MECHANISM OF THE MULTIPHOTON DISSOCIATION OF $SO_{2}$ VIA THE $\tilde{H}$ RYDBERG STATE

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2004

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Ohio State University

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We will present a study on the mechanism of multiphoton dissociation of the SO2 molecule through the H~ Rydberg state. For this study, a homemade Wiley-McLaren linear time-of-flight (TOF) spectrometer was constructed to characterize the fragments produced during irradiation of SO2 with a laser beam in the 222āˆ’234 nm region. Both SO+ and S+ fragment ions were detected but no parent SO2+ appeared. The mass resolved excitation spectra (MRES) of both SO+ and S+ display the SO2C~B2←X1A1 vibrational progressions. The first photon in the studied region pumps SO2 to the C~1B2 electronic state. The second photon further excites the molecule to the H~ Rydberg state, where it dissociates into SO+O and S+O2 fragments. The third photon then ionizes the SO fragment. From the power dependence of the ion intensity and a kinetic model we developed, we conclude that S+ is produced by a one-photon dissociation, SO++hν→S++O. The internal energy distributions of the fragmentation products from dissociation of SO2 via the H~ Rydberg state were also obtained using an ion-imaging spectrometer. The following five dissociation channels are observed: SO(B3Ī£āˆ’)+O(3P2),SO(A3Ī )+O(3P2), S(1D)+O2(b1Ī£g),S(1D)+O2(a1Ī”g), and S(1D)+O2(X3Ī£āˆ’).

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Author Institution: Department of Chemistry, University of Pennsylvania; Department of Chemistry, University of Puerto Rico; Department of Chemistry and Chemical Biology, Cornell University

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