Ultraviolet photodissociation dynamics of the SH radical
- Department of Chemistry, University of California, Riverside, California 92521 (United States)
Ultraviolet (UV) photodissociation dynamics of jet-cooled SH radical (in X {sup 2}{pi}{sub 3/2}, {nu}{sup ''}=0-2) is studied in the photolysis wavelength region of 216-232 nm using high-n Rydberg atom time-of-flight technique. In this wavelength region, anisotropy {beta} parameter of the H-atom product is {approx}-1, and spin-orbit branching fractions of the S({sup 3}P{sub J}) product are close to S({sup 3}P{sub 2}):S({sup 3}P{sub 1}):S({sup 3}P{sub 0})=0.51:0.36:0.13. The UV photolysis of SH is via a direct dissociation and is initiated on the repulsive {sup 2}{sigma}{sup -} potential-energy curve in the Franck-Condon region after the perpendicular transition {sup 2}{sigma}{sup -}-X {sup 2}{pi}. The S({sup 3}P{sub J}) product fine-structure state distribution approaches that in the sudden limit dissociation on the single repulsive {sup 2}{sigma}{sup -} state, but it is also affected by the nonadiabatic couplings among the repulsive {sup 4}{sigma}{sup -}, {sup 2}{sigma}{sup -}, and {sup 4}{pi} states, which redistribute the photodissociation flux from the initially excited {sup 2}{sigma}{sup -} state to the {sup 4}{sigma}{sup -} and {sup 4}{pi} states. The bond dissociation energy D{sub 0}(S-H)=29 245{+-}25 cm{sup -1} is obtained.
- OSTI ID:
- 20723009
- Journal Information:
- Journal of Chemical Physics, Vol. 123, Issue 5; Other Information: DOI: 10.1063/1.1961565; (c) 2005 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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