含能离子盐TKX-50状态方程及热力学性质的第一性原理研究

doi:10.19596/j.cnki.1001-246x.8740

摘要/Abstract

摘要：

采用基于密度泛函理论的第一性原理, 结合德拜模型和晶格动力学理论, 对二羟基联四唑羟铵盐(TKX-50)在温度和压力加载下的热力学性质和状态方程进行研究。计算表明: TKX-50在零温零压下的晶格参数与实验数据吻合较好。在此基础上分析了TKX-50在不同温度和压力下的晶格结构演化及相关热力学性质。结果表明: TKX-50晶格沿a轴方向最难压缩; 定容热容受压强和温度强烈的影响; 德拜温度、格林艾森常数、热膨胀系数受压强影响较大。计算结果不仅揭示了温度和压力对TKX-50热力学性质的影响规律, 为预测和解释其温压性能提供指导, 也能够为TKX-50工程应用和风险评估提供必要的理论支撑。

关键词: 高温高压, TKX-50, 热力学性质, 第一性原理

Abstract:

By employing first-principles based on density functional theory, combined with the Debye model and lattice dynamics theory, the themodynamic properties and state equation of TKX-50 under high temperture and pressure are calculated. It is shown that, the calculated lattice constants of TKX-50 agree well with the available experimental and other theoretical data. And then we calculate the lattice structure and relate thermodynamic properties under different temperature and pressure. The results show that the lattice of TKX-50 is the most difficult to compress along the a-axis; the thermal capacity is influenced by temperature and pressure strongly; the Debye temperature, Gruneison constant, and the thermal expansion coefficient changes rapidly with temperature. The results of this paper not only reveal how the thermodynamic properties of TKX-50 change with temperature and pressure, a guide to predict and explain its temperature pressure performance, but also provide necessary theoretical support, for the engineering application and risk assessment of TKX-50.

Key words: high temperature and high pressure, TKX-50, thermodynamic properties, first-principles

中图分类号:

周梦, 陶应奇, 周晓云, 张宇龙, 程才. 含能离子盐TKX-50状态方程及热力学性质的第一性原理研究[J]. 计算物理, 2024, 41(4): 487-493.

Meng ZHOU, Yingqi TAO, Xiaoyun ZHOU, Yulong ZHANG, Cai CHENG. First-principles Study on State Equation and Thermodynamic Properties of Energetic Ionic Salt TKX-50[J]. Chinese Journal of Computational Physics, 2024, 41(4): 487-493.

图/表 7

图1 TKX-50的分子结构

Fig.1 Molecular structure of TKX-50

图2 TKX-50在零温时能量随体积的变化

Fig.2 Variation of total energy with volume for TKX-50 at 0 K

表1 TKX-50在0 K时平衡结构参数计算值与实验值比较

Table 1 Comparison of calculated equilibrium structure parameters of TKX-50 at 0 K and experimental data

	TKX-50计算值	TKX-50实验值/(100 K)^[7]	TKX-50实验值/(173 K)^[7]	TKX-50实验值/(298 K)^[7]
a/nm	0.556 58	0.548 72	0.542 60	0.544 08
b/nm	1.137 64	1.172	1.165 97	1.175 14
c/nm	0.642 49	0.648 33	0.650 13	0.656 12
α/°	90	90	90	90
β/°	96.407 5	95.402	95.256	95.071
γ/°	90	90	90	90
V/nm³	0.406 816	0.408 97	0.409 58	0.417 86

图3 TKX-50 (a)晶格参数和(b)体积在不同温度下随压力P的变化

Fig.3 Variation of TKX-50 (a) lattice constants and (b) volume with P at different temparatures

图4 TKX-50在不同温度时(a)体模量及(b)其对压强的一阶导数随压强的变化

Fig.4 Variation of (a) bulk modulus and (b) its first derivative of pressure of TKX-50 with pressure at different temperatures

图5 TKX-50在不同压强下(a)定容热容和(b)德拜温度随温度的变化

Fig.5 Variation of (a) heat capacity CV and (b) Debye temperature of TKX-50 with T at different pressures

图6 TKX-50在不同温度下(a)格林艾森常数和(b)热膨胀系数随压强的变化关系

Fig.6 Variation of (a) Gruneison constant and (b) thermal expansion coefficient of TKX-50 with pressure at different temperatures

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