Chemiluminescent Reaction of As(4Su) Atoms with Azide Radicals

Article abstract of DOI:10.1021/j100327a011

Discharge-flow methods were used to study the reaction of As(⁴S_u) atoms with N3 radicals.Two band systems in AsN were identified in the chemiluminescence from this reaction.These were the A¹Π -> X¹Σ⁺ system in the UV region and a previously unobserved system in the visible region between 400 and 700 nm.From analysis of the spectrum, the molecular constants of the new excited state of AsN are T_e = 21 664 +/- 8 cm^-1, ω_e = 738 +/- 6 cm^-1, and ω_eκ_e = 5 +/- 1 cm^-1.The data suggest this state to be a metastable excited triplet of AsN, possibly a'³Σ⁺.It is significantly Franck-Condon shifted from the ground state, with (0,4) being the most intense band in the emission spectrum.The rate constant of the As + N3 reaction, determined from the time decay of the As atoms, was found to be k = (2.1 +/- 0.4) x 10^-11 cm³ s^-1.