Photoelectron spectra of small LaO n − clusters: decreasing electron affinity upon increasing the number of oxygen atoms

Klingeler, R.; Lüttgens, Günter; Pontius, N.; Rochow, R.; Bechthold, P. S.; Neeb, M.; Eberhardt, W.

doi:10.1007/978-3-642-88188-6_50

Cited by 11 publications

(29 citation statements)

References 9 publications

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“…As for the anion, the extra electron adds to the singly occupied σ * or 6s orbital to form the σ 2 σ * 2 f 0 configuration. The electron affinity of LaO is determined to be 0.99(1) eV which is very close to the value (0.97(10) eV) got previously from the photoelectron spectrum of LaO − [39]. The peak centered around 1.10 eV with an anisotropy parameter β value of 0.24 (4), is about 0.11 eV (851(30) cm −1 ) higher in electron binding energy than that of peak X 1 , which is similar to the vibrational frequency of ground state LaO (813 cm −1 ) (Table II) [37].…”

Section: Resultssupporting

confidence: 85%

“…We assign this peak as the transition to the first vibrational excited state of LaO X 2 Σ + (v =1). The peak centered around 0.90(2) eV with β=1.38 (5), having a band gap of about 0.09 eV with the peak X 1 , is also presented in the photoelectron spectrum reported previously and is assigned as the hot band [39], corresponding to the transition from the first vibrational excited state of LaO − to the ground vibronic state of LaO.…”

Section: Resultssupporting

confidence: 73%

“…The results are summarized in Table I. [31,39,55], i.e., the transition from the ground vibronic state of the LaO − to the ground vibronic state of LaO. The ligand field theory predicated that the ground state of neutral LaO molecule has an electronic configuration of σ 2 σ * 1 f 0 (Table I) [22], in which the σ * 1 f 0 part is derived from the free La 2+ 6s4f 0 configuration.…”

Section: Resultsmentioning

confidence: 99%

“…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.…”

Section: Introductionmentioning

confidence: 99%

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Electron Affinities of the Early Lanthanide Monoxide Molecules

Chi

Xie

Cong

et al. 2011

Chinese Journal of Chemical Physics

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The photoelectron imagings of LaO − , CeO − , PrO − , and NdO − at 1064 nm are reported. The well resolved photoelectron spectra allow the electron affinities to be determined as 0.99(1) eV for LaO, 1.00(1) eV for CeO, 1.00(1) eV for PrO, and 1.01(1) eV for NdO, respectively. Density functional calculations and natural atomic orbital analyses show that the 4f electrons tend to be localized and suffer little from the charge states of the molecules. The photodetached electron mainly originates from the 6s orbital of the metals. The ligand field theory with the δ=2 assumption is still an effective method to analyze the ground states of the neutral and anionic lanthanide monoxides.

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Section: Resultssupporting

confidence: 85%

Section: Resultssupporting

confidence: 73%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Electron Affinities of the Early Lanthanide Monoxide Molecules

Chi

Xie

Cong

et al. 2011

Chinese Journal of Chemical Physics

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“…Photoelectron spectra of small LaO 2 n (n = 1-4) clusters 88 show that, unlike in the above-mentioned and several other species such as AlO n and TiO n , the electron affinity decreases with increasing n, i.e. 0.97, 0.79, ≈ 0.3, and 0.35 eV for n = 1-4, respectively.…”

Section: Transition Metal Tetroxide Anionsmentioning

confidence: 75%

5 Gas-phase stabilities of small anions

Kalcher

2001

Annu. Rep. Prog. Chem., Sect. C

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Exceptionally Complex Electronic Structures of Lanthanide Oxides and Small Molecules

et al. 2019

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Conspectus Lanthanide (Ln) oxide clusters and molecular systems provide a bottom-up look at the electronic structures of the bulk materials because of close parallels in the patterns of Ln 4f N subshell occupancy between the molecular and bulk Ln 2O3 size limits. At the same time, these clusters and molecules offer a challenge to the theory community to find appropriate and robust treatments for the 4f N patterns across the Ln series. Anion photoelectron (PE) spectroscopy provides a powerful experimental tool for studying these systems, mapping the energies of the ground and low-lying excited states of the neutral relative to the initial anion state, providing spectroscopic patterns that reflect the Ln 4f N occupancy. In this Account, we review our anion PE spectroscopic and computational studies on a range of small lanthanide molecules and cluster species. The PE spectra of LnO– (Ln = Ce, Pr, Sm, Eu) diatomic molecules show spectroscopic signatures associated with detachment of an electron from what can be described as a diffuse Ln 6s-like orbital. While the spectra of all four diatomics share this common transition, the fine structure in the transition becomes more complex with increasing 4f occupancy. This effect reflects increased coupling between the electrons occupying the corelike 4f and diffuse 6s orbitals with increasing N. Understanding the PE spectra of these diatomics sets the stage for interpreting the spectra of polyatomic molecular and cluster species. In general, the results confirm that the partial 4f N subshell occupancy is largely preserved between molecular and bulk oxides and borides. However, they also suggest that surfaces and edges of bulk materials may support a low-energy, diffuse Ln 6s band, in contrast to bulk interiors, in which the 6s band is destabilized relative to the 5d band. We also identify cases in which the molecular Ln centers have 4f N+1 occupancy rather than bulklike 4f N , which results in weaker Ln–O bonding. Specifically, Sm centers in mixed Ce–Sm oxides or in Sm x O y – (y ≤ x) clusters have this higher 4f N+1 occupancy. The PE spectra of these particular species exhibit a striking increase in the relative intensities of excited-state transitions with decreasing photon energy (resulting in lower photoelectron kinetic energy). This is opposite of what is expected on the basis of the threshold laws that govern photodetachment. We relate this phenomenon to strong electron–neutral interactions unique to these complex electronic structures. The time scale of the interaction, which shakes up the electronic configuration of the neutral, increases with decreasing electron momentum. From a computational standpoint, we point out that special care must be taken when considering Ln cluster and molecular systems toward the center of the Ln series (e.g., Sm, Eu), where treatment of electrons explicitly or using an effective core potential can yield conflicting results on competing subshell occupancies. However, despite the complex electronic structures associated with parti...

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Photoelectron spectra of small LaO n − clusters: decreasing electron affinity upon increasing the number of oxygen atoms

Cited by 11 publications

References 9 publications

Electron Affinities of the Early Lanthanide Monoxide Molecules

Electron Affinities of the Early Lanthanide Monoxide Molecules

5 Gas-phase stabilities of small anions

Exceptionally Complex Electronic Structures of Lanthanide Oxides and Small Molecules

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