Molecules consisting of nitrogen have been the subject of much attention due to their potential as high-energy materials. Complex molecules consisting entirely of nitrogen can be subject to rapid decomposition, and therefore other atoms are incorporated into the structure to enhance stability. Previous studies have explored the incorporation of carbon atoms into otherwise all-nitrogen cages molecules. The current study involves two such cages, N10C2 and N16C2, whose structures are derived from N12 and N18, respectively. The N10C2 and N16C2 cages in this study are modified by bonding groups O3 and CO3 to determine the effect on the relative energies between the isomers and on the thermodynamic energy release properties. Energetic trends for N10C2 and N16C2 are calculated and discussed. 1. Introduction Molecules consisting entirely or predominantly of nitrogen have been the subject of much research because of their potential as high-energy materials. Decomposition reactions of the type can be exothermic by up to 50？kcal/mol per nitrogen atom (approximately 3.5 kilocalories per gram of material). Experimental synthetic successes in high-energy nitrogen materials include the and ions [1–4] as well as various azido compounds [5–9] and even a network polymer of nitrogen [10]. Additionally, nitrogen-rich salts [11] and the N7O+ ion [12] have been achieved experimentally. The production of such a diverse group of nitrogen systems demonstrates the potential for such materials as novel high-energy molecules. Nitrogen-based energetic systems have also been the subject of much theoretical research. Theoretical studies of high-energy nitrogen include cyclic and acyclic compounds [13–20], as well as nitrogen cages [21–27]. Structures and thermodynamics of energetic nitrogen systems have been calculated for both small molecules and larger structures with up to seventy-two atoms. Theoretical studies [28] of cage isomers of N24, N30, and N36 showed that the most stable isomers are narrow cylindrical structures consisting of bands of hexagons capped by triangle-pentagon endcaps in either or point group symmetry. A previous study [29] of molecules of N22C2 showed that the most stable isomer has a C2 parallel to the long axis of the molecule, which allows the C2 unit and its C=C double bond the most planar, ethylene-like environment. The least stable isomers have the C2 unit in proximity to the triangular endcaps, where angle strain around the C=C double bond becomes a destabilizing factor. In the current study, the smaller analogues N10C2 and N16C2 are considered, with
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