Photofragmentation translational spectroscopy of methyl azide (CH3N3) photolysis at 193 nm: molecular and radical channel product branching ratio |
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Authors: | Quinto-Hernandez Alfredo Doehla Jeremie Huang Wen-Tsung Lien Chien-Yu Lin Wei-Yen Lin Jim Jr-Min Wodtke Alec M |
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Institution: | Department of Chemistry and Biochemistry, University of California, Santa Barbara, California 93106-9510, USA. aquinto@chem.ucsb.edu |
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Abstract: | We describe molecular-beam photofragment translational spectroscopy (PTS) experiments using electron impact (EI) ionization product detection to investigate the 193 nm photodissociation of methyl azide (CH(3)N(3)) under collision-free conditions. These experiments are used to derive the branching ratio between channels 1 and 2 (1) radical channel: CH(3)N(3) + hν (λ = 193 nm) → CH(3) + N(3); (2) molecular channel: CH(3)N(3) + hν (λ = 193 nm) → CH(3)N + N(2)], which have been reported in a previous VUV-photoionization based PTS study. (1) Using electron impact ionization cross sections and ion fragmentation ratios for the various detected products, we derive the branching ratio (X(CH(3)-N(3)))/(X(CH(3)N-N(2))) = (0.017 ± 0.004)/(0.983 ± 0.004). Based on analysis of the kinetic energy release in the radical channel, we find that the cyclic form of N(3) is the dominant product in the radical channel. Only a small fraction of the radical channel produces ground state linear N(3). |
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