八硝基立方烷高温热分解分子动力学模拟

引用本文: 杨镇, 何远航. 八硝基立方烷高温热分解分子动力学模拟[J]. 物理化学学报, 2016, 32(4): 921-928. doi: 10.3866/PKU.WHXB201512251 shu

Citation: YANG Zhen, HE Yuan-Hang. Pyrolysis of Octanitrocubane via Molecular Dynamics Simulations[J]. Acta Physico-Chimica Sinica, 2016, 32(4): 921-928. doi: 10.3866/PKU.WHXB201512251 shu

八硝基立方烷高温热分解分子动力学模拟

杨镇 ,
何远航 ^,

1.
北京理工大学, 爆炸与科学国家重点实验室, 北京 100081

通讯作者: 何远航

摘要: 随着对高能量密度材料的性能要求不断提高,新型高能量密度材料成为近期研究热点,其中八硝基立方烷(ONC)由于其优越的性能成为其中典型的代表,然而关于八硝基立方烷热分解的动力学机理研究比较少。本文采用ReaxFF反应力场模拟高温条件下凝聚相八硝基立方烷初始热分解过程。研究发现热分解过程中八硝基立方烷笼状骨架结构中C-C键最先发生断裂,并逐步破坏形成八硝基环辛烯等,随后出现NO₂和O等,计算结果表明笼状骨架结构的破坏存在三种不同路径。八硝基立方烷在高温条件下热分解的主要产物有NO₂、O₂、CO₂、N₂、NO₃、NO、CNO以及CO等,其中N₂和CO₂是终态产物,不同温度对产物均产生不同程度的影响。

关键词:

English

Pyrolysis of Octanitrocubane via Molecular Dynamics Simulations

YANG Zhen ,
HE Yuan-Hang ^,

1.
State Key Laboratory of Explosion Science and Technology, Beijing Institute of Technology, Biejing 100081, P. R. China

Corresponding author: 何远航

Received Date: 14 October 2015
Available Online: 25 December 2015

Abstract: As the requirements for the performance of high-energy-density materials increase, research to develop new types of high-energy-density materials has become highly heated recently. Octanitrocubane, by virtue of its superior performance, is one of the typical representatives of recently developed high-energy-density materials. However, there have been few studies on the thermal decomposition mechanism of octanitrocubane, even though they are essential to analyze the thermostability and sensitivity of octanitrocubane, as well as to achieve its efficient application. In this study, the initial pyrolysis process of condensed-phase octanitrocubane at high temperature was investigated using ReaxFF reactive molecular dynamics simulation. The results showed that it is the C-C bond of the octanitrocubane cage skeleton structure that breaks first, and then octanitrocubane cage skeleton structure is gradually destroyed, and the small molecules such as NO₂ and O occur afterwards. The simulation identified three different damage pathways of the cage skeleton. The main products of octanitrocubane thermal decomposition at high temperature are NO₂, O₂, CO₂, N₂, NO₃, NO, CNO, and CO, of which N₂ and CO₂ are the final products. The products that form depend on temperature.

Key words:

