Investigation of the decomposition mechanism of MTNP melt-cast explosive at different temperatures and pressures through ReaxFF/lg molecular dynamics simulations

• Published in: Journal of molecular modeling 2023-11, Vol.29 (11), p.354-354, Article 354
• Main Authors: Mao, Jian-sen, Wang, Bao-guo, Zhu, Rui, Chen, Ya-fang, Fu, Jian-bo
• Format: Article
• Language: English
• Subjects: Algorithms; Boundary conditions; Characterization and Evaluation of Materials; Chemistry; Chemistry and Materials Science; Computer Appl. in Life Sciences; Computer Applications in Chemistry; Decomposition; Decomposition reactions; High temperature; Isomerization; Molecular dynamics; Molecular Medicine; Nitrogen dioxide; Optimization; Original Paper; Oxygen content; Simulation; Temperature; Theoretical and Computational Chemistry; Thermal decomposition; Thermal simulation
• ISSN: 1610-2940; 0948-5023
• DOI: 10.1007/s00894-023-05760-9

Context Thermal decomposition of 1-methyl-3,4,5-trinitropyrazole (MTNP), a melt-cast explosive, was investigated at different temperatures (2500, 2750, 3000, 3250, and 3500 K) and pressures (3000 K/0.5 GPa, 3000 K/1 GPa) using the ReaxFF/lg force field. The study aimed to analyze the changes in reactant quantities, initial reaction pathways, and final product yields. The results demonstrated that complete decomposition of MTNP molecules occurred within a timeframe of 200 ps, with shorter decomposition times observed as the temperature increased. The high-temperature thermal decomposition of MTNP was found to follow two primary reaction pathways. Reaction 1 involved denitration, while reaction 2 proceeded with nitro group isomerization. DFT calculations indicated that nitro group isomerization was the most favorable reaction. During the initial stages, higher quantities of NO 2 , NO, and N 2 were observed compared to other species. This can be attributed to the relatively higher nitrogen and oxygen content in the MTNP structure. Among the five reaction temperatures, it was observed that the quantities of small molecules followed the order of NO 2 > NO > N 2 > CO. Moreover, with increasing temperature, the quantities of all four small molecules increased, indicating that higher temperatures promoted the progression of the reactions. However, as the pressure increased, there was a trend of initially increasing and then decreasing to zero for the quantities of NO 2 and NO. This suggests that high temperature accelerated the high-temperature thermal decomposition of NO 2 and NO, leading to a significant increase in the content of N 2 . Methods A 3 × 5 × 5 supercell model of MTNP was constructed in Materials Studio, consisting of 75 unit cells and 300 MTNP molecules. The model was then subjected to a 20 ps geometric optimization using the Polak-Ribiere version of the conjugate gradient (CG) algorithm in the large-scale atomic/molecular massively parallel simulator (LAMMPS) under the isothermal-isobaric (NPT) ensemble at 1 atm pressure and 300 K temperature. Following the optimization, molecular dynamics simulations were performed on the model at five temperatures (2500, 2750, 3000, 3200, and 3500 K) under 1 atm using the NPT ensemble for a total duration of 1 ns. During the simulations, atomic trajectories, as well as information on atomic and molecular species, were output every 500 steps. Subsequently, a custom script was utilized to analyze the thermal decomp