Computational Study on Structure and Properties of New Energetic Material 3,7-BIS(DINITROMETHYLENE)-2,4,6,8-TETRANITRO-2,4,6,8-TETRAAZA-BICYCLO[3.3.0]OCTANE

Abstract

The IR spectrum, crystal structure, electronic structure, thermodynamic properties, heat of formation and detonation properties of a new polynitro heterocyclic energetic material 3,7-bis(dinitromethylene)-2, 4,6,8-tetranitro-2,4,6,8-tetraazabicyclo[3.3.0]octane were investigated theoretically. The calculated results show that this compound has a centrosymmetric structure and the molecular packing prediction indicates that the crystalline packing of the title compound is P2 1 2 1 2 1 and the corresponding cell parameters are as follows: Z=4, a= 22.03 Å, b=8.73 Å, c=8.42 Å, a=90°, b=90° and g=90°. ; detonation pressure P, 45.9 GPa), energy gap (ΔE LUMO-HOMO ) 4.19 eV and the molecular electrostatic potentials (MEP), it is predicted that 3,7-bis(dinitromethylene)-2, 4,6,8-tetranitro-2,4,6,8-tetraazabicyclo[3.3.0] octane could be may be a superior high-energy density compound (HEDC) to RDX and HMX.

Computational investigation and screening of [1,2,4]triazolo[4,3‐b][1,2,4,5]tetrazine‐based high energy materials

“…In the present work, some [1,2,4]triazolo [4,3-b] [1,2,4,5]tetrazine-based high energy compounds were designed. The electronic structures, heats of formation (HOF), detonation velocities (D), detonation pressures (P), and thermal stabilities (BDEs) of the titled high energy materials were calculated at B3LYP/6-311G (d,p) theoretical level of DFT method.…”

“…Finally, the electronic structures (such as distribution of frontier molecular orbitals and electrostatic potentials) were presented, which may provide a new research direction to high energy materials. [1,2,4]triazolo [4,3-b] [1,2,4,5]tetrazine, detonation properties, high energy materials, thermal stabilities…”

“…As a special type of high energy materials, energetic compounds have been attached much attention due to their high density (ρ), excellent detonation properties (contains detonation velocity (D) and detonation pressure (P)) and acceptable thermal stability. [1][2][3][4][5][6] However, it is still a remarkable challenge to synthesize high energy materials with high values of D, P, and thermal stabilities. [7][8][9] In order to solve this problem, a series of methods were employed to enhance the values of ρ, D, and P of an energy compound.…”

“…19,20 Consequently, fused nitrogen-rich heterocycle frameworks with strong hydrogen-bonds or conjugated systems were particularly interested by researchers, since this method can supply a possible approach to obtain energy materials with acceptable thermal stabilities and excellent detonation properties. Recently, Shreeve et al reported two kinds of [1,2,4] triazolo [4,3-b] [1,2,4,5]tetrazine-based high energy materials, which possess acceptable values of D, P, and thermal stabilities (Scheme 1). 21 In order to extend the species of high energy materials, it came to the idea that what properties will change if the -N=Nbridge was replaced by other bridges (such as -CH 2 CH 2 -, -CH=CH-, -NHNH-, -N=N-, -CH 2 NH-, -CH=N-) or C-H atoms were replaced by other energetic groups?…”

“…In this work, a series of systematic [1,2,4]triazolo [4,3-b] [1,2,4,5]tetrazine-based high energy materials were designed (Scheme 2). Their geometrical structures were optimized at B3LYP/6-311G (d,p) theoretical level.…”