Dissociative Electron Attachment to the Nitroamine HMX (Octahydro-1,3,5,7-Tetranitro-1,3,5,7-Tetrazocine)

Postler, Johannes; Goulart, Marcelo; Matias, C.; Mauracher, Andreas; Silva, F. Ferreira da; Scheier, P.; Limão-Vieira, P.; Denifl, Stephan

doi:10.1007/s13361-013-0588-y

Cited by 11 publications

(8 citation statements)

References 40 publications

(70 reference statements)

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“…These fragment ions are thought to result from in‐source dissociative electron capture (Equation ), producing abundant C 3 H 6 N 5 O 4 − and C 4 H 7 N 6 O 4 − ions, respectively. The identity of these fragment ions was previously assigned by Postler et al for the ionization of HMX via dissociated electron attachment . To maintain accuracy and confidence, the more abundant chlorine adduct ion ( m/z 331) was selected for further method development.…”

Section: Resultsmentioning

confidence: 99%

Rapid detection of explosive vapors by thermal desorption atmospheric pressure photoionization differential mobility analysis tandem mass spectrometry

McCulloch

Amo‐González²

2019

Rapid Comm Mass Spectrometry

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Rationale The increased frequency in the number of international terror threats has led to a corresponding increase in demand for fast, sensitive and reliable screening methods suitable for the detection of airborne explosive vapors. We demonstrate herein a workflow suitable for the determination of nitrogen‐based explosives at the picogram level in just minutes. Methods A method is described that combines Thermal Desorption (TD) sample introduction with Differential Mobility Analysis (DMA) Tandem Mass Spectrometry (MS/MS), enabling a sensitive and accurate workflow suitable for the rapid detection of trace nitroaromatic, nitroester and nitramine explosive vapors. The methods are bridged using a novel low‐flow, field‐free Atmospheric Pressure Photoionization (APPI) source, intended specifically for the analysis of gas‐phase analytes and airborne particles. Results Limits of detection within or below the picogram range were determined for the analysis of a range of explosives standards including 2,6‐DNT, TNT, TATB, Tetryl, RDX, EGDN, PETN, HMX, and NG. Practical application of the TD‐APPI‐DMA‐MS/MS workflow was demonstrated for the detection of real trace explosive vapors produced from the volatilization of solid explosive samples stored within a sealed cardboard box. A single complete analysis was performed in less than 2 min. Conclusions The highly sensitive and accurate detection of a variety of common nitrogen‐based explosive vapors has been demonstrated, at levels suitable for practical, high‐throughput security screening applications.

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Section: Resultsmentioning

confidence: 99%

Rapid detection of explosive vapors by thermal desorption atmospheric pressure photoionization differential mobility analysis tandem mass spectrometry

McCulloch

Amo‐González²

2019

Rapid Comm Mass Spectrometry

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“…More photodissociation studies using laser-induced fluorescence spectroscopy or ultrafast UV femtosecond laser pump–probe techniques find NO as the observed initial decomposition product of RDX and HMX from their neutral excited electronic states: NO 2 , HONO, or CH 2 NNO 2 are not intermediates for NO under these conditions. ,, A laser-induced breakdown spectroscopic study of RDX and HMX shows the presence of C and CN mass peaks, which are signatures of high-energy materials . Dissociative electron attachment to HMX with an electron energy range of 0–20 eV, gives rise to the two most intense ions NO 2 – and C 3 H 6 N 5 O 4 – . Electron affinity and mass spectral decomposition mechanisms of RDX isomers upon electron attachment have been investigated theoretically: The vertical detachment energies are calculated to be between 1.3 and 4.0 eV, with NO 2 – loss common for anions …”

Section: Introductionmentioning

confidence: 99%

RDX- and HMX-Related Anionic Species Explored by Photoelectron Spectroscopy and Density Functional Theory

Zeng

Bernstein

2018

J. Phys. Chem. C

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Anion photoelectron spectroscopy, supported by density functional theory (DFT) calculations, is employed to study energetic materials RDX (3,5-trinitroperhydro-1,3,5-triazine) and HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine). Their isolated anions and decomposition products are generated by matrix-assisted laser desorption ionization (MALDI). Their anionic parent species are not observed, but instead accessible fragmentation ions are detected. The vertical detachment energies (VDEs) of these anionic, dissociation-generated species are experimentally determined, and the corresponding structures are identified by comparing DFT-calculated VDEs to the experimental ones. RDX– and HMX– can fragmentate through the loss of HNO2, NO2, and NCH2 groups. RDX– loses up to two NO2 groups and one NCH2 moiety, and HMX– can fragment by up to three NO2 groups and two NCH2 moieties. The mass units of (RDX – H – NO2)−, (RDX – H – (NO2)2)−, and (RDX – NCH2 – (NO2)2)− are the same as those of (HMX – H – (NO2)2 – NCH2)−, (HMX – H – (NO2)3 – NCH2)−, and (HMX – (NO2)3 – (NCH2)2)−, respectively. These dissociation-related anions with the same mass units share nearly identical photoelectron spectra and geometrical structures, which suggest structural and dissociation routine similarities between RDX and HMX anions. By way of comparison, energetic material TATB (2,4,6-triamino-1,3,5-trinitrobenzene) has also been considered: Its parent anion generated through MALDI processes can be observed in the mass spectrum. The observation of TATB– parent anion, but not RDX– and HMX– parent anions, is consistent with TATB’s higher thermal stability than those of RDX and HMX.

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“…[3][4][5] While electron ejection from the irradiated material is one of the possible outcomes, that many of the organic energetic molecules do contain electron acceptor functional groups such as -NO 2 may also result in electron capturing by the same material. For the purpose of rapid explosive detection, [6] studies using mass spectroscopic methods that included laser photon ionization [7] and dissociative negative ions spectroscopy [8][9][10] have been conducted to identify and probe unique fragments.…”

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confidence: 99%

Determination of adiabatic ionization potentials and electron affinities of energetic molecules with the Gaussian-4 method

Manaa

2017

Chemical Physics Letters

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Adiabatic ionization potentials (IP ad) and electron affinities (EA ad) are determined with the Gaussian-4 (G4) method for the energetic molecules PETN, RDX, β--HMX, CL-17, TNB, TNT, CL-14, DADNE, TNA, and TATB. The IP ad and EA ad values are in the range of 8.43-11.73 and 0.74-2.86 eV, respectively. Variations are due to substitutional effects of electron withdrawing and donating functional groups. Enthalpies of formation are also determined for several of these molecules to augment the list of recently reported G4 values. The calculated IP ad and EA ad provide quantitative assessment of such molecular properties as chemical hardness, molecular electronegativity, and "intrinsic" molecular physical hardness.

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Dissociative Electron Attachment to the Nitroamine HMX (Octahydro-1,3,5,7-Tetranitro-1,3,5,7-Tetrazocine)

Abstract: Dissociative electron attachment (DEA) measurements to gas phase HMX, octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine, C4H8N8O8, have been performed by means of a crossed

Cited by 11 publications

References 40 publications

Rapid detection of explosive vapors by thermal desorption atmospheric pressure photoionization differential mobility analysis tandem mass spectrometry

Rapid detection of explosive vapors by thermal desorption atmospheric pressure photoionization differential mobility analysis tandem mass spectrometry

RDX- and HMX-Related Anionic Species Explored by Photoelectron Spectroscopy and Density Functional Theory

Determination of adiabatic ionization potentials and electron affinities of energetic molecules with the Gaussian-4 method

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