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Theoretical studies on stability and pyrolysis mechanism of salts formed by N5 − and metallic cations Na+, Fe2+ and Ni2+

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Abstract

The salts formed by N5 − and metallic cations (Na+, Fe2+ and Ni2+) may be potential candidates for superior energetic materials and were studied with the density functional theory B3LYP method and ab initio molecular orbital theory MP2 method using the 6-31G* and LanL2DZ basis sets. Thermal dissociations of these salts are initiated by breaking of the N5 ring, and those of Fe(N5)2 and Ni(N5)2 proceed sequentially through two transition states. In gas phase, the activation barriers (E as, in kJ/mol) of thermal dissociations decrease in the order of N5 − > NaN5 > HN5 > Ni(N5)2 > Fe(N5)2. Products of initial pyrolysis of these salts are N2 and metallic azide. The frontier orbital energy gaps (in eV) are N5 − (8.27) > HN5 (7.40) > NaN5 (5.10) > Fe(N5)2 (4.92) > Ni(N5)2 (3.43). The more stable salt has the smaller electron transfer between the cation and anion.

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Acknowledgments

Thanks to the 086 Project for supporting this research.

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  1. School of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, 210094, China

    Xueli Zhang, Junqing Yang, Ming Lu & Xuedong Gong

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  1. Xueli Zhang
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Correspondence to Xuedong Gong.

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Zhang, X., Yang, J., Lu, M. et al. Theoretical studies on stability and pyrolysis mechanism of salts formed by N5 − and metallic cations Na+, Fe2+ and Ni2+ . Struct Chem 26, 785–792 (2015). https://doi.org/10.1007/s11224-014-0536-x

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