New Photoelectron-Valence Electron Interactions Evident in the Photoelectron Spectrum of Gd₂O

Evidence of strong photoelectron-valence electron (PEVE) interactions has been observed in the anion photoelectron (PE) spectra of several lanthanide suboxide clusters, which are exceptionally complex from an electronic structure standpoint and are strongly correlated systems. The PE spectrum of Gd₂O^-, which should have relatively simple electronic structure because of its half-filled 4f subshell, exhibits numerous electronic transitions. The electron affinity determined from the spectrum is 0.26 eV. The intensities of transitions to excited states increase relative to the lower-energy states with lower photon energy, which is consistent with shakeup transitions driven by time-dependent electron-neutral interactions. A group of intense spectral features that lie between electron binding energies of 0.7 and 2.3 eV are assigned to transitions involving detachment of an electron from outer-valence σ_u and σ_g orbitals that have large Gd 6s contributions. The spectra show parallel transition manifolds in general, which is consistent with detachment from these orbitals. However, several distinct perpendicular transitions are observed adjacent to several of the vertical transitions. A possible explanation invoking interaction between the ejected electron and the high-spin neutral is proposed. Specifically, the angular momentum of electrons ejected from σ_u or σ_g orbitals, which is $$ = 1, can switch to $$ = 0, 2 with an associated change in the M_s of the remnant neutral, which is spin-orbit coupling between a free electron and the spin of a neutral.