Theoretical predictions of the decomposition mechanism of 1,3,3-trinitroazetidine (TNAZ)

Alavi, Saman; Reilly, Lisa; Thompson, Donald L.

doi:10.1063/1.1611471

Cited by 22 publications

(24 citation statements)

References 16 publications

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“…Generally, the whole scheme of kinetic details is confined by the fastest rate of the general reaction, which cannot easily be understood through experimental techniques. It is claimed that ''Theoretical calculations can play a crucial role in resolving the details not available from experiments [2],'' and many researchers have, therefore, recently proposed the use of theoretical calculation methods [3][4][5][6][7][8][9][10][11] to enhance the reliability of the design of reaction mechanisms and as a supplement for a shortage of experiments. Preliminary computational work can thus be performed to avoid encountering unexpected and complicated problems while the experimental process is ongoing.…”

Section: Introduction Ementioning

confidence: 99%

Computational study of the catalytic synthesis of 5‐nitro‐1,2,4‐triazol‐3‐one

Cheng¹,

Liu

Yang

2011

Int J of Quantum Chemistry

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In this study, 5-nitro-1,2,4-triazol-3-one (NTO) was theoretically synthesized from urea via chlorination followed by amination, formylation, and nitration under aqueous and gaseous environments based on experience of experimental methods, and metal chlorides and metal oxides were used as catalysts to promote reaction. Reaction routes closely related to experimental processes were successfully constructed, and the corresponding energy barriers were estimated for each elementary reaction. Reaction conditions distinct from those reported in the literature (including the adoption of aluminum chloride, ferric chloride, aluminum oxide, ferrous oxide, and chromium oxide catalysts, the use of nitric acid and dinitrogen pentoxide as nitration agents, and adjustment of the reaction temperature) were used in corresponding reaction systems, and the modeling results suggested that ferric chloride is a good catalyst for the chlorination reaction, ferrous oxide is suitable for catalyzing amination, formylation, and nitration, and nitric acid is the better agent for nitration. Estimates of the comparable energy barriers for each reaction stage were considered to imply more feasible pathways for NTO synthesis.

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Section: Introduction Ementioning

confidence: 99%

Computational study of the catalytic synthesis of 5‐nitro‐1,2,4‐triazol‐3‐one

Cheng¹,

Liu

Yang

2011

Int J of Quantum Chemistry

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“…These materials, such as TNAZ and FOX-7, pass through nitroalkyl radical or nitroalkene intermediates en route to their eventual decomposition products. 7,8 One route to study the decomposition of key intermediates such as nitroalkyl radicals is to produce them from the photodissociation of the appropriate halogenated precursor. Creating these intermediates photolytically allows the study of these intermediates in isolated environments without the possibility of side reactions.…”

mentioning

confidence: 99%

Further Studies into the Photodissociation Pathways of 2-Bromo-2-nitropropane and the Dissociation Channels of the 2-Nitro-2-propyl Radical Intermediate

et al. 2014

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These experiments investigate the decomposition mechanisms of geminal dinitro energetic materials by photolytically generating two key intermediates: 2-nitropropene and 2-nitro-2-propyl radicals. To characterize the unimolecular dissociation of each intermediate, we form them under collision-free conditions using the photodissociation of 2-bromo-2-nitropropane; the intermediates are formed at high internal energies and undergo a multitude of subsequent unimolecular dissociation events investigated herein. Complementing our prior work on this system, the new data obtained with a crossed-laser molecular beam scattering apparatus with VUV photoionization detection at Taiwan's National Synchrotron Radiation Research Center (NSRRC) and new velocity map imaging data better characterize two of the four primary 193 nm photodissociation channels. The C−Br photofission channel forming the 2-nitro-2-propyl radicals has a trimodal recoil kinetic energy distribution, P(E T ), suggesting that the 2-nitro-2-propyl radicals are formed both in the ground electronic state and in two low-lying excited electronic states. The new data also revise the HBr photoelimination P(E T ) forming the 2-nitropropene intermediate. We then resolved the multiple competing unimolecular dissociation channels of each photoproduct, confirming many of the channels detected in the prior study, but not all. The new data detected HONO product at m/e = 47 using 11.3 eV photoionization from both intermediates; analysis of the momentummatched products allows us to establish that both 2-nitro-2-propyl → HONO + CH 3 CCH 2 and 2-nitropropene → HONO + C 3 H 4 occur. Photoionization at 9.5 eV allowed us to detect the mass 71 coproduct formed in OH loss from 2-nitro-2-propyl; a channel missed in our prior study. The dynamics of the highly exothermic 2-nitro-2-propyl → NO + acetone dissociation is also better characterized; it evidences a sideways scattered angular distribution. The detection of some stable 2-nitropropene photoproducts allows us to fit signal previously assigned to H loss from 2-nitro-2-propyl radicals. Overall, the data provide a comprehensive study of the unimolecular dissociation channels of these important nitro-containing intermediates. ■ INTRODUCTIONThe decomposition pathways of energetic materials have been intensely studied both experimentally and theoretically for decades.1−9 These mechanisms can be difficult to elucidate in the bulk phase, however, due to the plethora of side reactions. To this end, theoretical predictions can be used to evaluate possible steps in a proposed decomposition mechanism. For example, the recent computational study on TNAZ decomposition pathways submitted this year by Veals and Thompson 9 re-examines previous computational and experimental results on TNAZ, clarifying the first few steps in the decomposition mechanism. A second potential method for studying these systems is to photolytically induce the decomposition of smaller model materials. Because a common functionality across organic based energe...

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“…It was motivated by the statement that "Theoretical calculations play a crucial role in resolving the details not available from experiments" [17]. All the work in this study has been performed on theoretical grounds.…”

Section: Resultsmentioning

confidence: 99%

A guiding simulation research on developing promising energetic materials

Liu

Cheng

Chen

et al. 2008

Int J of Quantum Chemistry

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This investigation is motivated by the representative synthesis reaction of 1,4,5,4,5,: ethylene diamine is replaced by 1,1,diamino-2,2-dinitroethene (FOX-7) or 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) to react with glyoxal in order to subsequently obtain promising high energy density materials. The hybrid density functional theory method is used in calculations for some series of compounds with ONONO 2 and OCONO 2 functional groups. First, we create the corresponding Cartesian coordinates of the molecules under investigation and obtain their optimized molecular geometry; the molecular enthalpy can then be used to calculate the molecular detonation heat upon explosion. Furthermore, the target molecular volumes are obtained using the group additivity approach, which are then transferred into molecular densities. The densities and detonation heats of the corresponding energetics are carried into the Kamlet-Jacobs empirical equations to determine the related detonation velocities and detonation pressures. It was found that 10 of 14 TATB-and FOX7-related molecular derivatives have detonation velocities between 9,302 and 1,1122 m/s and between 396 and 646 kbar, and are superior in performance to the traditional octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) explosive.

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Theoretical predictions of the decomposition mechanism of 1,3,3-trinitroazetidine (TNAZ)

Cited by 22 publications

References 16 publications

Computational study of the catalytic synthesis of 5‐nitro‐1,2,4‐triazol‐3‐one

Computational study of the catalytic synthesis of 5‐nitro‐1,2,4‐triazol‐3‐one

Further Studies into the Photodissociation Pathways of 2-Bromo-2-nitropropane and the Dissociation Channels of the 2-Nitro-2-propyl Radical Intermediate

A guiding simulation research on developing promising energetic materials

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