Chemiluminescent reactions of Group VI atoms [oxygen(3P) and selenium(3P)] with azide radicals

Kinetics of NCl(aΔ and b1Σ+) Generation: The Cl + N3 Rate Constant, the NCl(a1Δ) Product Branching Fraction, and Quenching of NCl(a1Δ) by F and Cl Atoms

“…The NCl(a) bimolecular self-destruction and the bimolecular NF(a 1 Δ) + NCl(a 1 Δ) rates are not important if concentrations below ∼2 × 10 12 molecule cm -3 are used. The competition between F and Cl atoms reacting with N 3 already has been reported; however, our experiments, similar work by Henshaw and co-workers,18a and a direct measurement using laser-induced fluorescence to monitor the decay of [N 3 ] with added [Cl] 19 support a k 1 value that is slightly smaller than the F + N 3 rate constant ((5 ± 2) × 10 -11 cm 3 s -1 ) 6,7 rather than eight times larger . Our value for k 1 is based upon the reduction in NF(a) concentration as Cl atoms are added to the system and on the time dependence for the generation of NF(a) and NCl(a).…”

“…The reactions of H atoms with NF 2 and F atoms with N 3 are excellent gas phase sources of NF(a 1 Δ). − In each case the ground singlet state molecule is formed, HNF 2 or FN 3 , that subsequently undergoes unimolecular decomposition before collisional stabilization at modest pressures. Since spin is conserved, NF(a 1 Δ) is formed rather than NF(X 3 Σ - ).…”