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Theoretical insights into the structures and mechanical properties of HMX/NQ cocrystal explosives and their complexes, and the influence of molecular ratios on their bonding energies

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Abstract

Molecular dynamics (MD) methods were employed to study the binding energies and mechanical properties of selected crystal planes of 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX)/nitroguanidine (NQ) cocrystals at different molecular molar ratios. The densities and detonation velocities of the cocrystals at different molar ratios were estimated. The intermolecular interaction and bond dissociation energy (BDE) of the N–NO2 bond in the HMX:NQ (1:1) complex were calculated using the B3LYP, MP2(full) and M06-2X methods with the 6-311++G(d,p) and 6-311++G(2df,2p) basis sets. The results indicated that the HMX/NQ cocrystal prefers cocrystalizing in a 1:1 molar ratio, and the cocrystallization is dominated by the (0 2 0) and (1 0 0) facets. The K, G, and E values of the ratio of 1:1 are smaller than those of the other ratios, and the 1:1 cocrystal has the best ductility. The N–NO2 bond becomes stronger upon the formation of the intermolecular H-bonding interaction and the sensitivity of HMX decreases in the cocrystal. This sensitivity change in the HMX/NQ cocrystal originates not only from the formation of the intermolecular interaction but also from the increment of the BDE of N–NO2 bond in comparison with isolated HMX. The HMX/NQ (1:1) cocrystal exhibits good detonation performance. Reduced density gradient (RDG) reveals the nature of cocrystallization. Analysis of the surface electrostatic potential further confirmed that the sensitivity decreases in complex (or cocrystal) in comparison with that in isolated HMX.

Binding energies and mechanical properties of HMX/NQ cocrystals in different molecular molar ratios were studied using molecular dynamics methods. The origin of the sensitivity change in the HMX/NQ cocrystal originates from formation of intermolecular interactions and the bond dissociation energy increment of the N–NO2 bond

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We have full control of all primary data and agree to allow the journal to review all the data if requested. We confirm the validity of the results from this manuscript. We have no financial relationships to declare. The manuscript has not been submitted to more than one journal, and it has not been published previously. This study is not split up into several parts to increase the quantity of submissions and submitted to various journals or to one journal over time. No data have been fabricated or manipulated.

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  1. School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China

    Yong-xiang Li & Shu-sen Chen

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

    Yong-xiang Li & Fu-de Ren

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  1. Yong-xiang Li
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Correspondence to Yong-xiang Li.

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Appendix A

Appendix A

Cell parameters and main stable surfaces of HMX in vacuum as well as the surface electrostatic potentials are in Appendix A.

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Li, Yx., Chen, Ss. & Ren, Fd. Theoretical insights into the structures and mechanical properties of HMX/NQ cocrystal explosives and their complexes, and the influence of molecular ratios on their bonding energies. J Mol Model 21, 245 (2015). https://doi.org/10.1007/s00894-015-2790-2

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