Ab initio molecular orbital and density functional theory calculations show that azidamines, a new family of polynitrogen compounds, are minima on their respective. potential energy surfaces. The geometries, vibrational frequencies, and heats of formation are predicted for N(N-3)(3), HN(N-3)(2), the N(N-3)(2)(-) anion, and the N(N-3)(4)(+) cation. All of these compounds are highly energetic materials with large positive heats of formation. The results suggest that these polynitrogen compounds could be synthetically accessible, and potential methods for their syntheses are proposed.