Abstract
The consensus value for the electron affinity of azide radical is 261 kJ mol−1, anomalously higher than many species that are also made of highly electronegative elements. N3− has two equivalent resonance structures analogous to NO2− that has a lower electron affinity. Electronegativity trends rationalize why the electron affinity of N3 is higher than that of P3; however, those of N and N2 are lower than those of P and P2. We suggest the reason for the observed high electron affinity of azide radical is Coulombic stabilization in the ionic triplet resonance structure, −N=N+=N−.
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