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Vacuum ultraviolet laser photoion and pulsed field ionization–Photoion study of Rydberg SERIES of chlorine atoms prepared in the {sup 2}P{sub J} (J = 3/2 and 1/2) fine-structure states

Journal Article · · Astrophysical Journal

We have measured the high-resolution vacuum ultraviolet (VUV) photoion (VUV-PI) and VUV pulsed-field ionization–photoion (VUV-PFI-PI) spectra of chlorine atoms (Cl) in the VUV energy range 103,580–105,600 cm{sup −1} (12.842–13.093 eV) using a tunable VUV laser as the photoexcitation and photoionization source. Here, Cl atoms are prepared in the Cl({sup 2}P{sub 3/2}) and Cl({sup 2}P{sub 1/2}) fine-structure states by 193.3 nm laser photodissociation of chlorobenzene. The employment of VUV-PFI-PI detection has allowed the identification of Rydberg transitions that are not observed in VUV-PI measurements. More than 180 new Rydberg transition lines with principal quantum number up to n = 61 have been identified and assigned to members of nine Rydberg series originating from the neutral Cl({sup 2}P{sub 3/2}) and Cl({sup 2}P{sub 1/2}) fine-structure states. Two of these Rydberg series are found to converge to the Cl{sup +}({sup 3}P{sub 2}), four to the Cl{sup +}({sup 3}P{sub 1}), and three to the Cl{sup +}({sup 3}P{sub 0}) ionization limits. Based on the convergence limits determined by least-squares fits of the observed Rydberg transitions to the modified Ritz formula, we have obtained a more precise ionization energy (IE) for the formation of the ionic Cl{sup +}({sup 3}P{sub 2}) from the ground Cl({sup 2}P{sub 3/2}) state to be 104,591.01 ± 0.13 cm{sup −1}. This is consistent with previous IE measurements, but has a smaller uncertainty. The analysis of the quantum defects obtained for the Rydberg transitions reveals that many high-n Rydberg transitions are perturbed.

OSTI ID:
22882657
Journal Information:
Astrophysical Journal, Journal Name: Astrophysical Journal Journal Issue: 2 Vol. 810; ISSN ASJOAB; ISSN 0004-637X
Country of Publication:
United Kingdom
Language:
English