Abstract
Gold and platinum both have the face-centered cubic crystal structure and are considered noble metals, yet they differ by one in atomic number. Near-edge ${M}_{4,5}$ x-ray absorption and resonant ${M}_{4,5}{N}_{6,7}{N}_{6,7}$ Auger spectra reveal ``dark'' edges and a photon-energy dependence of Auger electron ($4{f}^{12}$ final-state) energy distributions. These findings are a direct consequence of the delayed onset of $d\ensuremath{\rightarrow}f$ transitions and space quantization of the $3d$ core hole prepared by photoexcitation that is predominantly $d\ensuremath{\rightarrow}p$ vs $d\ensuremath{\rightarrow}f$ near the edge, in agreement with theoretical predictions. This study showcases the centrifugal barrier for $f$-wave electrons and spectral evolution arising from the existence of multiple intermediate-state channels and final states for both photoexcitation and Auger decay.
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