Computer simulations and analysis of structural and energetic features of crystalline cage energetic compound: 2, 4, 6, 8, 12-pentanitro-10-(3, 5, 6-trinitro (2-pyridyl))-2, 4, 6, 8, 12-hexaazatetracyclo [5.5.0.0^3,11 .0^5,9 ]dodecane

Abstract

Computer simulations and analysis of structural and energetic features of crystalline cage energetic compound: 2, 4, 6, 8, 12-pentanitro-10-(3, 5, 6-trinitro (2-pyridyl))-2, 4, 6, 8, 12hexaazatetracyclo [5.5.0.0 3,11 .0 5,9 ]dodecane Jian-ying Zhang a * and Xue-dong Gong bFirst principles molecular orbital and plane-wave ab initio calculations have been used to investigate the structural and energetic properties of a new cage compound 2, 4, 6, 8, 12-pentanitro-10-(3, 5, 6-trinitro (2-pyridyl))-2, 4, 6, 8, 12-hexaazatetracyclo [5.5.0.0 3,11 .0 5,9 ]dodecane (PNTNPHATCD) in both the gas and solid phases. The molecular orbital calculations using the density functional theory methods at the B3LYP/6-31G(d,p) level indicate that both the heat of formation and strain energy of PNTNPHATCD are larger than those of 2, 4, 6, 8, 10, 12-hexanitro-2, 4, 6, 8, 10, 12-hexaazatetracyclo [5.5.0The infrared spectra and the thermodynamic property in gas phase were predicted and discussed. The calculated detonation characteristics of PNTNPHATCD estimated using the Kamlet-Jacobs equation equally matched with those of CL-20. Bondbreaking results on the basis of natural bond orbital analysis imply that C-C bond in cage skeleton, C-N bond in pyridine, and N-NO 2 bond in the side chain of cage may be the trigger bonds in the pyrolysis. The structural properties of PNTNPHATCD crystal have been studied by a plane-wave density functional theory method in the framework of the generalized gradient approximation. The crystal packing predicted using the Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies (COMPASS) force fields belongs to the Pbca space group, with the lattice parameters a = 20.87 Å, b = 24.95 Å, c = 7.48 Å, and Z = 8, respectively. The results of the band gap and density of state suggest that the N-NO 2 bond in PNTNPHATCD may be the initial breaking bond in the pyrolysis step. As the temperature increases, the heat capacity, enthalpy, and entropy of PNTNPHATCD crystal all increase, whereas the free energy decreases. Considering that the cage compound has the better detonation performances and stability, it may be a superior high energy density compound.

Design and Selection of Pyrazolo[3,4-d][1,2,3] Triazole-based High-energy Materials

“…[7][8][9][10][11] Scheme 1 shows the structures of some energetic compounds such as 1,3,5-trinitro-1,3,5-triazinane (RDX), 12 1,3,5,7-tetranitro-1,3,5,7-tetrazocane (HMX), 13 and cage structures 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazatetracyclododecane (CL-20). 14 Among these structures, the detonation performance of cage-like energetic compounds is stronger than that of chain-like energetic compounds. However, the synthetic steps for the cage-like energetic compounds are more complex than those for the chain-like energetic compounds.…”

Effects of Electronic Delocalization and Hydrostatic Compression on Structure and Properties of Cage Compound 4‐Trinitroethyl‐2,6,8,10,12‐pentanitrohexaazaisowurtzitane

“…In the past decades, our group has done lots of studies about high energetic materials on various properties . Among them, a nitro cage compound, namely 4‐trinitroethyl‐2, 6, 8, 10, 12‐pentanitrohexaazaisowurtzitane (TNE‐CL‐20) (in Figure ) prepared in recent years (in Figure ), was researched on its structural and energetic properties in gas phase .…”

Theoretical insights on a series of difluoramino group-based energetic molecules

“…Energetic materials, especially high energy density materials (HEDMs), have been receiving considerable attention to meet the wide use in modern civil and military applications . Consequently, seeking and developing novel high explosives with high detonation properties, high thermal stability, and low sensitivity became one of the most interesting topics for scientists though it seems that there always exits contradictions between high detonation properties, stabilities, or low sensitivities .…”