Chemical interplay between components in overall thermolysis of CL-20/N2O revealed by ReaxFF molecular dynamics simulations
Understanding of the interplay reactions between components in CL-20 bicomponent crystals is fundamental for synthesis and applications of new CL-20 cocrystals and host-guest materials. This paper reports the thermal decomposition of CL-20/N2O host-guest crystal investigated using ReaxFF MD simulati...
| Main Authors: | , , |
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| Format: | Article |
| Language: | English |
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KeAi Communications Co. Ltd.
2022-03-01
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| Series: | Energetic Materials Frontiers |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2666647221000816 |
| _version_ | 1828046632243953664 |
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| author | Chun-xing Ren Xiao-xia Li Li Guo |
| author_facet | Chun-xing Ren Xiao-xia Li Li Guo |
| author_sort | Chun-xing Ren |
| collection | DOAJ |
| description | Understanding of the interplay reactions between components in CL-20 bicomponent crystals is fundamental for synthesis and applications of new CL-20 cocrystals and host-guest materials. This paper reports the thermal decomposition of CL-20/N2O host-guest crystal investigated using ReaxFF MD simulations under both isothermal and adiabatic conditions. The isothermal thermolysis simulation at low temperature of 800 K and adiabatic decomposition simulation initiated at 800 K were performed to reveal as much as the real and overall scenario of CL-20/N2O thermolysis. Two reference systems of ε-CL-20 and CL-20/H2O were employed for clear depiction of reaction mechanism. Permitted by VARxMD for reaction details and facilitated by the three-stage classification, the overall scenario of CL-20/N2O thermolysis and deep insight about the interplay reaction details between host CL-20 and guest N2O were obtained. The dominating of host CL-20 decomposition during entire thermolysis of CL-20/N2O is similar with that of CL-20/HMX and CL-20/TNT. However, the branching ratios of major reaction pathways of CL-20 initial decomposition were altered. The decomposition kinetics in initial thermolysis of CL-20/N2O was found significantly slowed when compared with ε-CL-20, which is caused by the guest N2O molecules that capture the NO2 intermediates generated from host CL-20 decomposition and prevent NO2 from their active participation in further decomposition of the system. It should be noted that the early formation of N2 from guest N2O in CL-20/N2O decomposition accelerates self-heating at certain extent and provides extra oxidative NO3, which slightly compensates to the slowed kinetics in the initial stage. The acceleration effect of guest oxidant N2O on CL-20/N2O decomposition will sustain through the oxygen migration of guest N2O in later secondary reactions to form more NOx than that of CL-20/H2O, consequently reducing the reaction zone of CL-20/N2O thermolysis. What was obtained in this work demonstrates that ReaxFF MD simulations combined with the analysis scheme of three-stage classification can facilitate the depiction of thermolysis mechanism of CL-20 bicomponent crystals and be useful in searching for leading candidates of guest molecules for CL-20 host-guest materials. |
| first_indexed | 2024-04-10T18:28:42Z |
| format | Article |
| id | doaj.art-4b3a8417b6bd4fa3923eab116e848ebe |
| institution | Directory Open Access Journal |
| issn | 2666-6472 |
| language | English |
| last_indexed | 2024-04-10T18:28:42Z |
| publishDate | 2022-03-01 |
| publisher | KeAi Communications Co. Ltd. |
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| series | Energetic Materials Frontiers |
