Chemical Insight on Decreased Sensitivity of CL-20/TNT Cocrystal Revealed by ReaxFF MD Simulations

doi:10.1021/acs.jcim.8b00952

	Chemical Insight on Decreased Sensitivity of CL-20/TNT Cocrystal Revealed by ReaxFF MD Simulations
	Ren, Chunxing 1,2; Li, Xiaoxia 1,2; Guo, Li 1,2
刊名	JOURNAL OF CHEMICAL INFORMATION AND MODELING
	2019-05-01
卷号	59 期号:5 页码:2079-2092
ISSN号	1549-9596
DOI	10.1021/acs.jcim.8b00952
英文摘要	Understanding the underlying mechanisms on sensitivity-decrease of the CL-20/TNT cocrystal is essential for wide applications of the promising high-energetic CL-20. This work presents the chemical scenario of CL-20/TNT thermolysis obtained from ReaxFF molecular dynamics simulations. Facilitated by the unique VARxMD for reaction analysis, the interplay reactions between CL-20 and TNT responsible for the sensitivity-decrease of CL-20/TNT was first revealed. The early response of CL-20/TNT to thermal stimulus is dominated by N-NO2 bond cleavage for NO2 formation and C-N bond scission leading to ring-opening of CL-20. The kinetics of N-NO2 and C-N bond cleavage, as well as the following oxygen-abstraction of NO2, are significantly slowed in the CL-20/TNT thermolysis against beta-CL-20, which are responsible for the low sensitivity at the stage of active intermediate generation. The early formed active intermediates of NO2, NO3, NO, and N2O are confined and consumed by the reactions of the surrounding TNT or ring intermediates from TNT conversion, accounting for over 40% reactions of NO2 consumption. The abundant active intermediates are consumed mainly by the direct linking of active NO2 and NO with the nitro groups of TNT, hydrogen-abstraction from TNT and oxidation of benzene rings. The complex interplay reactions between TNT and the active intermediates generated significantly retard the chain-like reactions for further exothermal process, decreasing the sensitivity of CL-20/TNT. The comprehensive chemical understanding on the sensitivity decrease of CL-20/TNT thermolysis revealed by ReaxFF MD simulations can offer assistance for tuned sensitivity of new energetic CL-20-based cocrystals.
资助项目	National Natural Science Foundation of China[21373227] ; China's State Key Laboratory of Multiphase Complex Systems[COM2015A004]
WOS关键词	REACTIVE MOLECULAR-DYNAMICS ; THERMAL-DECOMPOSITION ; ENERGETIC MATERIALS ; CO-CRYSTAL ; UNIMOLECULAR DECOMPOSITION ; REACTION-MECHANISMS ; INITIAL REACTIVITY ; LIGNIN PYROLYSIS ; FORCE-FIELD ; SCALE
WOS研究方向	Pharmacology & Pharmacy ; Chemistry ; Computer Science
语种	英语
出版者	AMER CHEMICAL SOC
WOS记录号	WOS:000469884900034
资助机构	National Natural Science Foundation of China ; China's State Key Laboratory of Multiphase Complex Systems
内容类型	期刊论文
源URL	[http://ir.ipe.ac.cn/handle/122111/29812]
专题	中国科学院过程工程研究所
通讯作者	Li, Xiaoxia
作者单位	1.Chinese Acad Sci, Inst Proc Engn, State Key Lab Multiphase Complex Syst, Beijing 100190, Peoples R China 2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China
推荐引用方式 GB/T 7714	Ren, Chunxing,Li, Xiaoxia,Guo, Li. Chemical Insight on Decreased Sensitivity of CL-20/TNT Cocrystal Revealed by ReaxFF MD Simulations[J]. JOURNAL OF CHEMICAL INFORMATION AND MODELING,2019,59(5):2079-2092.
APA	Ren, Chunxing,Li, Xiaoxia,&Guo, Li.(2019).Chemical Insight on Decreased Sensitivity of CL-20/TNT Cocrystal Revealed by ReaxFF MD Simulations.JOURNAL OF CHEMICAL INFORMATION AND MODELING,59(5),2079-2092.
MLA	Ren, Chunxing,et al."Chemical Insight on Decreased Sensitivity of CL-20/TNT Cocrystal Revealed by ReaxFF MD Simulations".JOURNAL OF CHEMICAL INFORMATION AND MODELING 59.5(2019):2079-2092.