Exploration of decomposition pathways of 2,4,6-trinitrotoluene (TNT) radical ions by means of density functional theory

•Major fragmentation channels of TNT radical ions were explored.•Mechanism of hydroxyl loss from TNT radical ions was proposed.•Stepwise mechanism for nitric oxide elimination from TNT radical anion was revealed. Methods of mass spectrometry are widely used for effective detection and identification...

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Bibliographic Details
Published inInternational journal of mass spectrometry Vol. 392; pp. 7 - 15
Main Authors Nguyen Van, B., Nikolaeva, E.V., Shamov, A.G., Khrapkovskii, G.M., Tsyshevsky, R.V.
Format Journal Article
LanguageEnglish
Published Elsevier B.V 03.12.2015
Subjects
2,4,6-Trinitrotoluene
DFT
Fragmentation
Radical anion
Radical cation
Radical anion
Radical cation
DFT
2,4,6-Trinitrotoluene
Fragmentation
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Summary:•Major fragmentation channels of TNT radical ions were explored.•Mechanism of hydroxyl loss from TNT radical ions was proposed.•Stepwise mechanism for nitric oxide elimination from TNT radical anion was revealed. Methods of mass spectrometry are widely used for effective detection and identification of explosives and high density energy materials. During last decade mass spectrum of most popular explosives such as PETN, HMX, RDX and TNT have been obtained and carefully inspected. Nevertheless, the reactivity of ionized nitro compounds and the mechanisms of their fragmentation are still to be understood. Inspired by the work of Sulzer et al. [23] on fragmentation of TNT under dissociative electron attachment, we carried out theoretical exploration of unimolecular decomposition of TNT radical ions. It was found that elimination of hydroxyl is the predominant fragmentation channel for both positively and negatively ionized TNT molecules, whereas in general decomposition of TNT radical ions involves complex stepwise processes.
ISSN:1387-3806
1873-2798
DOI:10.1016/j.ijms.2015.08.016