Broken-Symmetry Density Functional Theory Study on Pyrolysis Mechanisms of 3-Nitro-1,2,4-triazol-5-one (NTO)

doi:10.6023/cjoc202206027

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (1): 285-294.DOI: 10.6023/cjoc202206027 Previous Articles Next Articles

ARTICLES

3-硝基-1,2,4-三唑-5-酮(NTO)热分解机理的对称破缺密度泛函理论研究

凌琳^a, 王健^b, 李婧^c, 李玉学^a^,^*(), 吕龙^a^,^*()

a 中国科学院上海有机化学研究所院能量调控材料重点实验室上海 200032
b 北京系统工程研究所北京 100034
c 中国兵器科学研究院北京 100089

收稿日期:2022-06-17 修回日期:2022-07-20 发布日期:2022-08-17
通讯作者: 李玉学, 吕龙
基金资助:
国家自然科学基金(22175197)

Broken-Symmetry Density Functional Theory Study on Pyrolysis Mechanisms of 3-Nitro-1,2,4-triazol-5-one (NTO)

Lin Ling^a, Jian Wang^b, Jing Li^c, Yuxue Li^a(), Long Lu^a()

a CAS Key Laboratory of Energy Regulation Materials, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032
b Beijing System Engineering Institute, Beijing 100034
c Ordnance Science Institute of China, Beijing 100089

Received:2022-06-17 Revised:2022-07-20 Published:2022-08-17
Contact: Yuxue Li, Long Lu
Supported by:
National Natural Science Foundation of China(22175197)

1. .pdf(259KB)

Abstract

Homolytic cleavage of covalent bonds is very common during the pyrolysis of energetic molecules. However, instead of locating the transition state and calculating the free energy barrier ΔG, the bond dissociation energy (ΔH, BDE) is usually considered as the “energy barrier” of the homo-cleavage processes. This simplification brings large errors. In the present work, several pyrolysis pathways of 3-nitro-1,2,4-triazol-5-one (NTO) were studied using broken-symmetry density functional theory method (BS-UB3LYP/6-311+G**). Each transition state of homolytic cleavage was located. The results show that the best pyrolysis pathway under the experimental conditions proceeds via the homolytic cleavage of the C—NO₂ bond and the subsequent radical recombination, the energy barrier of the rate-determining step is 216.9 kJ•mol^–1 (523 K). Then, NO can promote the subsequent ring-opening, and finally yielding HNCO, N₂O and CO. Further reactions between these small molecules lead to NO₂, N₂ and CO₂. These products are consistent well with the experimental observations.

Key words: 3-nitro-1,2,4-triazol-5-one (NTO), energetic materials, pyrolysis mechanism, BS-UDFT (Broken Symmetry Density Functional Theory), open-shell singlet diradical, homolytic cleavage, theoretical study

Cite this article

Lin Ling, Jian Wang, Jing Li, Yuxue Li, Long Lu. Broken-Symmetry Density Functional Theory Study on Pyrolysis Mechanisms of 3-Nitro-1,2,4-triazol-5-one (NTO)[J]. Chinese Journal of Organic Chemistry, 2023, 43(1): 285-294.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 8

Table 1. Experimental and theoretical studies on NTO pyrolysis

Figure 1. Possible initial pathways of NTO pyrolysis

Figure 2. C—NO2 homo-cleavage initiated decomposition pathways (Path-a) (Part I) Energies are in kJ?mol–1, and selected bond lengths are in nanometers (nm)

Figure 3. IRC calculation (A), (B) and the spin density distribution (C), (D) of the key transition states TS-Homo-CN-a and TS-Recom- CO-a

Figure 4. Part II: formation of NO and NO promoted ring-opening (Path-a) Energies are in kJ?mol–1, and selected bond lengths are in nanometers (nm)

Figure 5. Further reactions/transformations between small intermediates/products Energies are in kJ?mol–1, and selected bond lengths are in nanometers (nm)

Figure 6. The proton transfer initiated decomposition pathways (Path-b) Energies are in kJ?mol–1, and selected bond lengths are in nanometers (nm)

Figure 7. Ring-opening initiated decomposition pathways (Path-c) Energies are in kJ?mol–1, and selected bond lengths are in nanometers (nm)

