Computational insights into novel dicobalt polynitrogen: structure, stability, intermolecular interaction, and application

Abstract

Previous studies have suggested that polynitrogen species are significant as potential candidates for superior energetic material. In this paper, the polynitrogen species of Co2(N5)4 were reasonably designed and studied by the density functional theory (DFT), and five isomers of Co2(N5)4 were selected. These species were explored in detail, including structure, stability, intermolecular interaction, and application. The five isomers, each with its own special structure feature, were stable enough based on the analysis of bond energy, chemical hardness, and aromaticity. Furthermore, the intermolecular interactions suggested the presence of a covalent interaction in the Co–Co and N–N bonds, the electronic delocalization in cyclo-N5, and the ionic feature in the Co–N bond. In addition, all of the title species held high-energy content. Compared with the known high energy density materials of HB(N5)3Be2(N5)3BH, energetic material of nitromethane, and famous nitramine explosive HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane), Co2(N5)4 holds a stronger advantage. The five Co2(N5)4 species were located at 27.8–35.8 kcal/mol per N2 unit, their energy densities were about 2.73 × 104 MJ/kg, and their mass densities were in the range of 2.60–2.74 g/cm3. Significantly, the 4-1 was the most stable, and its density was also the greatest among the five species. Thus, it has the most potential as a high energy density material.