High-pressure phase transitions of series of catenated nitrogen energetic crystals Nx (x = 4, 8, 10): A comparative DFT-D study

• Published in: Journal of molecular modeling 2024-11, Vol.30 (11), p.388, Article 388
• Main Authors: Wu, Xiaowei, Yu, Qiyao
• Format: Article
• Language: English
• Subjects: Characterization and Evaluation of Materials; Chemical bonds; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Crystals; Density functional theory; Energetic materials; High pressure; Hydrogen bonding; Mechanical properties; Molecular interactions; Molecular Medicine; Nitrogen; Original Paper; Phase transitions; Plane waves; Pressure effects; Surface analysis (chemical); Theoretical and Computational Chemistry
• ISSN: 1610-2940; 0948-5023; 0948-5023
• DOI: 10.1007/s00894-024-06190-x

Context High-pressure chemistry has advantages in exploring novel energetic materials and is the key to the development of new high-energy materials. The complexity and danger of experimental processes require a deeper understanding by advanced simulation techniques. Therefore, a high-precision comparative DFT-D study was performed to investigate the effect of pressure on series of catenated nitrogen energetic crystals. The results show that there exist phase transitions for N 4 , N 8 , and N 10 at 4 GPa, 3 GPa, and 2 GPa respectively, which are embodied in various properties of these crystals. Studies on band gap and DOS indicate pressure-induced improvement on the ability for electrons transition from occupied orbitals to empty ones. Hirshfeld surface analysis qualitatively suggests that hydrogen bonding interactions are becoming dominant inter-molecular interactions. The topological analysis quantitatively reveals that pressure is beneficial to enhancing the inter-molecular hydrogen bonding energy, thereby playing an important role in the stability of high-pressure phases. The discussions on mechanical properties imply that pressure can improve the rigidity of these energetic systems and enhance their mechanical properties. Our findings evidence the high-pressure phase transitions for catenated nitrogen energetic crystals, which lay the theoretical foundation for the development of novel energetic materials. Methods Series of catenated nitrogen energetic crystals N 4 , N 8 and N 10 were obtained from experiments. Optimizations were performed by GGA/PBE functional and G06 dispersion correction within the framework of CASTEP code, and the cutoff energies of the plane waves were set to 700 eV. The particular moiety in the crystals was extracted by Multiwfn 3.6 and subsequent analysis was conducted by Gaussian 09W package.