High-resolution photoabsorption near the sulfur [ital L][sub 2,3] thresholds: H[sub 2]S and D[sub 2]S

Journal Article · Fri Dec 31 23:00:00 EST 1993 · Physical Review A; (United States)

DOI:https://doi.org/10.1103/PhysRevA.49.161· OSTI ID:5285366

Hudson, E ^[1]; Shirley, D A ^[2]; Domke, M; Remmers, G; Kaindl, G ^[3]

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1. Department of Chemistry, University of California and Chemical Sciences Division, MS 2-300, Lawrence Berkeley Laboratory, 1 Cyclotron Road, Berkeley, California 94720 (United States)
2. Departments of Chemistry and Physics, Pennsylvania State University, University Park, Pennsylvania 16802 (United States)
3. Institut fuer Experimentalphysik, Freie Universitaet Berlin, Arnimallee 14, W-1000 Berlin 33 (Germany)

The x-ray-absorption near-edge structure of gas-phase H[sub 2]S, hydrogen sulfide, and D[sub 2]S, deuterium sulfide, at the sulfur [ital L][sub 2,3] ionization thresholds has been measured using synchrotron radiation with high-energy resolution from the SX700/II soft-x-ray monochromator at the Berliner Elektronenspeicherring-Gessellschaft fuer Synchrotronstrahlung m.b.H. Previously unobserved fine structure is resolved. The spectra of both molecules are characterized by multielectron excitations 8--14 eV above the [ital L][sub 2] threshold energy, broad valence-shell absorption features 5--8 eV below the [ital L][sub 2] edge, and many narrower Rydberg excitations 0--5 eV below the [ital L][sub 2] edge. Comparison of the H[sub 2]S and D[sub 2]S spectra allows the identification of transitions which include vibrational excitation, due to the isotopic dependence of vibrational energies. For the (2[ital p])[sup [minus]1] core-excited Rydberg states, a least-squares analysis was employed, which deconvoluted the core-level and excited-orbital splittings. Results show that the twofold degeneracy of the sulfur 2[ital p][sub 3/2] core level is removed by the molecular field, with a resulting splitting of 115 meV for the higher-energy core-excited Rydberg states. The energies of the higher Rydberg states were well described by the Rydberg formula with the quantum defects [delta][sub [ital p]]=1.63 and [delta][sub [ital d]]=0.32. Fine structure was resolved in the transitions to the dissociative (2[ital p])[sup [minus]1] core-excited valence-shell states. The regular spacing and isotopic dependence of this structure clearly identifies it as a vibrational progression.

• OSTI ID: 5285366
• Journal Information: Physical Review A; (United States), Journal Name: Physical Review A; (United States) Vol. 49:1; 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
CHALCOGENIDES
DEUTERIUM COMPOUNDS
ELECTROMAGNETIC RADIATION
ELEMENTS
ENERGY
ENERGY RESOLUTION
FLUIDS
GASES
HYDROGEN COMPOUNDS
HYDROGEN SULFIDES
ISOTOPE EFFECTS
NONMETALS
RADIATIONS
RESOLUTION
SPECTRA
SULFIDES
SULFUR
SULFUR COMPOUNDS
SYNCHROTRON RADIATION
THRESHOLD ENERGY
X-RAY SPECTRA