Photoelectron spectrum of PrO{sup −}
- Department of Chemistry, Indiana University, Bloomington, Indiana 47405 (United States)
The photoelectron (PE) spectrum of PrO{sup −} exhibits a short 835 ± 20 cm{sup −1} vibrational progression of doublets (210 ± 30 cm{sup −1} splitting) assigned to transitions from the 4f{sup 2} [{sup 3}H{sub 4}] σ{sub 6s}{sup 2} Ω = 4 anion ground state to the 4f{sup 2} [{sup 3}H{sub 4}] σ{sub 6s} Ω = 3.5 and 4.5 neutral states. This assignment is analogous to that of the recently reported PE spectrum of CeO{sup −}, though the 82 cm{sup −1} splitting between the 4f [{sup 2}F{sub 2.5}] σ{sub 6s} Ω = 2 and Ω = 3 CeO neutral states could not be resolved [Ray et al., J. Chem. Phys. 142, 064305 (2015)]. The origin of the transition to the Ω = 3.5 neutral ground state is 0.96 ± 0.01 eV, which is the adiabatic electron affinity of PrO. Density functional theory calculations on the anion and neutral molecules support the assignment. The appearance of multiple, irregularly spaced and low-intensity features observed ca. 1 eV above the ground state cannot be reconciled with low-lying electronic states of PrO that are accessible via one-electron detachment. However, neutral states correlated with the 4f{sup 2} [{sup 3}H{sub 4}] 5d superconfiguration are predicted to be approximately 1 eV above the 4f{sup 2} [{sup 3}H{sub 4}] σ{sub 6s} Ω = 3.5 neutral ground state, leading to the assignment of these features to shake-up transitions to the excited neutral states. Based on tentative hot band transition assignments, the term energy of the previously unobserved 4f{sup 2} [{sup 3}H{sub 4}] σ{sub 6s} Ω = 2.5 neutral state is determined to be 1840 ± 110 cm{sup −1}.
- OSTI ID:
- 22493506
- Journal Information:
- Journal of Chemical Physics, Vol. 143, Issue 6; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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