title: Ultraviolet photodissociation dynamics of the SH radical.
abstract: Ultraviolet (UV) photodissociation dynamics of jet-cooled SH radical (in X 2pi(3/2), nu"=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 approximately -1, and spin-orbit branching fractions of the S(3P(J)) product are close to S(3P2):S(3P1):S(3P0)=0.51:0.36:0.13. The UV photolysis of SH is via a direct dissociation and is initiated on the repulsive 2sigma- potential-energy curve in the Franck-Condon region after the perpendicular transition 2sigma(-)-X 2pi. The S(3P(J)) product fine-structure state distribution approaches that in the sudden limit dissociation on the single repulsive 2sigma- state, but it is also affected by the nonadiabatic couplings among the repulsive 4sigma-, 2sigma-, and 4pi states, which redistribute the photodissociation flux from the initially excited 2sigma- state to the 4sigma- and 4pi states. The bond dissociation energy D0(S-H)=29,245+/-25 cm(-1) is obtained.
authors.affiliation: Department of Chemistry, University of California, Riverside, California 92521, USA.
authors.forename: Weidong
authors.initials: W
authors.lastname: Zhou
authors.forename: Yan
authors.initials: Y
authors.lastname: Yuan
authors.forename: Shiping
authors.initials: S
authors.lastname: Chen
authors.forename: Jingsong
authors.initials: J
authors.lastname: Zhang