High-resolution measurements of near-edge resonances in the core-level photoionization spectra of SF[sub 6]

Journal Article · Thu Dec 31 23:00:00 EST 1992 · Physical Review A; (United States)

DOI:https://doi.org/10.1103/PhysRevA.47.361· OSTI ID:6942071

Hudson, E; Shirley, D A ^[1]; Domke, M; Remmers, G; Puschmann, A; Mandel, T; Xue, C ^[2]; Kaindl, G ^[3]

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1. Department of Chemistry, University of California, Berkeley, California 94720 (United States) Chemical Sciences Division, MS 2-300, Lawrence Berkeley Laboratory, 1 Cyclotron Road, Berkeley, California 94720 (United States)
2. Institut fuer Experimentalphysik, Freie Universitaet Berlin, Arnimallee 14, W-1000 Berlin 33 (Germany)
3. Institut fuer Experimentalphysik, Freie Universitaet Berlin, Arnimallee 14, W-1000 Berlin 33 (Germany) Chemical Sciences Division, MS 2-300, Lawrence Berkeley Laboratory, 1 Cyclotron Road, Berkeley, California 94720 (United States)

The x-ray-absorption near-edge structure (XANES) of sulfur hexafluoride, SF[sub 6], in the gas phase has been measured with high energy resolution at the sulfur [ital L][sub 2,3] and fluorine [ital K] ionization thresholds using synchrotron radiation from the SX700/II monochromator at BESSY. Besides dominant transitions to core-excited inner-well states, several series of Rydberg states with vibrational fine structure were resolved below the sulfur [ital L][sub 2,3] thresholds. Using the Rydberg formula, quantum defects of [delta][sub [ital s]]=1.80 and [delta][sub [ital d]]=[minus]0.03 were obtained for the [ital s] and [ital d] Rydberg orbitals of the central sulfur atom. A Franck-Condon analysis was used to determine the vibrational spacing and the S-F bond length of the (S 2[ital p][sub 3/2])[sup [minus]1]4[ital s][sup 1] core-excited state. The presence of vibronically coupled transitions below the sulfur [ital L][sub 2,3] edges was confirmed. The derived natural linewidths of the (S 2[ital p][sub 1/2,3/2])[sup [minus]1] Rydberg states were found to be strikingly narrower than those of the (S 2[ital p][sub 1/2,3/2])[sup [minus]1] inner-well resonances. Line-shape analysis also revealed significant inhomogeneous broadening of the (S 2[ital p][sub 1/2,3/2])[sup [minus]1][ital a][sub 1[ital g]][sup 1] states, which is attributed to unresolved vibrational structure. Large Lorentzian contributions to the line shapes of the (S 2[ital p][sub 1/2,3/2])[sup [minus]1][ital t][sub 2[ital g]][sup 1] resonances suggest that vibrational effects are relatively small for those states.

• DOE Contract Number: AC03-76SF00098
• OSTI ID: 6942071
• Journal Information: Physical Review A; (United States), Journal Name: Physical Review A; (United States) Vol. 47:1; ISSN 1050-2947; ISSN PLRAAN
• Country of Publication: United States
• Language: English

Related Subjects

664200* -- Spectra of Atoms & Molecules & their Interactions with Photons-- (1992-)
74 ATOMIC AND MOLECULAR PHYSICS
ABSORPTION SPECTRA
BREMSSTRAHLUNG
ELECTROMAGNETIC RADIATION
ELECTRON SPECTROSCOPY
ENERGY
ENERGY RESOLUTION
FINE STRUCTURE
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
IONIZATION
PHOTOELECTRON SPECTROSCOPY
PHOTOIONIZATION
RADIATIONS
RESOLUTION
RESONANCE
SPECTRA
SPECTROSCOPY
SULFUR COMPOUNDS
SULFUR FLUORIDES
SYNCHROTRON RADIATION
THRESHOLD ENERGY
X-RAY SPECTRA