RDX及其衍生物高温热解的反应分子动力学模拟

引用本文: 彭莉娟, 姚倩, 王静波, 李泽荣, 朱权, 李象远. RDX及其衍生物高温热解的反应分子动力学模拟[J]. 物理化学学报, 2017, 33(4): 745-754. doi: 10.3866/PKU.WHXB201701161 shu

Citation: PENG Li-Juan, YAO Qian, WANG Jing-Bo, LI Ze-Rong, ZHU Quan, LI Xiang-Yuan. Pyrolysis of RDX and Its Derivatives via Reactive Molecular Dynamics Simulations[J]. Acta Physico-Chimica Sinica, 2017, 33(4): 745-754. doi: 10.3866/PKU.WHXB201701161 shu

RDX及其衍生物高温热解的反应分子动力学模拟

彭莉娟 ^1, ,
姚倩 ^2, ,
王静波 ^3, ,
李泽荣 ^2, ,
朱权 ^3, ,
李象远 ^3,

1.
四川大学空天科学与工程学院, 成都 610065;
2.
四川大学化学学院, 成都 610064;
3.
四川大学化学工程学院, 成都 610065
基金项目:
国家自然科学基金（91441132）和教育部新世纪优秀人才支持计划（NCET-13-0398）资助项目

摘要: 本文采用ReaxFF 反应分子动力学方法，研究了RDX及其衍生物晶体在高温条件下（2000、2500 和3000 K）的热分解机理以及主要产物随时间的变化情况。结果表明：RDX及其衍生物晶体热解的第一步反应均为N―NO₂键断裂生成NO₂分子，随后反应由于六元环上和侧链基团的不同导致侧链脱除或开环反应的顺序不同。在这四种单胞体系热解中，NO₂和NO分子为共同的中间产物，形成之后迅速发生次级反应并最终生成N₂。各体系热解终产物一致，均为N₂、H₂O和CO₂，其中N₂分子数最多，大于20 个。由于原始分子结构和组成中C/N比、H/O比的不同，各体系热解后H₂O和CO₂分子数目相差较大。不同温度下，各单胞体系热分解生成的最大含碳团簇中C原子数均较小。在进一步超胞体系的模拟中，RDX和RDX-D2体系生成的含碳团簇中C原子数分别达到约30 和16 个，远高于单胞模拟，且受温度影响较大；而RDX-D1 和RDX-D3 单胞或超胞模拟结果相近，均未生成含碳团簇，仅存在小分子含碳碎片。因此，初始分子的结构和元素比对含碳团簇的生成有明显影响。

关键词:

English

Pyrolysis of RDX and Its Derivatives via Reactive Molecular Dynamics Simulations

1.
School of Aeronautics & Astronautics, Sichuan University, Chengdu 610065, P. R. China;
2.
College of Chemistry, Sichuan University, Chengdu 610064, P. R. China;
3.
School of Chemical Engineering, Sichuan University, Chengdu 610065, P. R. China
Received Date: 22 October 2016
Revised Date: 16 January 2017
Available Online: 16 January 2017
Fund Project:
The project was supported by the National Natural Science Foundation of China (91441132) and Program for New Century Excellent Talents in University of Ministry of Education of China (NCET-13-0398).

Abstract: The thermal decomposition mechanisms of cyclotrimethylene trinitramine (RDX) and its derivatives are investigated using ReaxFF reactive molecular dynamics simulation at high temperatures (2000, 2500, and 3000 K). It is shown that the first pyrolysis step of RDX and its derivatives is the N―NO₂ homolytic cleavage to produce NO₂; however, the subsequent reaction mechanism is completely different due to the different sixmembered rings and side chain groups. In these four model systems, NO₂ and NO molecules are common intermediates in the thermal decomposition process, which eventually transform to N₂ in the following reactions. The most stable products are N₂, H₂O, and CO₂ in the thermal process, among which N₂ has the maximum molecular number (more than 20). The numbers of cracked H₂O and CO₂ molecules are very different in the four model systems due to the different C/N and H/O ratios. At different temperatures, the maximum numbers of carbon atoms in the carbon clusters are all small in the unit cell simulations of the four systems. In the further super cell simulation for RDX and RDX-D2 the numbers of carbon atoms reach about 30 and 16, respectively, which are higher than those from the unit cell simulation. In both the unit and super cell simulations for RDX-D1 and RDX-D3, the carbon cluster cannot be formed and there exist only small carbon molecular fragments. Therefore, the initial molecular structure and elemental ratio have a large effect on the production of carbon clusters.

Key words:

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RDX及其衍生物高温热解的反应分子动力学模拟

English

Pyrolysis of RDX and Its Derivatives via Reactive Molecular Dynamics Simulations

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RDX及其衍生物高温热解的反应分子动力学模拟

English

Pyrolysis of RDX and Its Derivatives via Reactive Molecular Dynamics Simulations

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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