Computational study of energetic nitrogen‐rich derivatives of 1,1′‐ and 5,5′‐bridged ditetrazoles

Abstract

Density functional theory method was used to study the heats of formation (HOFs), electronic structure, energetic properties, and thermal stability for a series of bridged ditetrazole derivatives with different linkages and substituent groups. The results show that the -N3 group and azo bridge (-N=N-) play a very important role in increasing the HOF values of the ditetrazole derivatives. The effects of the substituents on the HOMO-LUMO gap are combined with those of the bridge groups. The calculated detonation velocities and detonation pressures indicate that the -NO2, -NF2, -N=N-, or -N(O)=N- group is an effective structural unit for enhancing the detonation performance for the derivatives. An analysis of the bond dissociation energies for several relatively weak bonds suggests that the N-N bond in the ring or outside the ring is the weakest one and the N-N cleavage is possible to happen in thermal decomposition. Overall, the -CH2-CH2- or -NH-NH- group is an effective bridge for enhancing the thermal stability of the bridged ditetrazoles. Because of their desirable detonation performance and thermal stability, five compounds may be considered as the potential candidates of high-energy density materials (HEDMs). These results provide basic information for the molecular design of novel HEDMs.

Theoretical Studies on Energetic Nitrogen‐Rich Heterocyclic Substituted Derivatives of Pyrazino [2, 3‐e] [1, 2, 3, 4] Tetrazine‐1, 3‐di‐N‐oxide

“…However, the four nitrogen atoms in this system that are attached directly to each other will destabilizes the entire fused system and the lack of energetic dense substituents makes the molecule possess low detonation performance. As the nitrogenous heterocyclic compounds possess large densities and high heat of formations, introducing two N‐oxide into pyrazino [2, 3‐e] [1, 2, 3, 4] tetrazine may overcome the problem of destabilization and substituting nitrogenous heterocycles and give the molecule to have high energetic properties.…”

Heats of formation and thermal stability of substituted 1,1′‐Azobis(tetrazole) compounds with an extended nitrogen chain

“…Quantum chemistry calculations have proven to be a valuable tool in studying structure–property relationships for compounds that would otherwise be difficult and dangerous to synthesize in the laboratory . In this study, the heats of formation and decomposition pathways for the N 10 compound and its functionalized derivatives are determined using quantum chemistry composite approaches (CA) and density functional theory (DFT) intrinsic reaction coordinate (IRC) analysis.…”

“…Quantum chemistry calculations have proven to be a valuable tool in studying structure-property relationships for compounds that would otherwise be difficult and dangerous to synthesize in the laboratory. [18][19][20][21][22] In this study, the heats of formation and decomposition pathways for the N 10 compound and its functionalized derivatives are determined using quantum chemistry composite approaches (CA) and density functional theory (DFT) intrinsic reaction coordinate (IRC) analysis. The main goal of this work is to probe the properties of the N 10 compounds by modifying the structure through the inclusion of substituents in the design of new energetic materials with acceptable thermal stabilities and energy content.…”

Assessing the Detonation Performance of New Tetrazole Base High Energy Density materials

“…1,3,5-Triazido-2,4,6-trinitrobenzene (TATNB) [33] is a green powerful lead-free initiating explosive with the density of 1.805 g cm À3 [33], D f H8 c of 1131.3 kJ mol À1 [38], VOD of 8.58 km s À1 [38], and impact sensitivity of 5.0 N m [33]. The effect of ÀN 3 group for increasing D f H8 c has also been studied for tetrazines [34], triazoles [36], and tetrazoles [39].…”