A vacuum ultraviolet laser photoionization and pulsed field ionization study of nascent S({sup 3}P{sub 2,1,0}) and S({sup 1}D{sub 2}) formed in the 193.3 nm photodissociation of CS{sub 2}
- Department of Chemistry, University of California, Davis, California 95616 (United States)
The photoionization efficiency (PIE) and pulsed field ionization-photoion (PFI-PI) spectra for sulfur atoms S({sup 3}P{sub 2,1,0}) and S({sup 1}D{sub 2}) resulting from the 193.3 nm photodissociation of CS{sub 2} have been measured using tunable vacuum ultraviolet (vuv) laser radiation in the frequency range of 82 750-83 570 cm{sup -1}. The PIE spectrum of S({sup 3}P{sub 2,1,0}) near their ionization threshold exhibits steplike structures. On the basis of the velocity-mapped ion-imaging measurements, four strong autoionizing peaks observed in the PIE measurement in this frequency range have been identified to originate from vuv excitation of S({sup 1}D{sub 2}). The PFI-PI measurement reveals over 120 previously unidentified new Rydberg lines. They have been assigned as Rydberg states [3p{sup 3}({sup 4}S{sup (convolutionsign)})nd{sup 3}D{sup (convolutionsign)} (n=17-64)] converging to the ground ionic state S{sup +}({sup 4}S{sup (convolutionsign)}) formed by vuv excitations of S({sup 3}P{sub 2,1,0}). The converging limits of these Rydberg series have provided more accurate values, 82 985.43{+-}0.05, 83 162.94{+-}0.05, and 83 559.04{+-}0.05 cm{sup -1} for the respective ionization energies of S({sup 3}P{sub 0}), S({sup 3}P{sub 1}), and S({sup 3}P{sub 2}) to form S{sup +}({sup 4}S{sup (convolutionsign)}). The relative intensities of the PFI-PI bands for S({sup 3}P{sub 0}), S({sup 3}P{sub 1}), and S({sup 3}P{sub 2}) have been used to determine the branching ratios for these fine structure states, S({sup 3}P{sub 0}):S({sup 3}P{sub 1}):S({sup 3}P{sub 2})=1.00:1.54:3.55, produced by photodissociation of CS{sub 2} at 193.3 nm.
- OSTI ID:
- 21024632
- Journal Information:
- Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 1 Vol. 128; ISSN JCPSA6; ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
AUTOIONIZATION
BRANCHING RATIO
CARBON SULFIDES
DISSOCIATION
EXCITATION
FAR ULTRAVIOLET RADIATION
FINE STRUCTURE
FREQUENCY RANGE
GROUND STATES
LASER RADIATION
PHOTOIONIZATION
PHOTOLYSIS
PHOTON-ATOM COLLISIONS
RYDBERG STATES
SULFUR IONS
ULTRAVIOLET SPECTRA