Photochemistry of the α-Al2O3-PETN Interface

Tsyshevsky, Roman; Зверев, А. С.; Mitrofanov, A. Yu.; Rashkeev, Sergey N.; Kuklja, Maija M.

doi:10.3390/molecules21030289

Cited by 10 publications

(6 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Because energetic materials are densely packed, we predict that there are many other manifestations of the crystal arrangement governing the decomposition chemistry and hence the sensitivity. To mention just a few vivid illustrations, we recall the shear-strain effect in DADNE [21,124,141], the aspects of autocatalysis analyzed for DADNE and TATB [124], polarization-induced charge transfer in δ-HMX [96], enhanced optical absorption on PETN-MgO interfaces [142], and photocatalytic dissociation of PETN molecules adsorbed on F 0 -centers on the α-Al 2 O 3 (0001) surfaces [143]. A variety of structural and electronic defects also play a role in changing decomposition chemistry in organic molecular crystals [19,122,133,144,145,146].…”

Section: Discussionmentioning

confidence: 99%

Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials

2016

Self Cite

View full text Add to dashboard Cite

This review presents a concept, which assumes that thermal decomposition processes play a major role in defining the sensitivity of organic energetic materials to detonation initiation. As a science and engineering community we are still far away from having a comprehensive molecular detonation initiation theory in a widely agreed upon form. However, recent advances in experimental and theoretical methods allow for a constructive and rigorous approach to design and test the theory or at least some of its fundamental building blocks. In this review, we analyzed a set of select experimental and theoretical articles, which were augmented by our own first principles modeling and simulations, to reveal new trends in energetic materials and to refine known existing correlations between their structures, properties, and functions. Our consideration is intentionally limited to the processes of thermally stimulated chemical reactions at the earliest stage of decomposition of molecules and materials containing defects.

show abstract

Section: Discussionmentioning

confidence: 99%

Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials

2016

Self Cite

View full text Add to dashboard Cite

show abstract

“…In addition, work on 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) did not consider cyclization as the primary method of initiation due to high activation barriers. [36] Although many factors unique to the solid state can influence the sensitivity of energetic materials, [1][2][3]27] gas-phase calculations can contribute to understanding how intramolecular interactions influence sensitivity. Theoretical measures of bond strength include the Atoms-In-Molecules (AIM) method, [37,38] unimolecular decomposition activation barriers, [22,23] bond dissociation energies (BDEs) [39] and Mulliken population analysis.…”

Section: Introductionmentioning

confidence: 99%

Trigger bond analysis of nitroaromatic energetic materials using wiberg bond indices

Shoaf

Bayse

2018

J Comput Chem

View full text Add to dashboard Cite

The identification of trigger bonds, bonds that break to initiate explosive decomposition, using computational methods could help direct the development of novel, "green" and efficient high energy density materials (HEDMs). Comparing bond densities in energetic materials to reference molecules using Wiberg bond indices (WBIs) provides a relative scale for bond activation (%ΔWBIs) to assign trigger bonds in a set of 63 nitroaromatic conventional energetic molecules. Intramolecular hydrogen bonding interactions enhance contributions of resonance structures that strengthen, or deactivate, the CNO trigger bonds and reduce the sensitivity of nitroaniline-based HEDMs. In contrast, unidirectional hydrogen bonding in nitrophenols strengthens the bond to the hydrogen bond acceptor, but the phenol lone pairs repel and activate an adjacent nitro group. Steric effects, electron withdrawing groups and greater nitro dihedral angles also activate the CNO trigger bonds. %ΔWBIs indicate that nitro groups within an energetic molecule are not all necessarily equally activated to contribute to initiation. %ΔWBIs generally correlate well with impact sensitivity, especially for HEDMs with intramolecular hydrogen bonding, and are a better measure of trigger bond strength than bond dissociation energies (BDEs). However, the method is less effective for HEDMs with significant secondary effects in the solid state. Assignment of trigger bonds using %ΔWBIs could contribute to understanding the effect of intramolecular interactions on energetic properties. © 2018 Wiley Periodicals, Inc.

show abstract

“…Quantum-chemical calculations lifted the contradiction and suggested that PETN–MgO interfaces, formed in the mixture, absorb light with the low energy of 1.3 eV due to oxygen vacancy-adsorbent interactions and electronic states generated in the band gap. , This absorption triggers the decomposition chemistry of PETN with a much lower activation barrier than the conventional thermal initiation . The similar situation was observed in the alumina-PETN mixtures . It was established that the interaction of energetics with defects leads to a formation of charged or excited radicals that govern photodecomposition.…”

Section: Introductionmentioning

confidence: 84%

“…50 The similar situation was observed in the alumina-PETN mixtures. 53 It was established that the interaction of energetics with defects leads to a formation of charged or excited radicals that govern photodecomposition. These developments provoked a set of outstanding questions, such as whether a photocatalytic additive can be deliberately chosen (for instance, as a dopant) to facilitate conventional decomposition reactions or initiate an unusual photodecomposition pathway in energetic materials.…”

Section: Introductionmentioning

confidence: 99%

Role of Hydrogen Abstraction Reaction in Photocatalytic Decomposition of High Energy Density Materials

et al. 2016

Self Cite

View full text Add to dashboard Cite

Explosive phenomena includes a stunningly wide range of diverse manifestations, such as supernova remnant shocks and solar flares, violent decomposition chemistry and synthesis of superior materials under extreme conditions, weapons, missiles, and high velocity impact damage, fuels for space rocket engines, festive fireworks, and applications of detonation waves in construction industry and microshocks in medicine. With the earliest stages of explosives chemistry in energetic materials remaining poorly understood and constantly posing new science questions, an achievement of a controllable initiation of detonation process represents a particular challenge. Precise tuning of sensitivity to initiation of detonation via photoexcitation appears unreachable because all known secondary explosives are wide band gap insulators. This research demonstrates how YAG:Nd laser irradiation triggers explosive decomposition of PQ−PETN composites formed by pentaerythritol tetranitrate (PETN), high energy density material, mixed with photosensitive 9,10phenanthrenequinone (PQ). We suggest, explore, and validate a feasible mechanism of photocatalytic decomposition of explosives activated by the laser excitation with the energy of 1.17−2.3 eV and the wavelength of 1064−532 nm.

show abstract

Photochemistry of the α-Al2O3-PETN Interface

Cited by 10 publications

References 57 publications

Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials

Molecular Theory of Detonation Initiation: Insight from First Principles Modeling of the Decomposition Mechanisms of Organic Nitro Energetic Materials

Trigger bond analysis of nitroaromatic energetic materials using wiberg bond indices

Role of Hydrogen Abstraction Reaction in Photocatalytic Decomposition of High Energy Density Materials

Contact Info

Product

Resources

About