Further Studies of the Classical Dynamics of the Unimolecular Dissociation of RDX

Chambers, Clarke A.; Thompson, Donald L.

doi:10.1021/j100043a029

Cited by 32 publications

(50 citation statements)

References 10 publications

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“…All the other researchers find C 12 Ͼ C 13 , while the opposite trend is found in this study. Although the absolute magnitudes of C 13 and C 23 vary somewhat among all previous works, the other researchers report similar relative internal values for C 13 Discrepancies between the theoretical studies and this experimental work are expected. In general, theoretical studies make use of potentials that often very accurately reproduce the unit-cell structure of a molecular system.…”

Section: Discussioncontrasting

confidence: 46%

The elastic constants and related properties of the energetic material cyclotrimethylene trinitramine (RDX) determined by Brillouin scattering

Haycraft

Stevens

Eckhardt

2006

The Journal of Chemical Physics

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Haycraft, James J.; Stevens, Lewis L.; and Eckhardt, Craig J., "The elastic constants and related properties of the energetic material cyclotrimethylene trinitramine (RDX) determined by Brillouin scattering" (2006 The acoustic phonons of cyclotrimethylene trinitramine ͑RDX͒ have been studied using Brillouin scattering. The analysis of the acoustic-phonon velocities allowed determination of the complete stiffness tensor for this energetic material. The results are compared to other recent experimental and theoretical determinations of the RDX elastic constants, bulk moduli, and shear moduli. The observed ordering of elastic constants, C 11 Ͼ C 22 Ͼ C 33 , is qualitatively associated with a ͑001͒ cleavage plane and molecular packing. This interpretation is further corroborated by the linear compressibilities plotted in three crystallographic planes, and a comparison to recent theoretical and experimental hydrostatic compression studies on RDX. Finally, the elasticity of RDX is compared to a recently published report on the beta polymorph of cyclotetramethylene tetranitramine's elasticity, and is related to several proposed mechanisms for detonation initiation.

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Section: Discussioncontrasting

confidence: 46%

The elastic constants and related properties of the energetic material cyclotrimethylene trinitramine (RDX) determined by Brillouin scattering

Haycraft

Stevens

Eckhardt

2006

The Journal of Chemical Physics

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“…In contrast, RDX, HMX and PETN eliminate HONO by extracting a hydrogen from a neighboring CH 2  group (Fig. b) . For the latter pathway, Green and Rowe proposed the oxidation of o ‐dinitroanilines to dinitroazobenzenes or the furazan oxides based on synthesis under neutral and alkaline conditions, respectively.…”

Section: Introductionmentioning

confidence: 99%

“…X-NO 2 (X 5 N,C,O) bonds substituted on energetic materials have been proposed to form "trigger bonds," activated (i.e., more readily cleaved) bonds that break to initiate an explosive reaction. [16] Initiation steps proposed based on mass spectrometry [17][18][19][20][21] and DFT [22][23][24][25][26] for common secondary explosives (1,3,5-trinitro-1,3,5-triazacyclohexane (RDX), 1,3,5,7-tetranitro-1,3,5,7-tetrazacyclooctane (HMX), 2,4,6trinitrotoluene (TNT), trinitrobenzene (TNB) and pentaerythritol tetranitrate (PETN)) generally include homolytic bond cleavage, interatomic rearrangements, molecular eliminations and/or ring fission. Studies of TNT [21,[26][27][28][29] suggest that CANO 2 homolytic cleavage is the most favorable initiation step.…”

Section: Introductionmentioning

confidence: 99%

“…1b). [22][23][24][25] For the latter pathway, Green and Rowe [34,35] proposed the oxidation of o-dinitroanilines to dinitroazobenzenes or the furazan oxides based on synthesis under neutral and alkaline conditions, respectively. However, decomposition by either of these two pathways would require the initial loss of either H 2 or H 2 O which are necessarily multi-step ( Fig.…”

Section: Introductionmentioning

confidence: 99%

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Trigger bond analysis of nitroaromatic energetic materials using wiberg bond indices

Shoaf

Bayse

2018

J Comput Chem

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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.

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“…1͒: the simple N-N bond rupture giving the radicals NO 2 and C 3 H 6 N 5 O 4 and the concerted ring fission reaction that yields three CH 2 N 2 O 2 molecules. Chambers and Thompson 15 have carried out classical trajectory simulations on three surfaces which are similar except for the barrier height for the ring fission reaction. We have calculated rate constants for both reaction channels on all three surfaces by using the IDDT approach.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular dynamics diffusion theory approach to complex unimolecular reactions

Guo

Shalashilin

Krouse

et al. 1999

The Journal of Chemical Physics

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A theory for nonisothermal unimolecular reaction rates We consider the relation between observed pump-probe signals in the femtosecond regime and the kinetics of unimolecular reactions, that is, the exponential decay of reactants and the exponential rise of the product population, respectively. It is shown that the signals cannot be fully accounted for within standard approaches of unimolecular decay, conventionally used in the past, since interference effects between the quasi-bound vibrational states within the bandwidth of the pump laser cannot be neglected. When these effects are included, all features of the signals can be accounted for. We apply this theoretical treatment of coherent interference to examine the dynamics and kinetics of the quasi-bound transition configurations, and relate them to the decay rates of individual quasi-bound resonance states. The signals show multi-exponential behavior, reflecting the different decay rates of the resonance states, with an average rate constant within the bandwidth of the pump laser which can be extracted directly from the signals. The persistence of coherence is evident in the observed signals. The predissociation of NaI is used as a prototype for numerical illustration.

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Further Studies of the Classical Dynamics of the Unimolecular Dissociation of RDX

Cited by 32 publications

References 10 publications

The elastic constants and related properties of the energetic material cyclotrimethylene trinitramine (RDX) determined by Brillouin scattering

The elastic constants and related properties of the energetic material cyclotrimethylene trinitramine (RDX) determined by Brillouin scattering

Trigger bond analysis of nitroaromatic energetic materials using wiberg bond indices

Intramolecular dynamics diffusion theory approach to complex unimolecular reactions

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