References 37

[1]	Viswanath, D. S.; Ghosh, T. K.; Boddu, V. M. Emerging Energetic Materials: Synthesis, Physicochemical, and Detonation Properties, Springer, Dordrecht, 2018, pp. 163-211.
[2]	Lee, K.; Chapman, L. B.; Cobura, M. D. J. Energ. Mater. 1987, 5, 27. doi: 10.1080/07370658708012347
[3]	Ma, H.-X.; Song, J.-R.; Hu, R.-Z. Chin. J. Expl. Propell. 2006, 29, 9. (in Chinese)
	(马海霞, 宋纪蓉, 胡荣祖, 火炸药学报, 2006, 29, 9.)
[4]	Rothgery, E. F.; Audette, D. E.; Wedlich, R. C.; Csejka, D. A. Thermochim. Acta 1991, 185, 235. doi: 10.1016/0040-6031(91)80045-K
[5]	Menapace, J. A.; Marlin, J. E.; Bruss, D. R.; Dascher, R. V. J. Phys. Chem. 1991, 95, 5509. doi: 10.1021/j100167a028
[6]	Östmark, H.; Bergman, H.; Åqvist, G. Thermochim. Acta 1993, 213, 165. doi: 10.1016/0040-6031(93)80014-2
[7]	Prabhakaran, K. V.; Naidu, S. R.; Kurian, E. M. Thermochim. Acta 1994, 241, 199. doi: 10.1016/0040-6031(94)87018-7
[8]	Brill, T. B.; Gongwer, P. E.; Williams, G. K. J. Phys. Chem. 1994, 98, 12242. doi: 10.1021/j100098a020
[9]	Hara, Y.; Taniguchi, H.; Ikeda, Y.; Takayama, S.; Nakamura, H. Kayaku Gakkaishi 1994, 55, 183.
[10]	Williams, G. K.; Palopoli, S. F.; Brill, T. B. Combust. Flame 1994, 98, 197. doi: 10.1016/0010-2180(94)90235-6
[11]	Oxley, J. C.; Smith, J. L.; Zhou, Z.; McKenney, R. L. J. Phys. Chem. 1995, 99, 10383. doi: 10.1021/j100025a047
[12]	Williams, G. K.; Brill, T. B. J. Phys. Chem. 1995, 99, 12536. doi: 10.1021/j100033a027
	Botcher, T. R.; Beardall, D. J.; Wight, C. A. J. Phys. Chem. 1996, 100, 8802.
[13]	Mcmillen, D. F.; Erlich, D. C.; He, C.; Becker, C. H.; Shockey, D. A. Combust. Flame 1997, 111, 133. doi: 10.1016/S0010-2180(97)00100-4
[14]	Long, G. T.; Brems, B. A.; Wight, C. A. J. Phys. Chem. B 2002, 106, 4022. doi: 10.1021/jp012894v
[15]	Kondrikov, B. N.; Smirnov, S. P.; Minakin, A. V. Propellants, Explos., Pyrotechnics 2004, 29, 27.
[16]	Sinditskii, V. P.; Smirnov, S. P.; Egorshev, V. Y. Propellants, Explos., Pyrotechnics 2007, 32, 277. doi: 10.1002/prep.200700029
[17]	Oxley, J. C.; Smith, J. L.; Rogers, E.; Dong, X. X. J. Phys. Chem. A 1997, 101, 3531. doi: 10.1021/jp9640078
[18]	Wang, K.; Wang, J.-L.; Xu, D.; Guo, T.-J.; Wang, W.; Tu, J. Acta Armamentarii 2018, 39, 1727. (in Chinese)
	(王凯, 王俊林, 徐东, 郭天吉, 王伟, 涂建, 兵工学报, 2018, 39, 1727.) doi: 10.3969/j.issn.1000-1093.2018.09.008
[19]	Harris, N. J.; Lammertsma, K. J. Am. Chem. Soc. 1996, 118, 8048. doi: 10.1021/ja960834a
[20]	Meredith, C.; Russell, T. P.; Mowrey, R. C.; McDonald, J. R. J. Phys. Chem. A 1998, 102, 471. doi: 10.1021/jp972602j
[21]	Wang, Y.-M.; Chen, C.; Lin, S.-T. J. Mol. Struct.: Theochem. 1999, 460, 79. doi: 10.1016/S0166-1280(98)00308-X
[22]	Yim, W.-L.; Liu, Z.-F. J. Am. Chem. Soc. 2001, 123, 2243. pmid: 11456870
[23]	Kohno, Y.; Takahashi, O.; Saito, K. Phys. Chem. Chem. Phys. 2001, 3, 2742. doi: 10.1039/b101745o
[24]	Xiao, H.-M.; Ju, X.-H.; Xu, L.-N.; Fang, J.-Y. J. Chem. Phys. 2004, 121, 12523. doi: 10.1063/1.1812258
[25]	Türker, L.; Atalar, T. J. Hazard. Mater. 2006, A137, 1333.
[26]	Xu, L.; Fang, G.; Li, X.; Yuan, J.; Hu, X.; Zhu, W.; Xiao, H.; Ji, G. J. Mol. Graphics Modell. 2007, 26, 415. doi: 10.1016/j.jmgm.2007.01.009
[27]	Hiyoshi, R. I.; Kohno, Y.; Nakamura, J. J. Phys. Chem. A 2004, 108, 5915. doi: 10.1021/jp049118i
[28]	Hiyoshi, R. I.; Kohno, Y.; Takahashi, O.; Nakamura, J.; Yamaguchi, Y.; Matsumoto, S.; Azuma, N.; Ueda, K. J. Phys. Chem. A 2006, 110, 9816. pmid: 16898682
[29]	Keshavarz, M. H.; Zohari, N.; Seyedsadjadi, S. A. J. Therm. Anal. Calorim. 2013, 114, 497. doi: 10.1007/s10973-013-3022-6
[30]	Liu, Z.; Wu, Q.; Zhu, W.; Xiao, H. Phys. Chem. Chem. Phys. 2015, 17, 10568. doi: 10.1039/C5CP00637F
[31]	Moxnes, J. F.; Frøyland, Ø.; Risdal, T. J. Mol. Model. 2017, 23, 240. doi: 10.1007/s00894-017-3408-7 pmid: 28744746
[32]	Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H. P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, Jr., J. A.; Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.; Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.; Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09, Revision D.01, Gaussian, Inc., Wallingford, CT, 2013.
[33]	Becke, A. D. J. Chem. Phys. 1993, 98, 5648. doi: 10.1063/1.464913
[34]	Szabo, A.; Ostlund, N. S. Modern Quantum Chemistry: Introduction to Advanced Electronic Structure Theory, Ed.: Mineola, N. Y., Dover, 1996, pp. 221-229.
[35]	Grafenstein, J.; Hjerpe, A. M.; Kraka, E. J. Phys. Chem. A 2000, 104, 1748. doi: 10.1021/jp993122q
[36]	Yao, Z.; Yu, Z. J. Am. Chem. Soc. 2011, 133, 10864. doi: 10.1021/ja2021476
[37]	Ling, L.; Liu, K.; Li, X.; Li, Y. ACS Catal. 2015, 5, 2458. doi: 10.1021/cs501892s

