-state energies. Comparisons with the solid-state photoelectron and Auger-electron measurements give free-atom-metal shifts of 1.3 eV for the 3d binding energies and 11.3 eV for the $M_{4,5}{N}_{4,5}{N}_{4,5}\left({}_{}{}^1{}_{}{}^{}G_4^{}{}_{}{}^{}\right)$ Auger energies, also referring the solid-state energies to the vacuum level.