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Klerk, W.P.C. de; Popescu, C.; Heijden, A.E.D.M. van der

doi:10.1023/a:1025038819979

Cited by 27 publications

(10 citation statements)

References 2 publications

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“…Experimental measurements of the activation energy for DADNE decomposition that became available over last two decades appear scattered in the range of 45–80 kcal/mol [117,119,120]. The CO 2 , HCN, N 2 O, NO 2 , HOCN, H 2 O, and NO species were registered among decomposition products of DADNE [117,119].…”

Section: Resultsmentioning

confidence: 99%

Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials

2016

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This review presents a concept, which assumes that thermal decomposition processes play a major role in defining the sensitivity of organic energetic materials to detonation initiation. As a science and engineering community we are still far away from having a comprehensive molecular detonation initiation theory in a widely agreed upon form. However, recent advances in experimental and theoretical methods allow for a constructive and rigorous approach to design and test the theory or at least some of its fundamental building blocks. In this review, we analyzed a set of select experimental and theoretical articles, which were augmented by our own first principles modeling and simulations, to reveal new trends in energetic materials and to refine known existing correlations between their structures, properties, and functions. Our consideration is intentionally limited to the processes of thermally stimulated chemical reactions at the earliest stage of decomposition of molecules and materials containing defects.

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Section: Resultsmentioning

confidence: 99%

Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials

2016

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“…The FOX-7 crystal appears golden yellow and has two-dimensional wave-shaped layers with extensive intermolecular hydrogen bonding within the layers and with weaker van der Waals interactions between the layers. 14,15 Stresses in the crystal are reduced by the relative movement of layers, and in this manner, the crystal is not sensitive to mechanical strain. 5 Compared to the presently most widely used and powerful explosives RDX and HMX, FOX-7 yields the same number of moles (0.0405) of gaseous product per gram of compound for the complete decomposia) Author to whom correspondence should be addressed.…”

Section: Introductionmentioning

confidence: 99%

Initial decomposition mechanism for the energy release from electronically excited energetic materials: FOX-7 (1,1-diamino-2,2-dinitroethene, C2H4N4O4)

Yuan

Bernstein

2014

The Journal of Chemical Physics

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Decomposition of the energetic material FOX-7 (1,1-diamino-2,2-dinitroethylene, C2H4N4O4) is investigated both theoretically and experimentally. The NO molecule is observed as an initial decomposition product subsequent to electronic excitation. The observed NO product is rotationally cold (<35 K) and vibrationally hot (2800 K). The initial decomposition mechanism is explored at the complete active space self-consistent field (CASSCF) level. Potential energy surface calculations at the CASSCF(12,8)/6-31G(d) level illustrate that conical intersections play an essential role in the decomposition mechanism. Electronically excited S2 FOX-7 can radiationlessly relax to lower electronic states through (S2/S1)CI and (S1/S0)CI conical intersections and undergo a nitro-nitrite isomerization to generate NO product on the S0 state. The theoretically predicted mechanism is consistent with the experimental results. As FOX-7 decomposes on the ground electronic state, thus, the vibrational energy of the NO product from FOX-7 is high. The observed rotational energy distribution for NO is consistent with the final transition state structure on the S0 state. Ground state FOX-7 decomposition agrees with previous work: the nitro-nitrite isomerization has the lowest average energy barrier, the C-NH2 bond cleavage is unlikely under the given excitation conditions, and HONO formation on the ground state surface is energy accessible but not the main process.

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“…However, a significantly strong external disturbance of the system by a mechanical impact, a shock wave or a laser beam may start the chemical decomposition leading to detonation. It is commonly believed that the first step in the decomposition of DADNE crystals is an endothermic detachment of N O 2 groups or CONO and/or HONO isomerizations [36][37][38]. The activation energy barriers for these reactions have the order of 1.8−4.1eV, which corresponds to the dissociation energy values between 40 and 90 kcal/mol.…”

Section: Application: Dadne Versus Tatbmentioning

confidence: 99%

Modeling of a self-sustaining ignition in a solid energetic material

Zimbovskaya

2017

Preprint

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In the present work we analyze some necessary conditions for ignition of solid energetic materials by low velocity impact ignition mechanism. Basing on reported results of ab initio computations we assume that the energetic activation barriers for the primary endothermic dissociation in some energetic materials may be locally lowered due to the effect of shear strain caused by the impact. We show that the ignition may be initiated in regions with the reduced activation barriers, even at moderately low exothermicity of the subsequent exothermic reactions thus suggesting that the above regions may serve as "hot spots" for the ignition. We apply our results to analyze initial steps of ignition in DADNE and TATB molecular crystals.

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Untitled

Cited by 27 publications

References 2 publications

Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials

Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials

Initial decomposition mechanism for the energy release from electronically excited energetic materials: FOX-7 (1,1-diamino-2,2-dinitroethene, C2H4N4O4)

Modeling of a self-sustaining ignition in a solid energetic material

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