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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 (CH3N3) under collision-free conditions. These experiments are used to derive the branching ratio between channels 1 and 2 [(1) radical channel: CH3N3 + hν (λ = 193 nm) → CH3 + N3; (2) molecular channel: CH3N3 + hν (λ = 193 nm) → CH3N + N2], 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 (XCH3–N3)/(XCH3N–N2) = (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 N3 is the dominant product in the radical channel. Only a small fraction of the radical channel produces ground state linear N3.