1. [1]
  (1) Qiu, L.; Xu, X. J.; Xiao, H. M. Chin. J. Energy Mater. 2005, 13, 262. [邱玲, 许晓娟, 肖鹤鸣. 含能材料, 2005, 13, 262.](1) Qiu, L.; Xu, X. J.; Xiao, H. M. Chin. J. Energy Mater. 2005, 13, 262. [邱玲, 许晓娟, 肖鹤鸣. 含能材料, 2005, 13, 262.]
2. [2]
  (2) Zhang, J. Quantum Chemical Studies on the Structures and Properties of Organic Caged Energetic Compounds Including Polynitrocubanes. Ph. D. Dissertation, Nanjing University of Science and Technology, Nanjing, 2003. [张骥. 多硝基立方烷等有机笼状高能化合物结构和性能的量子化学研究[D]. 南京: 南京理工大学, 2003.](2) Zhang, J. Quantum Chemical Studies on the Structures and Properties of Organic Caged Energetic Compounds Including Polynitrocubanes. Ph. D. Dissertation, Nanjing University of Science and Technology, Nanjing, 2003. [张骥. 多硝基立方烷等有机笼状高能化合物结构和性能的量子化学研究[D]. 南京: 南京理工大学, 2003.]
3. [3]
  (3) Ji, Y. P.;Wang, B. Z.; Zhang, Z. Z.; Lu, Q.; Zhu, C. H. Chin. J. Energy Mater. 2004, 12, 189. [姬月萍, 王伯周, 张志忠, 刘愆, 朱春华. 含能材料, 2004, 12, 189.](3) Ji, Y. P.;Wang, B. Z.; Zhang, Z. Z.; Lu, Q.; Zhu, C. H. Chin. J. Energy Mater. 2004, 12, 189. [姬月萍, 王伯周, 张志忠, 刘愆, 朱春华. 含能材料, 2004, 12, 189.]
4. [4]
  (4) Eaton, P. E.; Cole, T.W., Jr. J. Am. Chem. Soc. 1964, 86, 3157. doi: 10.1021/ja01069a041(4) Eaton, P. E.; Cole, T.W., Jr. J. Am. Chem. Soc. 1964, 86, 3157. doi: 10.1021/ja01069a041
5. [5]
  (5) Eaton, P. E.; Cole, T.W., Jr. J. Am. Chem. Soc. 1964, 86, 962. doi: 10.1021/ja01059a072(5) Eaton, P. E.; Cole, T.W., Jr. J. Am. Chem. Soc. 1964, 86, 962. doi: 10.1021/ja01059a072
6. [6]
  (6) Lukin, K.; Li, J. C.; Gilardi, R.; Eaton, P. E. Angew. Chem. Int. Edit. 1996, 35, 864. doi: 10.1002/anie.199608641(6) Lukin, K.; Li, J. C.; Gilardi, R.; Eaton, P. E. Angew. Chem. Int. Edit. 1996, 35, 864. doi: 10.1002/anie.199608641
7. [7]
  (7) Lukin, K.; Li, J. C.; Gilardi, R.; Eaton, P. E. Angew. Chem. Int. Edit. 1996, 35, 866. doi: 10.1002/anie.199608661(7) Lukin, K.; Li, J. C.; Gilardi, R.; Eaton, P. E. Angew. Chem. Int. Edit. 1996, 35, 866. doi: 10.1002/anie.199608661
8. [8]
  (8) Lukin, K. A.; Li, J. C.; Eaton, P. E.; Gilardi, R. J. Org. Chem. 1997, 62, 8490. doi: 10.1021/jo971308k(8) Lukin, K. A.; Li, J. C.; Eaton, P. E.; Gilardi, R. J. Org. Chem. 1997, 62, 8490. doi: 10.1021/jo971308k
9. [9]
  (9) Zhang, M. X.; Eaton, P. E.; Gilardi, R. Angew. Chem. Int. Edit. 2000, 39, 401. doi: 10.1002/(SICI)1521-3757(20000117)112: 2<422::AID-ANGE422>3.0.CO;2-2(9) Zhang, M. X.; Eaton, P. E.; Gilardi, R. Angew. Chem. Int. Edit. 2000, 39, 401. doi: 10.1002/(SICI)1521-3757(20000117)112: 2<422::AID-ANGE422>3.0.CO;2-2
10. [10]
  (10) Richard, R. M.; Ball, D.W. J. Hazard. Mater. 2009, 164, 1595. doi: 10.1016/j.jhazmat.2008.09.078(10) Richard, R. M.; Ball, D.W. J. Hazard. Mater. 2009, 164, 1595. doi: 10.1016/j.jhazmat.2008.09.078
11. [11]
  (11) Richard, R. M.; Ball, D.W. J. Hazard. Mater. 2009, 164, 1552. doi: 10.1016/j.jhazmat.2008.08.057(11) Richard, R. M.; Ball, D.W. J. Hazard. Mater. 2009, 164, 1552. doi: 10.1016/j.jhazmat.2008.08.057
12. [12]
  (12) Peköz, R.; Erkoç, Ş. Comput. Mater. Sci. 2009, 46, 849. doi: 10.1016/j.commatsci.2009.04.020(12) Peköz, R.; Erkoç, Ş. Comput. Mater. Sci. 2009, 46, 849. doi: 10.1016/j.commatsci.2009.04.020
13. [13]
  (13) Chi, W. J.; Li, L. L.; Li, B. T.;Wu, H. S. J. Mol. Model. 2013, 19, 571. doi: 10.1007/s00894-012-1582-1(13) Chi, W. J.; Li, L. L.; Li, B. T.;Wu, H. S. J. Mol. Model. 2013, 19, 571. doi: 10.1007/s00894-012-1582-1
14. [14]
  (14) Owens, F. J. J. Mol. Struct. 1999, 460, 137. doi: 10.1016/ S0166-1280(98)00312-1(14) Owens, F. J. J. Mol. Struct. 1999, 460, 137. doi: 10.1016/ S0166-1280(98)00312-1
