The potential energy surfaces for the low-lying doublet states of the azide radical (N-3) have been computed at the complete active space self-consistent field (CASSCF) level with the CAS(15,12) active space. The cc-pVTZ and aug-cc-pVTZ basis sets have been employed throughout the present work. Energies, geometries and harmonic frequencies were determined for the N-3 linear ground electronic state ((2)Pi(g)), a stable C-2v ring structure (B-2(1)), and a C-s transition state ((2)A(')) connecting the ring and linear structures. Other N-3 (C-2v) stationary points ((2)A(2), B-2(1), and (2)A(1)) have been characterized, as well. The vertical excitation energies for the doublet excited states of the N-3 linear ((2)Pi(g)) and stable ring (B-2(1)) isomers were calculated using CASSCF and multireference configuration interaction [MRCI-SD(Q)] methods. A new route to tetraazatetrahedrane [N-4(T-d)] has been proposed on the N-4 singlet potential energy surface within C-s symmetry. MRCI-SD(Q) calculations predict that N-4 (T-d) can be formed from atomic nitrogen in the D-2 state and N-3 (C-2v, B-2(1)) in a barrierless exothermic reaction. The energy difference (D-0) is 135.4 kcal/mol at the MRCI-SD(Q) level.