Density Functional Theory Study of Solvent Effects on the Structure and Vibrational Frequencies of Tetranitrotetraazabicyclooctane “bicyclo-HMX”

Abstract

Density Functional Theory (DFT) calculations have been performed on the high explosive compound tetranitrotetraazabicyclooctane (bicyclo-HMX) in gas phase employing the self-consistent field (SCF) theory and in different solvents, i.e. cyclohexane, dichloroethane, ethylalcohol, acetonitrile, and water, utilizing the self-consistent reaction field (SCRF) theory at a B3LYP/6-311G** level of theory. Reasonable agreement has been found between the computed and the available experimental data. The effects of different solvents on the geometry, electronic structure, and vibrational frequencies are discussed. Various solvents under consideration are found to have similar effects on the above properties. But some properties change regularly with the increasing polarity of the solvents, and the stronger the solvent polarity is, the larger the change is. In addition, based on the vibrational analysis, standard thermodynamic properties of bicyclo-HMX in gas phase are also computed by using the statistical thermodynamic principle.

A first‐principles investigation of the hydrogen bond interaction and the sensitive characters in cis‐1,3,4,6‐tetranitrooctahydroimidazo‐[4,5‐d]imidazole

“…Moreover, it contains fewer H atoms and larger ring strain than HMX and would have superior explosive performance to HMX. BCHMX has been studied from both theoretical and experimental sides [2][3][4][5][6]. Klasovity et al [2] investigated experimentally the thermal stability, ignition temperature, impact sensitivity, friction sensitivity, electric spark sensitivity, detonation characteristics, and solubility of BCHMX crystal and also suggested the intramolecular and intermolecular hydrogen bonding based on atomic/molecular distances.…”

cis-1,3,4,6-Tetranitrooctahydroimidazo-[4,5-d]imidazole (BCHMX), its properties and initiation reactivity

“…bicyclo-HMX or BCHMX) is one of attractive compounds predicted to possess higher density than 1,3,5,7-tetranitro-1,3,5,7-tetrazocan (HMX) [1]. This compound has drawn the attention of organic chemists since it was theoretically designed and its superior physical and explosive properties were predicted [2]. During the 1980s a very intense effort was dedicated to find undemanding and economically feasible chemical procedure to obtain this energetic material in larger amounts.…”

Molecular dynamics study of binding energies, mechanical properties, and detonation performances of bicyclo-HMX-based PBXs

“…As can be seen, it contains fewer H atoms and larger ring strain than HMX and may be able to exhibit superior explosive performance to HMX, which is one of the most powerful widely used explosives. Therefore, it inspired a significant history of interest in the structural and explosive properties since it was first reported [1][2][3][4][5][6][7][8][9][10][11][12][13][14].…”