Dissociative electron attachment to pentaerythritol tetranitrate: Significant fragmentation near 0 eV

Abstract

Gas phase dissociative electron attachment (DEA) measurements to pentaerythritol tetranitrate (PETN) are performed in a crossed electron-molecular beam experiment at high-energy resolution and high sensitivity. DEA is operative at very low energies close to approximately 0 eV showing unique features corresponding to a variety of fragment anions being formed. There is no evidence of the parent anion formation. The fragmentation yields are also observed for higher electron energies and are operative via several resonant features in the range of 0-12 eV. In contrast to nitroaromatic compounds, PETN decays more rapidly upon electron attachment and preferentially low-mass anions are formed. The dominant fragment ion formed through DEA is assigned to the nitrogen trioxide NO(3)(-) and represents about 80% of the total anion yield. Further intense ion signals are due to NO(2)(-) (11%) and O(-) (2.5%). The significant instability of PETN after attachment of an electron with virtually no kinetic energy confers a highly explosive nature to this compound.

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

“…22) lending evidence to their more explosive character when compared to other explosives such as TNT 20 and the other nitrocompounds. [16][17][18][19]23,24,26 In Figure 3 we show the fully optimized geometry obtained at MP2/6-311++G(2d,p)…”

“…[16][17][18][19][20][21][22][23][24][25][26] They have been performed in crossed electron-molecular beam experiments with high-energy resolution (~70 meV) 22 or high sensitivity (utilizing ~10 A of electron current). 27 These experiments have included free electron interactions with bare molecules in the gas-phase [16][17][18][19][20][21][22][23][24][25][26] and embedded in He droplets. 28 In the former, and generally speaking, we have observed that capture of an excess electron with virtually no kinetic energy leads to formation of a variety of dissociative electron attachment (DEA) fragments reflecting therefore the explosive nature of the compounds, whereas in the latter the ultra-cold environment efficiently quenches all the gas-phase dissociation channels.…”

Atmospheric pressure chemical ionization of explosives induced by soft X-radiation in ion mobility spectrometry: mass spectrometric investigation of the ionization reactions of drift gasses, dopants and alkyl nitrates

“…The DEA to pentaerythritol tetranitrate (PETN) was investigated in energy‐dependent (electron monochromator) cross‐beam experiments in vacuum (MS) . The most important ions detected are NO 3 – (80.5%), NO 2 – (11.1%), O – /OH – (3.5%) and N 2 O 4 – (1.4%) in addition to ions containing carbon, such as C 3 H 3 O – (1.6%).…”

“…Electron attachment to trinitrotoluene (TNT) in nitrogen as a drift gas at atmospheric pressure leads to the formation of TNT – . The primary processes governing electron attachment in vacuum were studied using a hemispherical electron monochromator for the production of electrons with a kinetic energy near 0 eV in a mass spectrometer . The product ion spectra obtained in vacuum and at atmospheric pressure display considerable differences .…”

“…The primary processes governing electron attachment in vacuum were studied using a hemispherical electron monochromator for the production of electrons with a kinetic energy near 0 eV in a mass spectrometer . The product ion spectra obtained in vacuum and at atmospheric pressure display considerable differences . The results of these vacuum experiments can further the understanding of the processes taking place at atmospheric pressure by combining the observations of primary and secondary reactions.…”