Prediction of structures and properties of 2,4,6-triamino-1,3,5-triazine-1,3,5-trioxide (MTO) and 2,4,6-trinitro-1,3,5-triazine-1,3,5-trioxide (MTO3N) green energetic materials from DFT and ReaxFF molecular modeling

Naserifar, Saber; Zybin, Sergey V.; Ye, Caichao; Goddard, William A.

doi:10.1039/c5ta06426k

Cited by 18 publications

(12 citation statements)

References 48 publications

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“…The equilibrium lattice parameters at 298 K and 1 atm for MTO and MTO3N crystals predicted by NPT-MD simulations are summarized in Table 1 and compared with the results from DFT calculations. 25 The relative errors are less than 2 %, indicating that ReaxFF provides an accurate description of the crystal structures for MTO and MTO3N. The predicted densities at 300 K are 1.898 g/cm 3 for MTO and 2.067 g/cm 3 for MTO3N, which are 1% to 2% smaller than DFT (since the MD is at 300 K whereas the DFT is at 0 K).…”

Section: Validation Of the Reaxff Description For Mto And Mto3nmentioning

confidence: 89%

“…The initial un-shocked state of MTO (MTO3N) was obtained by optimizing the predicted crystal structure at ambient condition (T = 300 K, P = 1 atm). To do this, we started with the unit cell 25 predicted by the PBE-D2 flavor of DFT that includes a good description of NB interacctions and extended it by 6 × 4 × 3 (2 × 4 × 4) times in the a, b, and c directions as shown in Fig. 1, leading to 2592 (2304) atoms in the extended cell.…”

Section: Predicting the Properties Of The Initial Un-shocked Statementioning

confidence: 99%

“…To understand the stability of MTO and MTO3N, we predicted the molecular and crystal structures using Monte Carlo methods and density functional theory (DFT) as reported previously. 25 Then we studied the initial reaction mechanisms for thermal decomposition using quantum mechanics dynamics simulations. 26 These simulations suggested that MTO3N would have good thermal stability while MTO would exhibit intermolecular hydrogen transfer processes that might lead to higher sensitivity.…”

Section: Introductionmentioning

confidence: 99%

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Predicted detonation properties at the Chapman–Jouguet state for proposed energetic materials (MTO and MTO3N) from combined ReaxFF and quantum mechanics reactive dynamics

Zhou

Zybin

Goddard

et al. 2018

Phys. Chem. Chem. Phys.

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Section: Validation Of the Reaxff Description For Mto And Mto3nmentioning

confidence: 89%

Section: Predicting the Properties Of The Initial Un-shocked Statementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Predicted detonation properties at the Chapman–Jouguet state for proposed energetic materials (MTO and MTO3N) from combined ReaxFF and quantum mechanics reactive dynamics

Zhou

Zybin

Goddard

et al. 2018

Phys. Chem. Chem. Phys.

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“…In order to stabilize the neutral gemdinitromethyl compound 2, the aqueous/ethyl ether solution of 2 was treated with different bases to obtain ionic Scheme 1. Several nitrogen-rich fused-ring energetic materials [21]. derivatives (compounds 3-6).…”

Section: Synthesis and Characterization Of Energetic Materialsmentioning

confidence: 99%

“…In pursuit of high-performance energetic materials, the N-functionalization strategies employed in the development of novel fused-ring energetic compounds are intriguing. Recently, several research groups have synthesized various fused-ring-based energetic materials, which exhibit favorable detonation properties (see Scheme 1) [21].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Properties of 3,6‐Dinitropyrazolo[4,3‐c]‐pyrazole (DNPP) Derivatives

Zhang

Xia

et al. 2020

Propellants Explo Pyrotec

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A series of novel fused‐ring pyrazolo[4,3‐c]pyrazole derivatives featuring N‐dinitromethyl and N‐fluorodinitromethyl energetic groups (compounds 3–7) were synthesized using a nine‐step reaction. All these compounds were characterized using multinuclear nuclear magnetic resonance (NMR) spectroscopy, infra‐red (IR) spectroscopy, and elemental analysis. X‐ray diffraction analysis was performed, and the single‐crystal structures of compounds 3, 4, 6, and 7 were obtained. For these newly prepared energetic materials, the thermal stability was determined using differential scanning calorimetry (DSC), while the sensitivities were evaluated using BAM drop hammer and friction test. The calculated heat of formation values and the measured densities were used to determine the detonation parameters, including detonation velocity and pressure, using the EXPLO5 program. Of all the prepared compounds, dipotassium 1,4‐bis(dinitromethyl)‐3,6‐dinitro‐1,4‐dihydropyrazolo[4,3‐c]pyrazole (3) was crystallized as a three‐dimensional energetic metal‐organic framework (MOF) and showed outstanding detonation performances, which even outperformed the traditional primary explosive lead azide. Compound 7 exhibited a high crystal density of 1.939 g cm−3, the high decomposition temperature of 213 °C and desirable impact and friction sensitivities (IS: 12 J; FS: 240 N). These combined properties and performances make these novel fused‐ring energetic compounds suitable candidates for high‐performance energetic materials.

