Thermal decomposition of isolated and crystal 4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazaisowurtzitane according to ab initio molecular dynamics simulations

Dong, Xiang; Zhu, Weihua

doi:10.1039/c6ra27255j

Cited by 20 publications

(14 citation statements)

References 23 publications

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“…We could gather h 50 values in centimeter measured with two similar approaches: five (TNCB, TNTriCB, CL20, DINGU, and TNAZ) out of the six molecules were obtained using the ERL Type 12 tooling with 2.5 kg impact hammer protocol . The TEX molecule, which was not included in the training group (see below), had its h 50 value also measured by a drop test using similar determination parameters . We expect that this approach minimizes the inconsistency of the used h 50 values hence their analysis with our mathematical models.…”

Section: Theoretical and Computational Methodsmentioning

confidence: 99%

“…[13,63,64] The TEX molecule, which was not included in the training group (see below), had its h 50 value also measured by a drop test using similar determination parameters. [2,[65][66][67] We expect that this approach minimizes the inconsistency of the used h 50 values hence their analysis with our mathematical models.…”

Section: On the Choice Of The Set Of Molecules And The Availabilitymentioning

confidence: 99%

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On the molecular origin of the sensitivity to impact of cyclic nitramines

Oliveira

Borges

2018

Int J of Quantum Chemistry

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Nitramine explosives can combine relative insensitivity to initiation and great energy content. In this work, based on a previous approach developed for nitroaromatic explosives, we propose four mathematical models to correlate impact sensitivity, given by the h50 value, to molecular charge properties. Fourteen cyclic nitramines were studied using Density Functional Theory (DFT). Six molecules of the set have measured h50 values, which were used to evaluate the sensitivity models. Converged DFT charge densities of the molecules were partitioned and analyzed according to the distributed multipole analysis (DMA) atom‐centered method. The sensitivity models were based on the DMA electric multipole values. The electron withdrawing role of the nitro group and the strong polarization of the charges of the nitrogen atom in the amine group were clearly identified. The influence of the electronic properties on the sensitivity of the explosives was characterized by including in the sensitivity models the charge values of the nitro or the nitramine groups and electron delocalization, the latter quantified by the DMA quadrupole values of the ring atoms. Inclusion of electron delocalization effects can improve the prediction of h50 values for two out of the five strained‐ring nitramines in the set. The charge values of the nitramine groups are the most important molecular property affecting the impact sensitivity. The h50 values of eight nitramine explosives of the set not available experimentally were computed.

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Section: Theoretical and Computational Methodsmentioning

confidence: 99%

Section: On the Choice Of The Set Of Molecules And The Availabilitymentioning

confidence: 99%

On the molecular origin of the sensitivity to impact of cyclic nitramines

Oliveira

Borges

2018

Int J of Quantum Chemistry

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“…For path (b), the C─H bond broke to release H radicals, which can catalyze the reactions of other molecules and radicals. Xiang et al [8] have ever reported that the generated H radicals are very active and can prompt other unreacted TEX molecules to decompose. This is similar to our findings of the decompositions of the cocrystal.…”

Section: Resultsmentioning

confidence: 99%

“…And these studies provide some useful information for understanding the complicated behaviors of the explosives. Xiang et al performed AIMD simulations to study the initiation mechanism and the subsequent decomposition process of the TEX crystal at 2160 K. Wu et al uncovered the thermal decomposition mechanisms of the 3,6‐di(azido)‐1,2,4,5‐tetrazine (DiAT) crystal at 3000 K. Later, Wu et al performed AIMD simulations to study coupling effects of temperature (534–873 K) and pressure (1–20 GPa) on the initiation mechanisms and subsequent chemical decompositions of nitramine explosive HMX. Xiang et al used the AIMD method to investigate initial decomposition mechanisms and subsequent chemical processes of β‐HMX crystals at high temperature coupled with high pressures.…”

Section: Introductionmentioning

confidence: 99%

Thermal decomposition mechanisms of the energetic benzotrifuroxan:1,3,3‐trinitroazetidine cocrystal using ab initio molecular dynamics simulations

Xie

Zhu

2019

J Chinese Chemical Soc

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Ab initio molecular dynamics simulations were performed to investigate the thermal decomposition mechanisms of the energetic benzotrifuroxan (BTF):1,3,3‐trinitroazetidine (TNAZ) cocrystal at high temperature. It is found that there are four initial reaction mechanisms involved in the decomposition of the cocrystal. Subsequent decomposition channels can be divided into three types: BTF‐chain isomerization, C─NO2 bond homolysis, and ring opening. After that, one main path is that long chains decomposed into small radicals gradually after the ring opening. The other is that a new ring was formed after the ring opening and then it will break by degrees. Releasing of the H radicals and oxygen‐containing groups plays an important role in the whole decomposition process. We also studied the release mechanisms of nitrogen gas and carbon dioxide in the later decomposition stage. Our study may provide new insights into the initiation mechanisms and subsequent decomposition of cocrystal explosives at high temperature.

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“…The chemical decomposition mechanism, kinetic parameters and thermodynamic properties are the key factors in understanding ignition and combustion process and product distribution during explosion . In the present study, isoconversional kinetic analysis methods are used to explore the kinetics of the multistep thermal decomposition .…”

Section: Introductionmentioning

confidence: 99%

Decomposition Kinetics of Substituted Energetic Isowurtzitane Cage Molecules Hexanitrohexaazaisowurtzitane (CL‐20) and TEX: A Comparative Study

Vargeese

2019

ChemistrySelect

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N‐substituted hexa(N‐Nitro) compound 2,4,6,8,10,12‐Hexanitro‐2,4,6,8,10,12‐hexaazatetracyclo‐ [5.5.0.05,9.03,11] dodecane (HNIW or CL‐20) and the O‐substituted di(N‐Nitro)) compound 4,10‐dinitro‐2,6,8,12‐tetraoxa‐4,10‐diazatetracyclo[5.5.0.05,9.03,11]‐dodecane (TEX) are two interesting energetic Isowurtzitane cage molecules. To develop an understanding about the underlying phenomena during explosion/combustion, the thermal decomposition behaviour and kinetics of HNIW and TEX is studied. The solid phase decomposition of HNIW shows a dependence on the extent of reaction (α), while the liquid phase decomposition of TEX is independent of α. This point towards the multistep reaction kinetics involved in the HNIW decomposition and a single stage decomposition or unification of multistep reactions exhibited by TEX during the melt phase decomposition. However, the sublimation process in TEX is defined by different activation energy values. The experimental results are presented here and theoretical possibilities are being explored through quantum chemical studies. Our study aims to provide a link between the decomposition behaviour of Isowurtzitane cage molecules and their combustion behaviour.

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Thermal decomposition of isolated and crystal 4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazaisowurtzitane according to ab initio molecular dynamics simulations

Abstract: We performed ab initio molecular dynamics simulations to study the initiation chemical reaction and subsequent decomposition mechanism of a 4,10-dinitro-2,6,8,12-tetraoxa-4,10-diazaisowutrzitane (TEX) crystal at 2160 K.

Cited by 20 publications

References 23 publications

On the molecular origin of the sensitivity to impact of cyclic nitramines

On the molecular origin of the sensitivity to impact of cyclic nitramines

Thermal decomposition mechanisms of the energetic benzotrifuroxan:1,3,3‐trinitroazetidine cocrystal using ab initio molecular dynamics simulations

Decomposition Kinetics of Substituted Energetic Isowurtzitane Cage Molecules Hexanitrohexaazaisowurtzitane (CL‐20) and TEX: A Comparative Study

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