FOX-7转晶行为的太赫兹光谱及理论计算研究

孟增睿; 张伟斌; 杜宇; 尚丽平; 邓琥

doi:10.7498/aps.64.073302

摘要

1, 1 -二氨基- 2, 2 -二硝基乙烯(FOX-7)是一款新型高能钝感炸药, 为了研究温度变化对其分子结构特性的影响, 利用太赫兹时域光谱技术对持续升温(298K→393 K)过程中FOX-7 在0.2—2.5 THz 频率范围内的吸收光谱进行了在线探测, 结果发现随着样品温度的升高, FOX-7 的吸收谱带发生变化, 于384 K 时出现一个新的吸收特征峰, 且该吸收峰的峰强逐渐升高. 基于密度泛函理论(DFT), 对样品在298 K 和393 K 温度下的晶体结构进行了小于2.5 THz 范围内吸收频谱的模拟计算, 完成了对FOX-7 两种晶型实验吸收特征峰的指认. 分析表明FOX-7 的分子结构会受温度的影响而发生改变, 互为异构晶型的基团表现出的振动模式不同, 温度384 K 时FOX-7 开始发生α→β 晶型转变, 且该晶型转变过程是可逆的, 新出现的1.12 THz 特征峰在393 K 时的振动是由—NO2 和—NH2 的摆动及各自的扭动所致.

关键词:

Abstract

1, 1-diamino-2, 2-dintroethylene (FOX-7) is a novel explosive of high energy and low sensibility. In order to study the effect of temperature changes on the molecular structural characteristics of the explosive, its absorption spectra in the frequency range of 0.2–2.5 THz at a constant rate of heating from 298 K to 393 K are detected by terahertz time-domain spectroscopy (THz-TDS). Results show that a number of characteristic absorption peaks with different intensities appear at 1.59–2.13 THz when the temperature is 298 K, while the absorption spectra change with the increase of temperature of the explosive sample; a new characteristic absorption peak located at 1.12 THz appears at 384 K, and its absorption peak intensity gradually increases, but disappears when the temperature drops to 298 K. The absorption spectra of FOX-7 molecular crystal at 298 and 393 K within the 0.2–2.5 THz region based on density functional theory (DFT) are also simulated by using Materials Studio 6.0 software in this article, and the simulated results agree well with the experimental data. In addition, the vibrational modes of the characteristic peaks of two kinds of crystalline in the experimental absorption spectra are analyzed and identified, showing that the formation of the characteristic absorption peaks is closely related to the molecular vibration, and the molecular structure may change under the influence of temperature, and the tautomeric polymorphism of the crystalline has different vibrational modes. This article indicates that the process of phase transformation of FOX-7 starts from 384 K, and this process is reversible; the characteristic absorption peak at 1.12 THz is composed of two kinds of vibrations (the swinging and torsional vibrations of the nitro and amido groups).

Keywords:

作者及机构信息

1.
中国工程物理研究院化工材料研究所, 绵阳 621900;

2.
西南科技大学信息工程学院, 绵阳 621010;

3.
中国工程物理研究院太赫兹科学技术研究中心, 绵阳 621900;

4.
西南科技大学极端物质特性实验室, 绵阳 621010

基金项目: 中国工程物理研究院太赫兹科学技术中心(批准号: T2014-005-0103)和国防技术基础项目(批准号: Z202013T001)资助的课题.

Authors and contacts

1.
Institute of Chemical Materials, CAEP, Mianyang 621900, China;

2.
School of Information Engineering, Southwest University of Science and Technology, Mianyang 621010, China;

3.
Terahertz Research Center, CAEP, Mianyang 621900, China;

4.
Laboratory for Extreme Conditions Matter Properties, Southwest University of Science and Technology, Mianyang 621010, China

Funds: Project supported by the Terahertz Research Center, CAEP (Grant No. T2014-005-0103), and the National Defense Foundation of China (Grant No. Z202013T001).

