Vacuum ultraviolet excitation spectroscopy of the autoionizing Rydberg states of atomic sulfur in the 73 350-84 950 cm{sup -1} frequency range
- Department of Chemistry, University of California, Davis, California, 95616 (United States)
The photoionization efficiency (PIE) spectra of metastable sulfur (S) atoms in the {sup 1}D and {sup 1}S states have been recorded in the 73 350-84 950 cm{sup -1} frequency range by using a velocity-mapped ion imaging apparatus that uses a tunable vacuum ultraviolet laser as the ionization source. The S({sup 1}D) and S({sup 1}S) atoms are produced by the 193 nm photodissociation of CS{sub 2}. The observed PIE spectra of S({sup 1}D) and S({sup 1}S) shows 35 autoionizing resonances with little or no contribution from direct photoionization into the S{sup +}({sup 4}S{sub 3/2})+e{sup -} ionization continuum. Velocity-mapped ion images of the S{sup +} at the individual autoionizing Rydberg resonances are used to distinguish whether the lower state of the resonance originates from the {sup 1}D, {sup 1}S, or {sup 3}P states. The analysis and assignment of the Rydberg peaks revealed 22 new Rydberg states that were not previously known. The autoionization lifetimes {tau} of the Rydberg states are derived from the linewidths by fitting the lines with the Fano formula. Deviations from the scaling law of {tau}(n*){proportional_to}n*{sup 3}, where n* is the effective quantum number of the Rydberg state, are observed. This observation is ascribed to perturbations by nearby triplet Rydberg states, which shorten the autoionization lifetimes of the singlet Rydberg levels.
- OSTI ID:
- 21103853
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 8 Vol. 128; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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