Decomposition mechanism scenarios of CL-20 co-crystals revealed by ReaxFF molecular dynamics: similarities and differences

Ren, Chunxing; Liu, Han; Li, Xiaoxia; Guo, Li

doi:10.1039/c9cp06102a

Cited by 42 publications

(46 citation statements)

References 62 publications

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“…To summarize, due to its molecular structure that is liable to deform under EF, CL-20 is more sensitive to EF than HMX. 16 and our results agree well with this trend.…”

Section: Electric Field Effect In Evolution Of Bond Lengthsupporting

confidence: 92%

“…This can be attributed to the molecular stability of HMX with a higher decomposition barrier than that of CL-20 as mentioned above. Moreover, it is found that the decomposition temperature of HMX is about the same ($1200 K) for both CEF and OEF, and close to that of thermal decomposition, 16 indicating that the decomposition of the HMX depends mostly on temperature rather than the heating process of the molecules. We find that the decomposition of CL-20 in CL-20/HMX cocrystal is significantly slower than that in pure CL-20 (CL-20/HMX cocrystal removing HMX molecules is viewed as pure CL-20) as shown in Figure 4A.…”

Section: Electric Field Effect In Evolution Of Chemical Speciesmentioning

confidence: 67%

“…28 ReaxFF-lg has also been widely used to study the decomposition mechanism and shock response of energetic cocrystals like CL-20/TNT [13][14][15] and CL-20/HMX. 16,17,30 A 2 Â 3 Â 3 supercell was constructed from the experimental unit-cell of the CL-20/HMX cocrystal 9 to perform the simulations.…”

Section: Methodsmentioning

confidence: 99%

“…11 This motivated researchers to gain an insight into the underlying mechanism of decreased impact sensitivity by investigating thermal decomposition of the cocrystals at atomic level. [12][13][14][15][16][17] For example, reactive molecular dynamics (RMD) simulations of thermal decomposition correctly reproduced the decreased sensitivity of CL-20/TNT, and the calculated sensitivity is lower than that of CL-20 by 22% $ 70%. 13 The underlying reason was attributed to the formation of clusters from TNT, 14 the interplay reactions between two components of cocrystal, 15 and heat transferred from CL-20 to the other component of cocrystal.…”

Section: Introductionmentioning

confidence: 91%

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The role of electric field on decomposition of CL‐20/HMX cocrystal: A reactive molecular dynamics study

Zhang

Guo

2021

J Comput Chem

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“…To summarize, due to its molecular structure that is liable to deform under EF, CL-20 is more sensitive to EF than HMX. 16 and our results agree well with this trend.…”

Section: Electric Field Effect In Evolution Of Bond Lengthsupporting

confidence: 92%

Section: Electric Field Effect In Evolution Of Chemical Speciesmentioning

confidence: 67%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 91%

See 2 more Smart Citations

The role of electric field on decomposition of CL‐20/HMX cocrystal: A reactive molecular dynamics study

Zhang

Guo

2021

J Comput Chem

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“…The quantum chemistry calculation by the simulation method of ReaxFF-MD was in good consistence with corresponding experimental results. This method was widely used in various reaction systems, such as the thermal decomposition of fossil fuels, the oxidation or combustion processes of alkanes and hydrocarbons, and the explosion of energetic materials [17,[22][23][24]. The bond formation and breakage in the molecular dynamic simulation was described by ReaxFF, a reactive force field based on the bond order firstly proposed by van Duin [25,26].…”

Section: Reaxff MD Simulationsmentioning

confidence: 99%

Experimental and ReaxFF‐based molecular dynamics studies of the reaction of oxygen with DR‐2 as a low global warming potential working fluid

Tao¹,

Cheng²,

Lu³

et al. 2021

Int J of Quantum Chemistry

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The cis-1,1,1,4,4,4-hexafluoro-2-butene (DR-2 or HFO-1336mzz(Z)) is a novel environmentally friendly working fluid with appropriate physicochemical characteristics.The present work firstly investigated the decomposition mechanism and thermal stability of DR-2 in a oxygen (O 2 )-containing atmosphere at high temperature experimentally. The oxidative degradation features of DR-2 were explored at the temperature of 473-1073 K and the products were monitored by GC-MS and IC. The experimental and ReaxFF-based molecular dynamics results demonstrated the promotion effects of O 2 on the DR-2 decomposition. The participation of O 2 molecules was supposed to lower the initial thermal decomposition temperature by 240 K approximately and increase the number of products such as hydrogen fluoride (HF), but the enhancement effect was weakened by the increasing reaction temperature. The reasonable Arrhenius parameters were calculated from the first-order kinetic analyses-based reactive molecular dynamics (RMD) simulations. Combined with the density functional theory, the pathways of initial oxidation decomposition product firstly observed in the experiment and RMD simulations were proposed in this study. These results may pave the way for further study of DR-2 as a working fluid with lower global warming potential.

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Vibrational Spectra of HNIW and its Isotopologues: A Combined Experimental and Computational Study

Burton

Steele

Crowhurst

et al. 2023

Propellants Explo Pyrotec

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Incorporating isotopically labelled materials in degradation experiments could help unravel the mechanism(s) of decomposition through use of the kinetic isotope effect. Characterizing synthesized isotopologues however requires an understanding of what observable signals are affected by the isotopic substitution. As vibrational spectroscopy can distinguish between isotopologues, it is an ideal characterization technique to evaluate isotopic variants. To this end, the vibrational spectra of HNIW and its deuterated ( 2 H), 13 C, 15 N (all), 15 N (nitro), and 18 O isotopologues have been computationally predicted in the gas phase using density functional theory. These results are compared to experimentally measured FTIR/ATR and Raman spectra of both unsubstituted HNIW and 15 N-labeled HNIW in which the six nitro groups were synthetically tagged with 15 N atoms ( 15 N nitro À HNIW). The experimental isotopic frequency shift for the À NO 2 asymmetric stretching frequencies agrees with that theoretically calculated (~35.7 cm À 1 vs. 36.5 cm À 1 , respectively). Furthermore, analysis of the theoretically predicted frequency shifts for all isotopologues suggest the À NO 2 bending modes are lower in frequency than previously reported. This assignment is supported by the experimentally measured isotopic shift of ~10.1 cm À 1 for these features (consistent with the predicted shift of ~13.1 cm À 1 ). This work expands our current understanding of the vibrational modes in HNIW as well as provides a method for future work on similar systems.

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Decomposition mechanism scenarios of CL-20 co-crystals revealed by ReaxFF molecular dynamics: similarities and differences

Abstract: Overall scenarios first revealed clearly by ReaxFF MD for self-heating, similar product distributions and altered kinetics in the three-stage decomposition of CL-20 and its cocrystals under adiabatic conditions.

Cited by 42 publications

References 62 publications

The role of electric field on decomposition of CL‐20/HMX cocrystal: A reactive molecular dynamics study

The role of electric field on decomposition of CL‐20/HMX cocrystal: A reactive molecular dynamics study

Experimental and ReaxFF‐based molecular dynamics studies of the reaction of oxygen with DR‐2 as a low global warming potential working fluid

Vibrational Spectra of HNIW and its Isotopologues: A Combined Experimental and Computational Study

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