碱金属卤化物键长、德拜温度和热膨胀系数的温度效应

doi:10.19596/j.cnki.1001-246x.8402

摘要/Abstract

摘要：

以碱金属卤化物为研究对象，根据局域键平均近似方法，从热膨胀系数的定义出发，建立热膨胀系数和键长的温度效应函数表达式。定量获取碱金属卤化物的键长、刚性因子、德拜温度和热膨胀系数。结果表明：①碱金属卤化物的热膨胀系数与结合能成反比；②同类碱金属卤化物中，从氟碱化物到碘碱化物德拜温度逐渐减小而热膨胀系数逐渐增大；③碱金属卤化物的键长在其德拜温度的三分之一处，由非线性转变为线性热伸长。

关键词: 碱金属卤化物, 化学键, 局域键平均近似, 热学性能

Abstract:

Temperature dependence functional expressions of bond length and thermal expansion coefficient of alkali halides without empirical parameters were established with local bond average approach and definition of thermal expansion coefficient. We obtained quantitatively the bond length, rigidity factor, Debye temperature and thermal expansion coefficient of alkali halides. It was found that: ① The thermal expansion coefficient of alkali halides is inversely proportional to the cohesive energy; ② The Debye temperature decreases and the thermal expansion coefficient increases gradually from alkali fluorides to alkali iodides in the same kind of alkali halides; ③ The bond length of alkali halides changes from nonlinear to linear thermal elongation at one third of its Debye temperature.

Key words: alkali halides, chemical bond, local bond average approach, thermal properties

刘进, 孙恩奇, 杨学弦, 朱岭, 黄勇刚. 碱金属卤化物键长、德拜温度和热膨胀系数的温度效应[J]. 计算物理, 2022, 39(3): 335-340.

Jin LIU, Enqi SUN, Xuexian YANG, Ling ZHU, Yonggang HUANG. Temperature Dependence of Bond Length, Debye Temperature and Thermal Expansion Coefficient of Alkali Halides[J]. Chinese Journal of Computational Physics, 2022, 39(3): 335-340.

图/表 3

表1 碱金属卤化物的键长、熔点、原子结合能、德拜温度和刚性因子

Table 1 Bond length, melting point, atomic cohesive energy, Debye temperature and rigidity factor of alkali halides

Material	α(T)		l(T)			References
Material	θ_D(0)/K	A₁(r)	θ_D(0)/K	A₁(r)	l₀/nm	θ_D(0)/K^{[28, 35]}	T_m/K^[33]	E_B(0)/eV^[29]
LiF	742	0.977	735	0.979	0.200 03	735, 751	1 143	5.42
LiCl	429	1.153	429	1.153	0.254 97	429, 530	887	4.43
LiBr	321	1.119	300	1.119	0.272 39	274, 465	820	4.26
LiI	310	1.022	290	1.014	0.297 06	410	719	3.96
NaF	488	1.401	488	1.414	0.230 45	488, 470	1 205	4.81
NaCl	350	1.438	321	1.430	0.279 86	321, 320	1 050	4.09
NaBr	270	1.489	270	1.489	0.296 28	225, 264	1 028	3.86
NaI	235	1.518	235	1.493	0.320 49	164, 230	928	3.66

图1 (a) 锂类和(b)钠类碱金属卤化物热膨胀系数温度效应(实线为理论曲线，散点为实验数据[27-28]。)

Fig.1 Theoretical curves (lines) and experimental data[27-28] (scattered dots) of temperature dependence of thermal expansion coefficients of (a) Li and (b) Na group alkali halides

图2 (a) 锂类和(b) 钠类碱金属卤化物键长温度效应(黑线为理论值，红线表示理论值在高温线性范围的切线，散点为实验数据[27, 33-34]。)

Fig.2 Theoretical values (black lines) and experimental data[27, 33-34] (scattered dots) of temperature dependence of bond length of (a) Li group and (b) Na group alkali halides (The red lines denote tangents of theoretical values over the linear range of high temperature.)

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