Molecular simulation progress in studying thermodynamic properties and potential functions of fluorides

doi:10.11949/0438-1157.20220575

Abstract

Abstract:

Developing chemical process of uranium purification is significant to the improvement in China’s nuclear energy industry. However, it is always limited by the deficiency in fundamental thermodynamics property information. Molecular simulation methods provide an opportunity to address the above challenges due to their efficient, environmentally friendly, and economical properties for predicting properties. In this paper, firstly, various of simulation methods on thermodynamics properties are summarized, the development and advantage/disadvantage of common force-field (FF) and potential function are introduced, most importantly, their applicability on computing fluorides is discussed. Then, the progress of simulating thermodynamics properties of fluorides is summarized, and the impact on applied FF and potential function is discussed and evaluated. High computation efficiency and accuracy of temperature dependent intermolecular potential (TDIP) are found in calculating the second virial coefficient, viscosity, and vapor-liquid coexistence properties. However, the summary shows that there are lots of fundamental questions needed to be solved before further improving the accuracy of computation of fluorides. Therefore, the development of molecular simulation method of fluoride thermodynamics was prospected, hoping to provide a practical basis of design of uranium purification process.

Key words: fluoride, molecular simulation, temperature dependent intermolecular potential, thermodynamic properties

摘要：

发展干法铀纯化工艺对我国核能产业发展至关重要，但一直受基础热力学数据缺失的限制。因分子模拟方法具有高效、环保、经济的预测特性，为解决以上挑战提供了机遇。本文归纳总结了分子模拟计算物质热力学性质的多种方法，系统地介绍了模拟计算中不同力场和势能函数的发展情况和优势/缺陷，指明了对氟化物体系的适用性。随后，综述了氟化物热力学性质的分子模拟进展，分析并评价了力场与势能函数选择对计算结果的影响，表明与温度相关的分子间势能函数(TDIP)在第二维里系数、黏度和气液共存性质等的模拟中展现的较高模拟效率和准确性。为进一步提升计算数据的准确性，尚有很多基础科学问题需要解决。因此，本文最后对分子模拟方法在氟化物热力学领域的发展进行了展望，以期为工艺设计提供实践基础。

关键词: 氟化物, 分子模拟, 与温度相关的分子间势能函数, 热力学性质

CLC Number:

O 641.3

Songtao YANG, Dongyang LI, Yuqing NIU, Xingang LI, Shaohui KANG, Hong LI, Kaikai YE, Zhiquan ZHOU, Xin GAO. Molecular simulation progress in studying thermodynamic properties and potential functions of fluorides[J]. CIESC Journal, 2022, 73(9): 3828-3840.

杨松涛, 李东洋, 牛玉清, 李鑫钢, 康绍辉, 李洪, 叶开凯, 周志全, 高鑫. 氟化物势能函数和热力学性质的分子模拟研究进展[J]. 化工学报, 2022, 73(9): 3828-3840.

Figures/Tables 11

References 85

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分类	方法	特点
直接模拟法	GEMC	适合简单流体和较复杂流体
	CBMC	适合复杂大分子或含有氢键等强相互作用的稠密流体
	RGEMC	适合模拟反应体系的相平衡
间接模拟法	NPT+TP	模拟时间长，较为烦琐，应用较少
	GCMC	适合非均相系统
	GDI	主要用于纯物质的计算，应用较多
	HRW	气液相波动剧烈的临界区的模拟
新方法	HRW和GEMC相结合	尚不成熟
	kMC	适合模拟稀薄流体和缔合流体的相平衡
	Bin-CMC	气固相平衡

分类	方法	特点
直接模拟法	GEMC	适合简单流体和较复杂流体
	CBMC	适合复杂大分子或含有氢键等强相互作用的稠密流体
	RGEMC	适合模拟反应体系的相平衡
间接模拟法	NPT+TP	模拟时间长，较为烦琐，应用较少
	GCMC	适合非均相系统
	GDI	主要用于纯物质的计算，应用较多
	HRW	气液相波动剧烈的临界区的模拟
新方法	HRW和GEMC相结合	尚不成熟
	kMC	适合模拟稀薄流体和缔合流体的相平衡
	Bin-CMC	气固相平衡

方法	文献	RMSD（B）
TDIP	[18]	35.449
TDIP	[22]	3.8931
TIIP	[8]	38.895
	[9]	151.31
	[10]	147.66
	[11]	261.01
	[22]	11.187

方法	文献	RMSD（B）
TDIP	[18]	35.449
TDIP	[22]	3.8931
TIIP	[8]	38.895
	[9]	151.31
	[10]	147.66
	[11]	261.01
	[22]	11.187

数据来源	RMSD (B)/(cm³/mol)
数据来源	Oh关联式	Tsonopoulos 关联式	Dymond关联式	Zarkova & Hohm关联式
Ref.[10]	71	49.7	98.9	70.8
Ref.[12]	77	94.3	40	77.3
all data	68	82.6	65.1	75.2
数据来源	RMSD (η)/%
数据来源	Oh关联式	Lucas关联式	Zarkova & Hohm关联式
Ref.[83]	3.2	3	1.8
Ref.[84]	2.9	4.2	0.7
Ref.[85]	3.7	4.9	2.3
Ref.[10]	3.5	4.8	0.7
all data	3.4	4.4	1.5