参考文献

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[4]	Anniyappan M, Talawar M B, Gore G M, Venuqopalan S, Gandhe B R 2006 J. Hazard Mater. 137 812
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[6]	Kempa P B, Herrmann M 2005 Part. Part. Syst. Char. 22 418
[7]	Pellizzeri S, Korter T M, Zubieta J 2011 J. Mol. Struct. 1003 21
[8]	Qiao W, Stephan D, Hasselbeck M, Liang Q, Dekorsy T 2012 Opt. Express 20 19769
[9]	Oppenheim K C, Korter T M, Melinger J S, Grischkowsky D 2010 J. Phys. Chem. A 114 12513
[10]	Delaney S P, Witko E M, Simith T M, Korter T M 2012 J. Phys. Chem. A 116 8051
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[15]	Ewelina M W, Timothy M K 2012 J. Phys. Chem. A 116 6879
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[17]	Pellizzeri S, Delaney S P, Korter T M, Zubieta J 2013 J. Mol. Struct. 1050 27
[18]	Allis D G, Zeitler J A, Taday P F, Korter T M 2008 Chem. Phys. Lett. 463 84
[19]	Huang L, Shabaev A, Lambrakos S G, Massa L 2013 Vib. Spectrosc. 64 62
[20]	Wu Q, Zhu W, Xiao H 2013 J. Mol. Model 19 4039
[21]	Wang W N, Li Y B, Yue W W 2007 Acta Phys. Sin. 56 0781 (in Chinese) [王卫宁, 李元波, 岳伟伟 2007 56 0781]
[22]	Wang W N 2009 Acta Phys. Sin. 58 7640 (in Chinese) [王卫宁 2009 58 7640]
[23]	Nickel D V, Delaney S P, Bian H T, Zheng J R, Korter T M, Mittleman D M 2014 J. Phys. Chem. A 118 2442
[24]	Dorney T D, Baraniuk R G, Mittleman D M 2001 J. Opt. Soc. Am. A: Opt. Image Sci. Vis. 18 1562
[25]	Allen F H, Kennard O 1993 Chemical Design Automation News 8 1&31

施引文献

[1]	Latypov N V, Bergman J, Langlet A, Wellmar U, Bemm U 1998 Tetrahedron 54 11525
[2]	Huang B, Qiao Z Q, Nie F D, Cao M H, Su J, Huang H, Hu C W 2010 J. Hazard Mater. 184 561
[3]	Xu K Z, Song J R, Zhao F Q, Ma H X, Gao H X, Chang C R, Ren Y H, Hu R Z 2008 J. Hazard Mater. 158 333
[4]	Anniyappan M, Talawar M B, Gore G M, Venuqopalan S, Gandhe B R 2006 J. Hazard Mater. 137 812
[5]	Ren X L, Zuo X G, Xu K Z, Ren Y H, Huang J, Song J R, Wang B Z, Zhao F Q 2011 B Korean Chem. Sol. 32 2267
[6]	Kempa P B, Herrmann M 2005 Part. Part. Syst. Char. 22 418
[7]	Pellizzeri S, Korter T M, Zubieta J 2011 J. Mol. Struct. 1003 21
[8]	Qiao W, Stephan D, Hasselbeck M, Liang Q, Dekorsy T 2012 Opt. Express 20 19769
[9]	Oppenheim K C, Korter T M, Melinger J S, Grischkowsky D 2010 J. Phys. Chem. A 114 12513
[10]	Delaney S P, Witko E M, Simith T M, Korter T M 2012 J. Phys. Chem. A 116 8051
[11]	Delaney S P, Pan D, Galella M, Yin S X, Korter T M 2012 Cryst. Growth Des. 12 5017
[12]	Allis D G, Prokhorova D A, Korter T M 2006 J. Phys. Chem. A110 1951
[13]	Fitch M J, Leahy-Hoppa M R, Ott E W, Osiander R 2007 Chem. Phys. Lett. 443 284
[14]	Li R, Zeitler J A, Tomerini D, Parrott E P J, Gladden L F, Day G M A 2010 Phys. Chem. Chem. Phys. 12 5329
[15]	Ewelina M W, Timothy M K 2012 J. Phys. Chem. A 116 6879
[16]	Wang C L, Tian Z, Xiong Q R, Gu J Q, Liu F, Hu M L, Chai L, Wang Q Y 2010 Acta Phys. Sin. 59 7857 (in Chinese) [王昌雷, 田震, 邢岐荣, 谷建强, 刘丰, 胡明列, 柴路, 王清月 2010 59 7857]
[17]	Pellizzeri S, Delaney S P, Korter T M, Zubieta J 2013 J. Mol. Struct. 1050 27
[18]	Allis D G, Zeitler J A, Taday P F, Korter T M 2008 Chem. Phys. Lett. 463 84
[19]	Huang L, Shabaev A, Lambrakos S G, Massa L 2013 Vib. Spectrosc. 64 62
[20]	Wu Q, Zhu W, Xiao H 2013 J. Mol. Model 19 4039
[21]	Wang W N, Li Y B, Yue W W 2007 Acta Phys. Sin. 56 0781 (in Chinese) [王卫宁, 李元波, 岳伟伟 2007 56 0781]
[22]	Wang W N 2009 Acta Phys. Sin. 58 7640 (in Chinese) [王卫宁 2009 58 7640]
[23]	Nickel D V, Delaney S P, Bian H T, Zheng J R, Korter T M, Mittleman D M 2014 J. Phys. Chem. A 118 2442
[24]	Dorney T D, Baraniuk R G, Mittleman D M 2001 J. Opt. Soc. Am. A: Opt. Image Sci. Vis. 18 1562
[25]	Allen F H, Kennard O 1993 Chemical Design Automation News 8 1&31

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