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题名: Thermal unimolecular decomposition mechanism of 2,4,6-trinitrotoluene: a first-principles DFT study
作者: Chen, Xiao-Fang1;  Liu, Ji-Feng1;  Meng, Zi-Hui2;  Han, Ke-Li1
关键词: Nitroaromatics ;  2,4,6-Trinitrotoluene (TNT) ;  Energetic materials ;  Density function theory ;  Thermal decomposition
刊名: THEORETICAL CHEMISTRY ACCOUNTS
发表日期: 2010-11-01
DOI: 10.1007/s00214-009-0720-z
卷: 127, 期:4, 页:327-344
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical
研究领域[WOS]: Chemistry
英文摘要: Simple C-NO(2) homolysis, 4,6-dinitroanthranil (DNAt) production by dehydration, and the nitro-nitrite rearrangement-homolysis for gas-phase TNT decomposition were recently studied by Cohen et al. (J Phys Chem A 111:11074, 2007), based on DFT calculations. Apart from those three pathways, other possible initiation processes were suggested in this study, i.e., CH(3) removal, O elimination, H escape, OH removal, HONO elimination, and nitro oxidizing adjacent backbone carbon atom. The intermediate, 3,5-dinitro-2(or 4)-methyl phenoxy, is more favor to decompose into CO and 3,5-dinitro-2(or 4)-methyl-cyclopentadienyl than to loss NO following nitro-nitrite rearrangement. Below similar to 1,335 K, TNT condensing to DNAt by dehydration is kinetically the most favor process, and the formations of substituted phenoxy and following cyclopentadienyl include minor contribution. Above similar to 1,335 K, simple C-NO(2) homolysis kinetically dominates TNT decomposition; while the secondary process changes from DNAt production to CH(3) removal above similar to 2,112 K; DNAt condensed from TNT by dehydration yields to that by sequential losses of OH and H above similar to 1,481 K and to nitro-nitrite rearrangement-fragmentation above similar to 1,778 K; O elimination replaces DNAt production above similar to 2,491 K, playing the third role in TNT decomposition; H escaping directly from TNT thrives in higher temperature (above similar to 2,812 K), as the fourth largest process. The kinetic analysis indicates that CH(3) removal, O elimination, and H escape paths are accessible at the suggested TNT detonation time (similar to 100-200 fs), besides C-NO(2) homolysis. HONO elimination and nitro oxidizing adjacent backbone carbon atom paths are negligible at all temperatures. The calculations also demonstrated that some important species observed by Rogers and Dacons et al. are thermodynamically the most favor products at all temperatures, possibly stemmed from the intermediates including 4,6-dinitro-2-nitroso-benzyl alcohol, 3,5-dinitroanline, 2,6-dinitroso-4-nitro-phenylaldehyde, 3,5-dinitro-1-nitrosobenzene, 3,5-dinitroso-1-nitrobenzene, and nitrobenzene. All transition states, intermediates, and products have been indentified, the structures, vibrational frequencies, and energies of them were verified at the uB3LYP/6-311++G(d,p) level. Our calculated energies have mean unsigned errors in barrier heights of 3.4-4.2 kcal/mol (Lynch and Truhlar in J Phys Chem A 105:2936, 2001), and frequencies have the recommended scaling factors for the B3-LYP/6-311+G(d,p) method (Andersson and Uvdal in J Phys Chem A 109:2937, 2005; Merrick et al. in J Phys Chem A 111:11683, 2007). All calculations corroborate highly with the previous experimental and theoretical results, clarifying some pertinent questions.
关键词[WOS]: DENSITY-FUNCTIONAL THERMOCHEMISTRY ;  SPECTRAL FRAGMENTATION PATHWAYS ;  COLLISION-INDUCED DISSOCIATION ;  MOLECULAR-ORBITAL METHODS ;  TANDEM MASS-SPECTROMETRY ;  AROMATIC NITRO-COMPOUNDS ;  GAUSSIAN-BASIS SETS ;  PULSE SHOCK-TUBE ;  AB-INITIO ;  ENERGETIC MATERIALS
语种: 英语
WOS记录号: WOS:000282692700007
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/142193
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, State Key Lab Mol React Dynam, Dalian Inst Chem Phys, Dalian 116023, Peoples R China
2.Beijing Inst Technol, Dept Chem & Environm Engn, Beijing 100081, Peoples R China

Recommended Citation:
Chen, Xiao-Fang,Liu, Ji-Feng,Meng, Zi-Hui,et al. Thermal unimolecular decomposition mechanism of 2,4,6-trinitrotoluene: a first-principles DFT study[J]. THEORETICAL CHEMISTRY ACCOUNTS,2010,127(4):327-344.
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