3-硝基-1,2,4-三唑-5-酮(NTO)热分解机理的对称破缺密度泛函理论研究

Broken-Symmetry Density Functional Theory Study on Pyrolysis Mechanisms of 3-Nitro-1,2,4-triazol-5-one (NTO)

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 8

References 37

Related Articles 6

Recommended Articles

Metrics

Comments

[1]	Zhai Lianjie, Zhang Junlin, Zhang Jiarong, Wu Minjie, Bi Fuqiang, Wang Bozhou. Progress in Synthesis and Properties of High Energy Density Compounds Regulated by N—F Bond [J]. Chinese Journal of Organic Chemistry, 2020, 40(6): 1484-1501.
[2]	Liu Yuejia, Zhang Xiaojuan, Ning Hongli, Yang Haijun. Studies on the Synthesis and Properties of Energetic Ionic Liquids Based on Imidazolium Compounds [J]. Chin. J. Org. Chem., 2016, 36(5): 1133-1142.
[3]	Dai Lingling, Cui Shengfeng, Damu Guri L. V., Zhou Chenghe. Recent Advances in the Synthesis and Application of Tetrazoles [J]. Chin. J. Org. Chem., 2013, 33(02): 224-244.
[4]	WANG Bo-Zhou*^,a,LAI Wei-Peng^a,LIU Qian^a,LIAN Peng^a,XUE Yong-Qiang^b. Synthesis, Characterization and Quantum Chemistry Study on 3,6-Bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine [J]. Chin. J. Org. Chem., 2008, 28(03): 422-427.
[5]	XU Xiao-Juan^1,2,XIAO He-Ming*^,1, JU Xue-Hai,GONG Xue-Dong². Theoretical Study on Pyrolysis Mechanism forε-Hexanitrohexaazaisowurtzitane [J]. Chin. J. Org. Chem., 2005, 25(05): 536-539.
[6]	CUI Yan-Bin, WANG Hui, RAN Xin-Quan, WEN,Zhen-Yi, SHI Qi-Zhen. Thermodynamic Research on Pyrolysis Mechanism of Carbon Matrix Precursor Ethylbenzene Used for Carbon/Carbon Material [J]. Chinese Journal of Organic Chemistry, 2004, 24(9): 1075-1081.