| spelling | doaj.art-4b3a8417b6bd4fa3923eab116e848ebe2023-02-02T04:50:13ZengKeAi Communications Co. Ltd.Energetic Materials Frontiers2666-64722022-03-013119Chemical interplay between components in overall thermolysis of CL-20/N2O revealed by ReaxFF molecular dynamics simulationsChun-xing Ren0Xiao-xia Li1Li Guo2State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, China; Innovation Academy for Green Manufacture, Chinese Academy of Sciences, Beijing, 100190, ChinaState Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, China; Innovation Academy for Green Manufacture, Chinese Academy of Sciences, Beijing, 100190, China; University of Chinese Academy of Sciences, Beijing, 100049, China; Corresponding author.State Key Laboratory of Multiphase Complex Systems, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, China; Innovation Academy for Green Manufacture, Chinese Academy of Sciences, Beijing, 100190, China; University of Chinese Academy of Sciences, Beijing, 100049, ChinaUnderstanding of the interplay reactions between components in CL-20 bicomponent crystals is fundamental for synthesis and applications of new CL-20 cocrystals and host-guest materials. This paper reports the thermal decomposition of CL-20/N2O host-guest crystal investigated using ReaxFF MD simulations under both isothermal and adiabatic conditions. The isothermal thermolysis simulation at low temperature of 800 K and adiabatic decomposition simulation initiated at 800 K were performed to reveal as much as the real and overall scenario of CL-20/N2O thermolysis. Two reference systems of ε-CL-20 and CL-20/H2O were employed for clear depiction of reaction mechanism. Permitted by VARxMD for reaction details and facilitated by the three-stage classification, the overall scenario of CL-20/N2O thermolysis and deep insight about the interplay reaction details between host CL-20 and guest N2O were obtained. The dominating of host CL-20 decomposition during entire thermolysis of CL-20/N2O is similar with that of CL-20/HMX and CL-20/TNT. However, the branching ratios of major reaction pathways of CL-20 initial decomposition were altered. The decomposition kinetics in initial thermolysis of CL-20/N2O was found significantly slowed when compared with ε-CL-20, which is caused by the guest N2O molecules that capture the NO2 intermediates generated from host CL-20 decomposition and prevent NO2 from their active participation in further decomposition of the system. It should be noted that the early formation of N2 from guest N2O in CL-20/N2O decomposition accelerates self-heating at certain extent and provides extra oxidative NO3, which slightly compensates to the slowed kinetics in the initial stage. The acceleration effect of guest oxidant N2O on CL-20/N2O decomposition will sustain through the oxygen migration of guest N2O in later secondary reactions to form more NOx than that of CL-20/H2O, consequently reducing the reaction zone of CL-20/N2O thermolysis. What was obtained in this work demonstrates that ReaxFF MD simulations combined with the analysis scheme of three-stage classification can facilitate the depiction of thermolysis mechanism of CL-20 bicomponent crystals and be useful in searching for leading candidates of guest molecules for CL-20 host-guest materials.http://www.sciencedirect.com/science/article/pii/S2666647221000816CL-20 host-guest crystalCL-20 cocrystalInterplay reaction mechanismThermal decompositionReaxFF MD |
| spellingShingle | Chun-xing Ren Xiao-xia Li Li Guo Chemical interplay between components in overall thermolysis of CL-20/N2O revealed by ReaxFF molecular dynamics simulations Energetic Materials Frontiers CL-20 host-guest crystal CL-20 cocrystal Interplay reaction mechanism Thermal decomposition ReaxFF MD |
| title | Chemical interplay between components in overall thermolysis of CL-20/N2O revealed by ReaxFF molecular dynamics simulations |
| title_full | Chemical interplay between components in overall thermolysis of CL-20/N2O revealed by ReaxFF molecular dynamics simulations |
| title_fullStr | Chemical interplay between components in overall thermolysis of CL-20/N2O revealed by ReaxFF molecular dynamics simulations |
| title_full_unstemmed | Chemical interplay between components in overall thermolysis of CL-20/N2O revealed by ReaxFF molecular dynamics simulations |
| title_short | Chemical interplay between components in overall thermolysis of CL-20/N2O revealed by ReaxFF molecular dynamics simulations |
| title_sort | chemical interplay between components in overall thermolysis of cl 20 n2o revealed by reaxff molecular dynamics simulations |
| topic | CL-20 host-guest crystal CL-20 cocrystal Interplay reaction mechanism Thermal decomposition ReaxFF MD |
| url | http://www.sciencedirect.com/science/article/pii/S2666647221000816 |
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