15. [15]
  (15) Chi, W.;Wang, X. Y.; Li, B. T.;Wu, H. S. J. Mol. Model. 2012, 18, 4217. doi: 10.1007/s00894-012-1430-3(15) Chi, W.;Wang, X. Y.; Li, B. T.;Wu, H. S. J. Mol. Model. 2012, 18, 4217. doi: 10.1007/s00894-012-1430-3
16. [16]
  (16) Li, J. S. Theor. Chem. Acc. 2009, 122, 101. doi: 10.1007/s00214-008-0489-5(16) Li, J. S. Theor. Chem. Acc. 2009, 122, 101. doi: 10.1007/s00214-008-0489-5
17. [17]
  (17) Liu, L. C.; Bai, C.; Sun, H.; Goddard, W. A., III. J. Phys. Chem. A 2011, 115, 4941. doi: 10.1021/jp110435p(17) Liu, L. C.; Bai, C.; Sun, H.; Goddard, W. A., III. J. Phys. Chem. A 2011, 115, 4941. doi: 10.1021/jp110435p
18. [18]
  (18) Zhan, J. H.;Wu, R. C.; Liu, X. X.; Gao, S. Q.; Xu, G. G. Fuel 2014, 134, 283. doi: 10.1016/j.fuel.2014.06.005(18) Zhan, J. H.;Wu, R. C.; Liu, X. X.; Gao, S. Q.; Xu, G. G. Fuel 2014, 134, 283. doi: 10.1016/j.fuel.2014.06.005
19. [19]
  (19) Ghenoweth, K.; van Duin, A. C. T.; Dasgupta, S.; Goddard, W. A., III. J. Phys. Chem. A 2009, 113, 1740. doi: 10.1021/jp8081479(19) Ghenoweth, K.; van Duin, A. C. T.; Dasgupta, S.; Goddard, W. A., III. J. Phys. Chem. A 2009, 113, 1740. doi: 10.1021/jp8081479
20. [20]
  (20) Cheung, S.; Deng, W. Q.; van Duin, A. C. T.; Goddard, W. A., III. J. Phys. Chem. A 2005, 109, 851. doi: 10.1021/jp0460184(20) Cheung, S.; Deng, W. Q.; van Duin, A. C. T.; Goddard, W. A., III. J. Phys. Chem. A 2005, 109, 851. doi: 10.1021/jp0460184
21. [21]
  (21) Mueller, J. E.; van Duin, A. C. T.; Goddard, W. A., III. J. Phys. Chem. C 2010, 114, 4939. doi: 10.1021/la4006983(21) Mueller, J. E.; van Duin, A. C. T.; Goddard, W. A., III. J. Phys. Chem. C 2010, 114, 4939. doi: 10.1021/la4006983
22. [22]
  (22) Kim, S. Y.; Kumar, N.; Persson, P.; Sofo, J.; van Duin, A. C. T.; Kubicki, J. D. Langmuir 2013, 29, 7838. doi: 10.1021/la4006983(22) Kim, S. Y.; Kumar, N.; Persson, P.; Sofo, J.; van Duin, A. C. T.; Kubicki, J. D. Langmuir 2013, 29, 7838. doi: 10.1021/la4006983
23. [23]
  (23) Strachan, A.; Kober, E. M.; van Duin, A. C. T.; Oxgaard, J.; Goddard, W. A. J. Chem. Phys. 2005, 122, 54502. doi: 10.1063/1.1831277(23) Strachan, A.; Kober, E. M.; van Duin, A. C. T.; Oxgaard, J.; Goddard, W. A. J. Chem. Phys. 2005, 122, 54502. doi: 10.1063/1.1831277
24. [24]
  (24) Liu, H.; Dong, X.; He, Y. H. Acta Phys. -Chim. Sin. 2014, 30, 232. [刘海, 董晓, 何远航. 物理化学学报, 2014, 30, 232.] doi: 10.3866/PKU.WHXB201312101(24) Liu, H.; Dong, X.; He, Y. H. Acta Phys. -Chim. Sin. 2014, 30, 232. [刘海, 董晓, 何远航. 物理化学学报, 2014, 30, 232.] doi: 10.3866/PKU.WHXB201312101
25. [25]
  (25) Liu, H.; Li, Q. K.; He, Y. H. Acta Phys. Sin. 2013, 62, 1. [刘海, 李启楷, 何远航. 物理学报, 2013, 62, 1.] doi: 10.7498/aps.62.208202(25) Liu, H.; Li, Q. K.; He, Y. H. Acta Phys. Sin. 2013, 62, 1. [刘海, 李启楷, 何远航. 物理学报, 2013, 62, 1.] doi: 10.7498/aps.62.208202
26. [26]
  (26) Zhou, T. T.; Huang, F. L. J. Phys. Chem. B 2011, 115, 278. doi: 10.1021/jp105805w(26) Zhou, T. T.; Huang, F. L. J. Phys. Chem. B 2011, 115, 278. doi: 10.1021/jp105805w
27. [27]
  (27) http://lammps.sandia.gov/ (accessed Nov 16, 2015).(27) http://lammps.sandia.gov/ (accessed Nov 16, 2015).

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

八硝基立方烷高温热分解分子动力学模拟

通讯作者: 何远航

English

Pyrolysis of Octanitrocubane via Molecular Dynamics Simulations

Corresponding author: 何远航

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

八硝基立方烷高温热分解分子动力学模拟

通讯作者: 何远航

English

Pyrolysis of Octanitrocubane via Molecular Dynamics Simulations

Corresponding author: 何远航

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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