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含能材料  2009 

椅式(5,5)单壁碳纳米管内硝基甲烷热解反应的理论研究

DOI: 10.3969/j.issn.1006-9941.2009.05.005

Keywords: 物理化学,碳纳米管,硝基甲烷,热解反应,从头算

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Abstract:

采用完全活性空间自洽场方法(CASSCF)以及组合的量子化学ONIOM方法,研究了硝基甲烷受限于椅式(5,5)单壁碳纳米管内的结构及热解过程。分子结构分析表明,椅式(5,5)碳纳米管内的硝基甲烷其构型发生扭转,Cs对称性消失,C—N键长略微缩短。热解势能面分析发现,硝基甲烷单体沿C—N键的热解是一个无过渡态的解离过程,而硝基甲烷在椅式(5,5)碳纳米管内的热解需经历一个过渡态,所需克服的能垒约为198kJ·mol-1,比硝基甲烷单体的解离能降低了21kJ·mol-1左右。此外,计算结果还表明,椅式(5,5)碳纳米管内的硝基甲烷热解过程中的分子结构、NO2和CH3基团电荷变化与单体解离过程亦有所不同。

References

[1]  Okotrub A V, Bulusheva L G,Tomanek D. X-ray spectroscopic and quantum-chemical study of carbon tubes produced in arc-discharge [J]. Chem PhyJ Lett,1998,289:341 -349.
[2]  Ricca A, C Bauschlicher Jr W, Maiti A. Comparison of the reactivity of O2 with a (10,0) and a (9,0) carbon nanotube[J]. Phys Rev B, 2003,68 : 035433.
[3]  Ricca A,Drocco J A. Interaction of O2 with a (9,0) carbon nanotube [J]. Chem Phys Lett,2002,362:217 -223.
[4]  Arenas J F, Otero J C, Pelaez D, et al. The ground and excited state potential energy surfaces of nitromethane related to its dissociation dynamics after excitation at 193 nm [J]. J Chem Phys, 2003,119(15): 7814 -7823.
[5]  Frisch M J,Trucks G W, Schlegel H N, et al. Gaussian 03 Revision E. 01 [ C P ]. Gaussian, Inc. , Wallingford, CT, 2005.
[6]  Nguyen M T, Le H T, Hajgato B, et al. Nitromethane-methyl nitrite rearrangement: A persistent discrepancy between theory and experlment[J]. J Phys Chem A ,2003,107 : 4286 -4291.
[7]  McKee M L. MCSCF study of the rearrangement of nitromethane to methyl nitrite[J]. J Phys Chem, 1989,93 : 7365 - 7369.
[8]  Hu W F,He T J, Chen D M, et al. Theoretical study of the CH3 NO2 unimolecular decomposition potential energy surface[J]. J Phys them A ,2002,106 : 7294 - 7303.
[9]  Benson S W, O\\'Neal H E. Kinetic data on gas-phase unimolecular reactions,washington,DC: National Bureau of Standards,1970.
[10]  Arenas J F,Centeno S P,Lopez-Tocon I,et al. DFT and EASPT2 study of two thermal reactions of nitromethane: C-N bond cleavage and nitro-to-nitrite isomerization. An example of the inverse symmetry breaking deficiency in density functional calculations of a homolytie dissociation[J]. J Mol Strut(Theochem) ,2003,630: 17 -23.
[11]  Loiseau A,Launois P,Petit P,et al. Salvetat J-P Eds. Understanding Carbon Nanotubes[M]. Berlin Heidelberg: Springer,2006.
[12]  王晗 赵凤起 李上文 等.碳物质在固体推进剂中的功能及其作用机理[J].火炸药学报,2006,29(4):32-35.
[13]  Wang Y, Malhotra S, Iqbal Z. Nanoscale energetics with carbon nanotubes[J]. Mat Res Soc Syrup Proc ,2004,800 : AA9.1.1 - AA9.1.9.
[14]  Ajayan P M,Terrones M,de la Guardia A,et al. Nanotubes in a flash ignition and reconstruction[J]. Science,2002,296 : 705.
[15]  Assovskiy I G. Metallized SWCNT: Promising way to low sensitive high energetic nanocomposites [J]. Propell, Explos, Pyrot, 2008,33 (1) : 51 -54.
[16]  Abou-Rachid H, Hu A ,Timoshevskii V, et al. Nanoscale high energetic materials a polymeric nitrogen chain Ns confined inside a carbon nanotube[J]. Phys Rev Left,2008,100: 196401.
[17]  于宪峰.纳米碳管对CL-20热分解性能的影响[J].火炸药学报,2004,27(3):78-80.
[18]  张维 李晓萌 李杰 罗运军.纳米碳管对7-氨基-6-硝基苯并二氧化呋咱热分解的影响[J].燃烧科学与技术,2004,10(1):92-95.
[19]  Sorescu D C,Rice B M,Thompson D L. Molecular dynamics simulations of liquid nitromethane[J]. Phys Chem A,2001,105 (41) : 9336 - 9346.
[20]  Sorescu D C, Rice B M, Thompson D L. Theoretical studies of solid nitromethane[J]. J Phys Chem B,2000,104 (35) : 8406 - 8419.
[21]  Itoh K, Iwa A, Uriu Y, et al. Infrared absorption spectroscopic and DFT calculation studies on the adsorption structures of nitromethane on the single crystals of Cu and Ag Surface Science[J]. Surf Sci,2008, 602:2148-2156.
[22]  Manaa M R, Fried L E. DFT and ab inltlo study of the unimolecular decomposition of the lowest singlet and triplet states of nitromethane [J]./Phys Chera A,1998,102(48) : 9884-9889.
[23]  Ellison M D, Morris S T, Sender M R, et al. Infrared and computational studies of the adsorption of methanol and ethanol on single-walled carbon nanotubes[J]. JPhys Chem C,2007,111(49) : 18127 -18134.

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