Photoelectron spectroscopy ofGdO−

Abstract

We present vibrationally resolved photoelectron spectra of the gadolinium oxide anion GdO Ϫ using 3.495-eV photons. The molecules have been produced in a laser vaporization source and have been mass selected prior to the detachment process. An electron affinity of 1.19Ϯ0.1 eV is measured. The vibrational frequencies of the ground state and the first excited state are determined to be 790Ϯ40 and 887Ϯ40 cm Ϫ1 , respectively. A group of states at 2.6-eV binding energy is interpreted to correlate with the 4 f 7 ( 8 S) 6p( 2 P 1/2 ) ͉⍀ 6 p ͉ϭ1/2 configuration.

Electron Affinities of the Early Lanthanide Monoxide Molecules

“…and density functional theory methods [5−37]. The electron affinities (EAs) of LaO (0.97±0.10 eV) and GdO (1.19±0.10 eV) were reported from photoelectron spectroscopic studies [38,39]. Density functional calculations using the hybrid B3LYP functional underestimated the electron affinities of LaO and GdO.…”

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

“…While not explicitly described as such, an intense group of excited state transitions in the PE spectrum of GdO − was assigned to a shake-up transition as well. 32 These ca. 1 eV excitations appear to be general for systems with doubly occupied 6s-based MOs, underscoring the role of the polarizability of the remnant neutral by the photoelectron being conducive to two-electron excitation.…”

“…10,11,19 The position of manifold II relative to manifold I is nearly identical to a group of excited state transitions observed in the PE spectrum of GdO − , which had been assigned to final neutral states with 4f 7 6p occupancies. 32 Our own calculations on GdO excited states (Table 1) suggest that the final state has 4f 7 5d occupancy, but either way, the transitions are better described as shake-up transitions, where electron promotion accompanies electron detachment. We note here that lower-intensity signal at similar e − BE values in numerous LnxOy − (Ln = Ce, Pr, Sm, Eu) suboxide clusters has been observed, and attributed to shake-up transitions.…”

“…There are four distinct features in manifold I in Figure 2(a), labeled X, A, b, and c. X and b are broader than A and c, and the X-b and A-c energy splitting is very similar to the X 9  − − a 7  − splitting in the GdO diatomic (0.23 eV). 31,32 The states of the diatomic both have 4f 7 6s electronic configurations and differ only in the spin of the electron in the 6s orbital. It is therefore tempting to assign these two sets of peaks to transitions associated with detaching either an  or  electron from one of the 6s MOs of Gd2O2.…”

Monoxides of small terbium clusters: A density functional theory investigation

“…Meanwhile, several theoretical works have been done on Ln n (Ln = Ce, Pr, Gd, Tb) clusters [14][15][16][17][18][19][20] to interpret these measured properties. Despite the amount of studies, little effort has been devoted to the lanthanide oxide clusters, where LnO dimers [21][22][23] as well as the early lanthanide oxide clusters such as LaO n 24 and Ce n O m 25-27 were concerned. Recently, we carried out the theoretical calculations on stoichiometric (Gd 2 O 3 ) n (n = 1-10) clusters.…”