Quantum Mechanical Investigation on Decomposition Pathways of BuNENA

The unimolecular decomposition pathways of n‐butyl nitroxyethylnitramine (BuNENA) were computationally investigated. The O−NO2 bond dissociation energies (BDEs) are found to be smaller than the N−NO2 BDEs. The consecutive NO2 elimination via TSA1 is more favorable kinetically than that via TSA2 alth...

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Published in:Propellants, explosives, pyrotechnics explosives, pyrotechnics, 2022-03, Vol.47 (3), p.n/a
Main Authors: Shim, Hong‐Min, Kim, Sung June, Park, Young Chul, Min, Byoung Sun
Format: Article
Language:English
Subjects:
BuNENA
Decomposition
Energy of dissociation
Free energy
Heat of formation
homolysis
HONO elimination
Isomerization
Nitrogen dioxide
Quantum mechanics
rate constants
Saddle points
unimolecular decomposition
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Summary:The unimolecular decomposition pathways of n‐butyl nitroxyethylnitramine (BuNENA) were computationally investigated. The O−NO2 bond dissociation energies (BDEs) are found to be smaller than the N−NO2 BDEs. The consecutive NO2 elimination via TSA1 is more favorable kinetically than that via TSA2 although both of them form the same intermediate of n‐butyl‐aminoacetaldehyde (BuAAA). Isomerization of n‐butyl‐nitramineethyloxidanyl radical (BuNEȮ) formed by homolytic cleavage of O−NO2 bond was found to eliminate NO2 with a negative bond dissociation energy. Among the NO2 elimination pathways, the formation of C4H9NCH2 (PB2b), CH2O, and NO2 from BuNEȮ via the saddle point TSB2a was found to be the most kinetically favorable with a low activation energy barrier. In contrast, the consecutive HONO elimination is the most thermodynamically favorable with a high exothermicity (−▵H0). The first‐principle kinetic Monte Carlo (kMC) simulations show that the NO2 elimination of BuNEȮ via TSB2a plays an important role in driving the decomposition of BuNENA.
ISSN:0721-3115
1521-4087
DOI:10.1002/prep.202100194