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}

Journal Article · Mon Jan 07 04:00:00 EST 2008 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.2816749· OSTI ID:21024632

Jingang, Zhou; Jones, Brant; Xueliang, Yang; Jackson, W M; Ng, C Y ^[1]

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1. 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

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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