Abstract
The method of velocity map imaging was applied to study the photodissociation dynamics of ClN3 near 235 nm under collision-free conditions. Derived kinetic energy distributions of state-selected Cl (2PJ) provide a medium-resolution energy spectrum of the N3 fragment. Markedly bimodal distributions are observed that suggest simultaneous formation of the linear-N3 (X 2Π) isomer as well as an energetic form of N3, consistent with recent theoretical predictions of a cyclic isomer, resembling an isosceles triangle. Angular distributions of the photofragments indicate that 21A‘ ← 11A‘ excitation is the most important pathway to photoproducts. Branching ratio measurements between the dominant spin−orbit excited-state Cl* (2P1/2) and the spin−orbit ground-state Cl (2P3/2) showed Cl*/Cl ≈ 0.8/0.2. The branching ratio between linear-N3 and cyclic-N3 formation was determined to be ≈ 0.8/0.2.
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