Electronic structures and spin frustration in Ln3O (Ln = Ce, Sm, Gd) neutrals and anions determined by anion photoelectron spectroscopy

The results of a combined experimental and computational study on Ln3O (Ln = Ce, Sm, and Gd) anion and neutral clusters are presented and analyzed. These three Ln's were specifically targeted because they vary in their spin state and orbital angular momentum associated with the 4fN subshell occupancies. From the anion PE spectra of Ce3O-, Sm3O-, and Gd3O- measured with 2.330 and 3.495 eV photon energies, we determine the adiabatic electron affinities of the corresponding neutrals to be 0.83 ± 0.03, 1.11 ± 0.05, and 1.17 ± 0.05 eV, respectively. The lowest energy features in all three spectra can readily be reconciled with molecular structures in which the O-atom is central to all three Ln centers, with Ce3O-/Ce3O assuming pyramidal structures and Sm3O-/Sm3O and Gd3O-/Gd3O assuming planar structures. Computationally, the lowest-energy structure of neutral Ce3O is a kite-like structure, which is not consistent with the observed spectrum. The kite-like and pyramidal structures of Ce3O- are predicted to be nearly isoenergetic. Electronic states in which all three 4fN centers are ferromagnetically coupled are predicted to be energetically favored for all species, but spin-frustrated states in which one 4fN center is antiferromagnetically coupled to the remaining centers are computed to lie 0.05 eV higher in energy than the FM-coupled states for Ce3O- and Sm3O-. The PE spectrum of Sm3O- exhibits striking anomalies in the photoelectron angular dependence. This effect is attributed to strong photoelectron-valence electron interactions that drive nominally forbidden changes in the Mf state of the remnant neutral.