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Theoretical insights into the stabilities, detonation performance, and electrostatic potentials of cocrystals containing α- or β-HMX and TATB, FOX-7, NTO, or DMF in various molar ratios

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Abstract

A molecular dynamics method was employed to study the binding energies associated with the cocrystallization (at selected crystal planes) of either 1,3,5-triamino-2,4,6-trinitro-benzene (TATB), 1,1-diamino-2,2-dinitroethylene, 3-nitro-1,2,4-triazol-5-one (TATB, FOX-7, and NTO, respectively, all of which are explosives), or N,N-dimethylformamide (DMF, a nonenergetic solvent) in various molar ratios with 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane in its α and β conformations (α-HMX and β-HMX, respectively). The results showed that the cocrystals with low molar ratios (2:1, 1:1, 1:2, and 1:3) were the most stable. The binding energies of HMX/NTO and HMX/DMF were larger than those of HMX/TATB and HMX/FOX-7. According to the calculated stabilities, HMX prefers to adopt its α form in HMX/TATB and its β form in HMX/NTO, whereas the two forms coexist in HMX/FOX-7. For HMX/TATB, HMX/NTO, and α-HMX/FOX-7, increasing the proportion of the cocrystal component with the highest detonation heat (HMX in the first two cases, FOX-7 in the latter) increases the detonation heat, velocity, and pressure of the cocrystal. However, increasing the proportion of the component with the highest detonation heat in β-HMX/FOX-7 and γ-CL-20/FOX-7 increases the detonation heat of the cocrystal but decreases its detonation velocity. An investigation of the surface electrostatic potential revealed how the sensitivity changes upon cocrystal formation.

Surface electrostatic potential of HMX/TATB

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Authors and Affiliations

  1. College of Chemical Engineering and Environment, North University of China, Taiyuan, 030051, China

    Ken-peng Song, Fu-de Ren & Shu-hai Zhang

  2. The Third Hospital of Shanxi Medical University, Taiyuan, 030053, China

    Wen-jing Shi

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  1. Ken-peng Song
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  2. Fu-de Ren
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Correspondence to Fu-de Ren.

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We have full control over all primary data and we allow the journal to review all of the data and confirm the validity of the results. We have no financial relationships to declare. This manuscript was not submitted to more than one journal, and it was not published previously. This study has not been split into several parts to increase the quantity of submissions. Except for the data involving γ-CL-20/FOX-7 in Table 6 (see [39] below Table 6), no data have been fabricated or manipulated.

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ESM 1

The optimized geometries of β-HMX···TATB, β-HMX···FOX-7, β-HMX···NTO, and HMX···DMF as well as intermolecular interactions are shown in Appendix A. (DOC 2401 kb)

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Song, Kp., Ren, Fd., Zhang, Sh. et al. Theoretical insights into the stabilities, detonation performance, and electrostatic potentials of cocrystals containing α- or β-HMX and TATB, FOX-7, NTO, or DMF in various molar ratios. J Mol Model 22, 249 (2016). https://doi.org/10.1007/s00894-016-3111-0

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