LASER-INDUCED PHOTO-DISSOCIATION OF HN3 AT 266 NM .1. PRIMARY PRODUCTS, PHOTOFRAGMENT ENERGY-DISTRIBUTIONS AND REACTIONS OF INTERMEDIATES

A detailed analysis of the primary photodissociation products resulting from the 266 nm laser photolysis of HN3 is reported. The major primary fragments are N2(1Σg+) and NH(1Δ). The NH(1Δ) fragment is formed ≳ 99.8% in the ν = 0 level with ≈ 900 cm-1 of rotational energy and ≤ 5000 cm-1 of translational energy for the axially scattered fragments. A new chemiluminescent reaction is reported: NH(1Δ) + HN3 (1A′) → NH 2(2A1) + N3(2Πg), which appears to be a major reaction channel of the primary NH(1Δ) fragment. A kinetic analysis of this reaction and several other NH(1Δ) reactions are the subject of the following associated paper. A correlation study of the NH(1Δ) and N2(1Σg+) products with the dissociating states of HN3 is made which requires a reassignment of the lower-lying HN3 transitions. © 1978.