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Molecular design of long intra‐annular nitrogen chains: 3H‐tetrazolo[1,5‐d]tetrazole‐based high‐energy‐density materials

Zhao

Zhang

Xie

et al. 2021

Int J of Quantum Chemistry

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Energetic compounds containing long nitrogen chain, have been a research hotspot.Fused heterocycles are stable due to their aromatic systems. Compounds obtained by combining long nitrogen chain and fused ring can not only retain good energetic property, but also ensure better stability. In this work, eight fused heterocycle-based energetic compounds, 3H-tetrazolo [1,5-d]tetrazole (1) and its derivatives (2-8), were designed, containing a nitrogen chain with seven nitrogen atoms. The HOF, thermal stability, and energetic properties of these compounds were studied using the DFT method. The results show that the introduction of -NO 2 , -N 3 , -NF 2 , -ONO 2 , and -NHNO 2 groups greatly increased the density, HOF, detonation velocity, and detonation pressure. The densities of 3, 5, 7, and 8 fall within the range designated for high-energy-density materials. The calculated detonation velocities of the compounds 3 and 8 are as high as 9.86 and 9.78 km s À1 , which are superior to that of CL-20. Kinetic study of the thermal decomposition mechanism indicates that the N-R bonds may not be the weakest bonds in these compounds. The tetrazole ring opening of the heterocycle-based energetic compounds, followed by N 2 elimination, is predicted to be the primary decomposition channel, regardless of whether substituent groups are present.energetic compounds, fused heterocycles, nitrogen chain, thermal stability 1 | INTRODUCTION Energetic materials have been widely used in explosives, propellants, and pyrotechnic agents. The development of high-performance, high-density, high-stability and environmentally friendly energetic materials has been a focus in recent years. Nitrogen-rich heterocyclic compounds are rich in high-energy chemical bonds such as N=N, N-N, C-N, and N-O and have large ring tension, and therefore, they have high heat of formation. Their high-nitrogen, low-carbon structure makes it easier for them to achieve oxygen balance. Furthermore, most of the explosion products of nitrogen-rich heterocyclic compounds are N 2 , which is friendly to the environment. So they are one of the most promising high-energy-density materials (HEDMs) [1][2][3].The heat of formation of nitrogen-rich heterocyclic compounds is related to the nitrogen content and the connection mode of the nitrogen atoms. The heat of formation increases with increasing nitrogen content and the number of directly connected nitrogen atoms [4][5][6][7]. The commonly used method to obtain long nitrogen chain is to oxidize the N-NH 2 moiety of a nitrogen heterocycle to form a tetrazene structure (N=N-N=N). Such growth of catenated nitrogen atom chains mainly occurs between two heterocycles (inter-annular nitrogen chains) [8-10].

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Prediction of structures and properties of 2,4,6-triamino-1,3,5-triazine-1,3,5-trioxide (MTO) and 2,4,6-trinitro-1,3,5-triazine-1,3,5-trioxide (MTO3N) green energetic materials from DFT and ReaxFF molecular modeling

Abstract: Structures and properties of new green energetic materials: I. MTO (P21): ρ=1.92 g cm-3, ΔHrxn = 1036 kcal kg-1 II. MTO3N (P21/c): ρ=2.1 g cm-3, ΔHrxn =1412 kcal kg-1.

Cited by 18 publications

References 48 publications

Predicted detonation properties at the Chapman–Jouguet state for proposed energetic materials (MTO and MTO3N) from combined ReaxFF and quantum mechanics reactive dynamics

Predicted detonation properties at the Chapman–Jouguet state for proposed energetic materials (MTO and MTO3N) from combined ReaxFF and quantum mechanics reactive dynamics

Synthesis and Properties of 3,6‐Dinitropyrazolo[4,3‐c]‐pyrazole (DNPP) Derivatives

Molecular design of long intra‐annular nitrogen chains: 3H‐tetrazolo[1,5‐d]tetrazole‐based high‐energy‐density materials

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