A theoretical study of the subshell photoionization of the Xe atom endohedrally confined in C 60 is presented. Powerful hybridization of the Xe 5s state with the bottom edge of C 60 π band is found that induces strong structures in the 5s ionization, causing the cross section to differ significantly from earlier results that omit this hybridization. The hybridization also affects the angular distribution asymmetry parameter of Xe 5p ionization near the Cooper minimum. The 5p cross section, on the other hand, is greatly enhanced by borrowing considerable oscillator strength from the C 60 giant plasmon resonance via the atom-fullerene dynamical interchannel coupling. Beyond the C 60 plasmon energy range the atomic subshell cross sections display confinement-induced oscillations in which, over the large 4d shape resonance region, the dominant 4d oscillations induce their "clones" in all degenerate weaker channels known as correlation confinement resonances.

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We predict that the oscillations in the subshell photoionization of C60 evolve with the orbital angular momentum of the bound electrons such that the structures of the highest and the lowest angular momentum subshell cross sections differ dramatically. The effect results from a decrease in the photoelectron production at the molecular inner edge due to the angular momentum generated repulsion on the electron. Fourier analysis of the cross sections at energies below the carbon K-shell continuum indicates that the effect can be observed by photoelectron spectroscopy. The phenomenon should be generic in the photoionization of nanoparticles containing delocalized electrons.

Considering the photoionization of the Xe@C 60 endohedral compound, we study in detail the ionization cross sections of various levels of the system at energies higher than the plasmon resonance region. Five classes of single-electron levels are identified depending on their spectral character. Each class engenders distinct oscillations in the cross section, emerging from the interference between active ionization modes specific to that class. Analysis of the cross sections based on their Fourier transforms unravels oscillation frequencies that carry unique fingerprints of the emitting level.