From intermolecular interactions to structures and properties of a novel cocrystal explosive: a first-principles study

Zhang, Lei; Wu, Ji-Zhou; Jiang, Sheng-Li; Yu, Yi; Chen, Jun

doi:10.1039/c6cp03526d

Cited by 30 publications

(19 citation statements)

References 36 publications

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“…The valence electrons were described by linear combinations of numerical pseudoatomic orbitals. The reliability of this method to predict the intermolecular interaction energies and to predict the nature of high-energy-density molecular crystals has been confirmed in the previous work 27,29–31 .…”

Section: Resultssupporting

confidence: 59%

“…The predicted macro solid properties include detonation performances and sensitivities to accidental initiation of detonation. For the prediction of the detonation performance, we used a recently developed method by taking into account of the statistical correction from experimental data, which were detailed in our previous work 29 (Supplementary Fig. S5).…”

Section: Resultsmentioning

confidence: 99%

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Revealing Solid Properties of High-energy-density Molecular Cocrystals from the Cooperation of Hydrogen Bonding and Molecular Polarizability

Zhang

Jiang

2019

Sci Rep

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In the domain of high-energy-density materials, the understanding to physico-chemical properties has long been primarily based on molecular structures whereas the crystal packing effect that significantly affects solid properties has been seldom involved. Herewith we predict the solid properties of six novel energetic cocrystals by taking into account of the crystal packing effect using a quantum chemistry method. We discover that the hydrogen bonding causes an increase in the molecular polarizability and their cooperation significantly changes the solid-state nature of the cocrystals compared to the pristine crystal and the gas counterparts. For example, stabilizing the multi-component molecular association by increasing the binding energy by 19–41% over the pristine crystals, improving the detonation performance by 5–10% and reducing the sensitivity to external stimuli compared to their pure crystal or gas counterparts. Therefore, the solid nature of the cocrystal is not a simple combination of the pure crystalline properties of its components and the heterogeneous molecular coupling effects must be considered to design improved functional cocrystals.

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Section: Resultssupporting

confidence: 59%

Section: Resultsmentioning

confidence: 99%

Revealing Solid Properties of High-energy-density Molecular Cocrystals from the Cooperation of Hydrogen Bonding and Molecular Polarizability

Zhang

Jiang

2019

Sci Rep

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“…The valence electrons, described by linear combinations of numerical pseudoatomic orbitals, were calculated on a three-dimensional real-space grid. The reliability of the DFT calculations to describe the structures, energetics, dynamics, mechanical properties, detonation performance and sensitivity of EM crystals has been extensively confirmed in previous work [8,11,12,13,14,15].…”

Section: Methodsmentioning

confidence: 70%

A Study of the Shock Sensitivity of Energetic Single Crystals by Large-Scale Ab Initio Molecular Dynamics Simulations

Zhang

Xiang

2019

Nanomaterials

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Understanding the reaction initiation of energetic single crystals under external stimuli is a long-term challenge in the field of high energy density materials. Herewith, we developed an ab initio molecular dynamics method based on the multiscale shock technique (MSST) and reported the reaction initiation mechanism by performing large-scale simulations for the sensitive explosive benzotrifuroxan (BTF), insensitive explosive triaminotrinitrobenzene (TATB), four polymorphs of hexanitrohexaazaisowurtzitane (CL-20) pristine crystals and five novel CL-20 cocrystals. A theoretical indicator, tinitiation, the delay of decomposition reaction under shock, was proposed to characterize the shock sensitivity of energetic single crystal, which was proved to be reliable and satisfactorily consistent with experiments. We found that it was the coupling of heat and pressure that drove the shock reaction, wherein the vibrational spectra, the specific heat capacity, as well as the strength of the trigger bonds were the determinants of the shock sensitivity. The intermolecular hydrogen bonds were found to effectively buffer the system from heating, thereby delaying the decomposition reaction and reducing the shock sensitivity of the energetic single crystal. Theoretical rules for synthesizing novel energetic materials with low shock sensitivity were given. Our work is expected to provide a useful reference for the understanding, certifying and adjusting of the shock sensitivity of novel energetic materials.

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“…In the case of deep-well oil and gas drilling, perforating guns, based on thermostable EMs, ensure efficient penetration and easier access to soil-embedded deposits at great depth, where temperatures may reach above 250 °C [4,5]. Designing EMs that would fit the criteria of thermostability (temperature of decomposition, T d > 250 °C) imposes certain molecular and crystal architectures [6]. In recent years, several innovative molecular design strategies were introduced to obtain EMs with improved thermostability, which are based on advanced understanding of the relationships between molecular and crystal structures of an explosive and its properties [7].…”

Section: Introductionmentioning

confidence: 99%

Energetic Butterfly: Heat-Resistant Diaminodinitro trans-Bimane

et al. 2019

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Due to a significant and prolific activity in the field of design and synthesis of new energetic molecules, it becomes increasingly difficult to introduce new explosophore structures with attractive properties. In this work, we synthesized a trans-bimane-based energetic material—3,7-diamino-2,6-dinitro-1H,5H-pyrazolo-[1,2-a]pyrazole-1,5-dione (4), the structure of which was comprehensively analyzed by a variety of advanced spectroscopic methods and by X-ray crystallo-graphy (with density of 1.845 g·cm−3 at 173 K). Although obtained crystals of 4 contained solvent molecules in their structure, state-of-the-art density functional theory (DFT) computational techniques allowed us to predict that solvent-free crystals of this explosive would preserve a similar tightly packed planar layered molecular arrangement, with the same number of molecules of 4 per unit cell, but with a smaller unit cell volume and therefore higher energy density. Explosive 4 was found to be heat resistant, with an onset decomposition temperature of 328.8 °C, and was calculated to exhibit velocity of detonation in a range of 6.88–7.14 km·s−1 and detonation pressure in the range of 19.14–22.04 GPa, using for comparison both HASEM and the EXPLO 5 software. Our results indicate that the trans-bimane explosophore could be a viable platform for the development of new thermostable energetic materials.

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From intermolecular interactions to structures and properties of a novel cocrystal explosive: a first-principles study

Cited by 30 publications

References 36 publications

Revealing Solid Properties of High-energy-density Molecular Cocrystals from the Cooperation of Hydrogen Bonding and Molecular Polarizability

Revealing Solid Properties of High-energy-density Molecular Cocrystals from the Cooperation of Hydrogen Bonding and Molecular Polarizability

A Study of the Shock Sensitivity of Energetic Single Crystals by Large-Scale Ab Initio Molecular Dynamics Simulations

Energetic Butterfly: Heat-Resistant Diaminodinitro trans-Bimane

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