Gas-phase ESCA studies of valence and core levels in xenon difluoride and xenon tetrafluoride

Bancroft, G. M.; Malmquist, P. A.; Svensson, S.; Basilier, E.; Gelius, U.; Siegbahn, K.

doi:10.1021/ic50184a040

Cited by 46 publications

(16 citation statements)

References 32 publications

(6 reference statements)

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“…A similar difference in linewidth was seen between the XPS of the Xe 3d and Xe 4d lines [47] in Xe gas (0.87 eV versus 0.64 eV, at moderate instrumental resolution), and this is due to the difference in lifetime linewidth of 0.5 eV for Xe 3d compared to 0.1 eV for Xe 4d [48].…”

Section: Linewidths and Assignment To Different Sb And S Sitessupporting

confidence: 56%

High resolution XPS study of the large-band-gap semiconductor stibnite (Sb2S3): Structural contributions and surface reconstruction

et al. 2006

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Section: Linewidths and Assignment To Different Sb And S Sitessupporting

confidence: 56%

High resolution XPS study of the large-band-gap semiconductor stibnite (Sb2S3): Structural contributions and surface reconstruction

et al. 2006

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“…Several spectroscopic studies have been made in various energy ranges that compare transition energies and transition strengths of Xe and XeF 2 . The Xe 4d, Xe 3d, and F 1s ionization energies are sensitive to the shielding effects of valence electron charge distributions, i.e., "chemical shifts" [80][81][82]. Also, an intense, antibonding 7σ u lowest unoccupied molecular orbital (LUMO) [79] is observed in vacuum-ultraviolet [78,83], farultraviolet [84], and soft x-ray [45] photoabsorption spectra of XeF 2 .…”

Section: Xe K -Edge Of Xefmentioning

confidence: 99%

Observing pre-edgeK-shell resonances in Kr, Xe, andXeF2

et al. 2019

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The 1s → np Rydberg transitions below the 1s ionization thresholds of Kr and Xe are obscured in x-ray absorption spectra due to core-hole lifetime broadening. However, the np spectator electrons associated with those resonances can affect the core-hole decay spectra. We report on ion chargestate distributions of Kr and Xe measured in coincidence with KL 2,3 (Kα 1,2 ), KM 2,3 (Kβ 1,3 ) and KN 2,3 (Kβ 2 ) x-ray fluorescence as the incident x-ray energy is scanned through pre-edge resonances and ionization thresholds. The coincidence measurements select vacancy cascades that begin with a radiative transition that transfers 1s holes to the 2p, 3p, and 4p shells followed by emission of Auger electrons. We observe shifts of ion yields from higher to lower charge states that we attribute to np spectator electrons. For the special case of Kr 1+ that is produced in coincidence with Kβ 2 x rays, the ion yield decreases in the pre-edge region. This is attributed to production of neutral, metastable Kr 4p −1 np states that reduce the Kr 1+ yield. Model fits to the x-ray absorption spectra are presented to show the lifetime broadened pre-edge resonances and ionization thresholds. High-level relativistic coupled-cluster calculations that treat relativistic, electron correlation, and wavefunction relaxation effects on the same footing obtain agreement with the experimental 1s ionization energies of Kr and Xe to <2 eV. The Xe K -edge x-ray absorption spectrum and ion charge-state distributions of XeF 2 were also recorded. Excitation of the 7σ u lowest unoccupied molecular orbital (LUMO) in XeF 2 is observed in the pre-edge region. Our ab initio calculations find that the 6p z Rydberg state is strongly perturbed by the presence of the 7σ u LUMO. A fit to the measured LUMO, 6p x , 6p y , 6p z Rydberg states, and ionization threshold is guided by the relativistic coupled-cluster calculations. The F ligands modify the valence electron charge distribution and result in a ∼2.3-eV chemical shift of the Xe 1s ionization energy relative to atomic Xe. Xe 1s −1 core-hole decay in XeF 2 results in ionization of the F ligands and energetic fragmentation into atomic ions. Ion charge-state spectra of XeF 2 were recorded in coincidence with x-ray fluorescence for excitation on the LUMO resonance and above the Xe 1s ionization threshold.For the ion time of flight spectra recorded on the LUMO resonance, the F q+ (q=1-4) peaks are split into two peaks along the linear polarization direction of the incident x-ray beam. This effect is attributed to spatial alignment of XeF 2 molecules by resonant x-ray absorption, and the peak splittings are used to measure the F ion fragmentation energies following Kα 1,2 , Kβ 1,3 , and Kβ 2 xray fluorescence. We observe variations of the F ion charge state yields and fragmentation energies for the three fluorescence pathways that leave the molecule in different outer-shell hole states.

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“…As in the case of the 4d resonances, the position is shifted to higher energy in XeF2 due to the electron withdrawing characteristics of the F atoms. The second weak feature is observed at 207.8(4) eV, as compared to the XeF2 4s -1 threshold at 216.04 ± 0.10 eV, 33 yielding a binding energy of ~8.24 eV. Based on the binding energy of the u* valence orbital with respect to the 4d -1 threshold, the most likely assignment for the 207.8 eV feature is 4s → u*.…”

Section: Please Cite This Article Asmentioning

confidence: 95%

“…The currently accepted ordering of the configuration of XeF2 is: …(Xe 4s) 2 (Xe 4p) 6 (Xe 4d) 10 8g 2 5u 2 9g 2 6u 2 4u 4 3g 4 10g 2 5u 4 . 33 More recently, Buth et al 38 performed detailed calculations on the single-ionization spectra of XeF2, XeF4, and XeF6 from the first ionization energy to the Xe 4d ionization threshold. In a subsequent paper, 39 they performed calculations and analysis of the double ionization thresholds, as well as a study of the decay mechanisms for the Xe 4d hole states.…”

Section: Please Cite This Article Asmentioning

confidence: 99%

“…bound resonances just below the Xe 4d -1 threshold and by a large 4d → f shape resonance in the region above it. This work was followed by photoelectron spectroscopy studies of XeF2, XeF4, and XeF6 by Carroll et al 32 and Bancroft et al 33 at the F 1s and Xe 3d thresholds. Auger electron spectroscopy following Xe 3d hole formation was also characterized by Aksela et al, 34 and most recently Southworth et al 35 performed a detailed study of the fragmentation dynamics of XeF2 following 3d hole production.…”

Section: Introductionmentioning

confidence: 99%

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