Rotation-Electronic Deperturbation Analysis of the 4f 6s Configurational States of CeO

Low‐Lying Excited States of Lanthanide Diatomics Studied by Four‐Component Relativistic Configuration Interaction Methods

“…[61,62] Many observations have since been performed. [7,[63][64][65] Linton et al [64] gave an almost complete table of spectra in the range 0-3.546 eV. Kaledin et al [65] investigated the spectra in the same range, using ligand field theory (LFT) as refined by Field.…”

“…The electronic structure of these molecules has previously been studied by methods such as ligand field theory, [6][7][8] molecular orbital theory with/without spin-orbit configuration interaction (SOCI), [9][10][11][12][13] and four-component relativistic theory. [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29] Although theory and computer programs have developed rapidly in recent decades, the behavior of f electrons in lanthanide compounds remains a challenging subject.…”

Photoelectron Spectra of Gd2O2− and Non-Monotonic Photon-Energy Dependent Variations in Populations of Close-Lying Neutral States

“…If we consider LnO diatomic molecules, in which the valence orbital occupancy can be described in general terms as [2p 2 2p 4 ] 4f n 6s, numerous close-lying states associated with the coupling between the 4f and 6s electrons, and the manifold states associated with the projection of jf and j6s onto the internuclear axis (). As an example, CeO (4f 1 6s) has 16 states within a 0.5 eV window of energy, [5][6][7] SmO (4f 5 6s) has 30 states in the same window, plus tens more slightly higher in energy. 8 EuO (4f 7 ) and GdO (4f 7 6s), near the center of the row are much simpler, having one and two states arising from those occupancies, respectively, because of the zero-orbital angular momentum associated with the half-filled 4f ( 8 S) subshell.…”

“…As an example, CeO (4f 1 6s) has 16 states within a 0.5 eV window of energy, [5][6][7] SmO (4f 5 6s) has 30 states in the same window, plus tens more slightly higher in energy. 8 EuO (4f 7 ) and GdO (4f 7 6s), near the center of the row are much simpler, having one and two states arising from those occupancies, respectively, because of the zero-orbital angular momentum associated with the half-filled 4f ( 8 S) subshell. 8 Electron correlation is also an important governing factor in photoionization and photodetachment processes.…”

“…In this report, we present a new and striking example of this intriguing inverse-threshold phenomenon by examining the Gd2O2 − cluster. We hypothesized this system would provide a useful canvas for exploring the fundamental physics of this effect due to the much simpler electronic structure afforded by the 4f 7 subshell occupancy. Based on DFT calculations, Gd2O2 − is expected to have D2h symmetry, with the two O-atoms bridging the Gd centers which are separated by ca.…”