基体（TDI-TMP-T313）与氧化剂（AP）相互作用的第一性原理研究

doi:10.11949/0438-1157.20220262

摘要/Abstract

摘要：

采用密度泛函理论（DFT）研究了氧化剂高氯酸铵（001）、（210）、（011）、（201）四种晶面的表面能并对其进行从头算分子动力学（AIMD）模拟，测试其稳定性。基体组分甲苯二异氰酸酯（TDI）、三羟基甲基丙烷（TMP）、三氟化硼三乙醇胺络合物（T313）在氧化剂晶面的吸附能同样由DFT进行计算。针对基体和氧化剂之间的相互作用进行了化学理论分析，最后选取吸附物和晶面相互作用最强的T313-AP（201）体系，模拟其分子电子结构并观察原子间的电荷转移情况。通过多种理论方法在分子尺度上揭示键合剂（T313）与氧化剂（AP）的作用机制，证实老化过程中产生的关键产物来源。

关键词: 基体, 氧化剂, 键合剂, 叠氮推进剂, 密度泛函理论, 燃料, 计算化学, 表面

Abstract:

Density functional theory (DFT) is used to study the surface energies of four crystal planes of oxidant-ammonium perchlorate (001), (210), (011), (201), and the surfaces' stability is tested by ab initio molecular dynamics (AIMD) simulation. The adsorption energies of the matrix components-toluene diisocyanate (TDI), trihydroxymethyl propane (TMP) and boron trifluoride tritylamine complex (T313) on the crystal planes of oxidizing agent are also calculated by DFT. The interaction between matrix and oxidizing agent is analyzed theoretically. Eventually, the T313-AP (201) system with the strongest interaction between adsorbent and crystal plane is selected for bader charge analysis to simulate its molecular electronic structure and observe the charge transfer between atoms. The mechanism of interaction between bonding agent (T313) and oxidizing agent (AP) is revealed on a molecular scale by various theoretical methods. The sources of critical products produced in the ageing process are confirmed.

Key words: matrix, oxidizing agent, bonding agent, azide propellant, density functional theory, fuel, computational chemistry, surface

中图分类号:

TJ 763

俞夏琪, 冯格, 赵金燕, 李嘉远, 邓声威, 郑靖楠, 李雯雯, 王亚秋, 沈榄, 刘旭, 徐威威, 王建国, 王式彬, 姚子豪, 毛成立. 基体（TDI-TMP-T313）与氧化剂（AP）相互作用的第一性原理研究[J]. 化工学报, 2022, 73(8): 3511-3517.

Xiaqi YU, Ge FENG, Jinyan ZHAO, Jiayuan LI, Shengwei DENG, Jingnan ZHENG, Wenwen LI, Yaqiu WANG, Lan SHEN, Xu LIU, Weiwei XU, Jianguo WANG, Shibin WANG, Zihao YAO, Chengli MAO. A first-principles study of the interaction between TDI-TMP-T313 and AP[J]. CIESC Journal, 2022, 73(8): 3511-3517.

图/表 9

图1 高氯酸铵晶胞模型示意图(a) 主视图; (b) 侧视图; (c) 俯视图; (d) 立体图

Fig.1 Schematic representation of unit cell of AP(a) front view; (b) side view; (c) top view; (d) stereogram

图2 AP晶面结构优化（左侧为前视图，右侧为俯视图）

Fig.2 AP crystal plane structure optimization(front view for the left and top view for the right)

图3 基于AIMD计算的AP各晶面稳定性研究（红色圆圈内为H2O,蓝色为NH3,绿色为HClO4,黑色为ClO3）

Fig.3 Study on the stability of AP crystal planes based on AIMD(inside the red circle is H2O, blue is NH3, green is HClO4, black is ClO3)

图4 固化剂TDI、交联剂TMP、键合剂T313在氧化剂AP上的相互作用

Fig.4 The interaction of curing agent TDI, crosslinking agent TMP and bonding agent T313 on oxidizer AP

表1 固化剂TDI、交联剂TMP、键合剂T313在氧化剂AP上的吸附能

Table 1 Adsorption energy of curing agent TDI， crosslinking agent TMP and bonding agent T313 on oxidizer AP

物质-AP晶面	吸附能/eV	物质-AP晶面	吸附能/eV
TDI-(001)	-1.47	TMP- (201)	-1.68
TMP-(001)	-1.63	TDI- (201)	-0.66
T313-(001)	-1.43	T313-(201)	-2.20
TDI- (011)	-0.59	TMP-(210)	-1.08
TMP- (011)	-1.32	TDI-(210)	-0.58
T313-(011)	-0.86	T313-(210)	-0.27

图5 T313-AP（201）解离情况

Fig.5 Dissociative situation of T313-AP(201)

图6 T313-AP（201）的CDD图（粉色，紫色，红色和绿色分别代表H，N，O和Cl原子）

Fig.6 CDD for T313-AP(201)(pink, purple, red and green represent H, N, O and Cl atoms, respectively)

表2 T313-AP（201）的Bader电荷分析

Table 2 Bader charge analysis of T313-AP（201）

原子	数量	价态	电荷	得失电子情况
B	1	3	0.67	2.33
C	6	4	3.89	0.11
Cl	32	7	3.94	3.06
F	3	7	7.81	-0.81
H	143	1	0.42	0.58
N	33	5	6.39	-1.39
O	133	6	7.02	-1.02

表3 T313在T313-AP（201）的Bader电荷分析

Table 3 Bader charge analysis of T313 in T313-AP（201）

原子	数量	价态	电荷	得失电子情况
B	1	3	0.67	2.33
C	6	4	3.54	0.46
F	3	7	7.81	-0.81
H	15	1	0.79	0.21
N	1	5	6.09	-1.09
O	3	6	7.15	-1.15
总体	29	—	—	1.21

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