高压下Th2N2S的结构相变: 第一性原理计算研究

doi:10.3969/j.issn.1000-5641.2024.03.004

摘要/Abstract

摘要：

基于第一性原理计算和粒子群优化算法, 研究了Th₂N₂S在0~200 GPa压强范围内的晶体结构和物理性质. 研究结果成功再现了常压下的实验相:$P\bar {{3}}m1$相, 同时预测了2个高压下的新结构, 即I4/mmm相和Cmmm相. 确定了一系列由压强诱导的结构相变序列: 由$P\bar {{3}}m1$相转变为I4/mmm相, 然后转变为Cmmm相, 相应的相变压强分别为48.2 GPa和156.2 GPa. Th₂N₂S材料声子色散曲线及弹性常数的结果表明, Th₂N₂S的3相是动力学和力学稳定的. 力学性质的计算结果表明,$P\bar {{3}}m1$相、I4/mmm相和Cmmm相均为韧性材料, 其中, Cmmm相的各向异性程度是3相中最大的. 电子结构的计算表明,$P\bar {{3}}m1$相到I4/mmm相的相变是一个半导体–金属相变.

关键词: 高压结构相变, 结构预测, 晶体结构, 第一性原理计算, 钍基核材料

Abstract:

Based on the first-principles calculations and particle swarm optimization algorithm, the crystal structures and physical properties of Th₂N₂S are examined in the pressure range of 0~200 GPa. Our results successfully reproduce the experimental phase$P\bar {{3}}m1$ at ambient pressure and predicted two new structures at high pressure: the I4/mmm and Cmmm phases. A series of pressure-induced structural phase transitions were determined, namely from the$P\bar {{3}}m1$ phase to the I4/mmm phase, and then to the Cmmm phase, with corresponding phase transition pressures of 48.2 GPa and 156.2 GPa. The phonon dispersion curves and elastic constants of Th₂N₂S indicate that these three phases are dynamically and mechanically stable. The obtained mechanical properties demonstrate the natural ductility of the $P\bar {{3}}m1$, I4/mmm and Cmmm phases. Among them, the anisotropy degree of the Cmmm phase is the largest. Further, our electronic structure calculations show that the phase transition from the$P\bar {{3}}m1$ to I4/mmm is a semiconductor-metal phase transition.

Key words: high-pressure structural phase transition, structure prediction, crystal structure, first-principles calculation, thorium-based nuclear material

中图分类号:

O469

杜润润, 王珊, 柯学志. 高压下Th₂N₂S的结构相变: 第一性原理计算研究[J]. 华东师范大学学报（自然科学版）, 2024, 2024(3): 36-44.

Runrun DU, Shan WANG, Xuezhi KE. Structural phase transitions of Th₂N₂S under high pressure: A first-principles calculation study[J]. Journal of East China Normal University(Natural Science), 2024, 2024(3): 36-44.

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相	压强/GPa	晶格常数/?			原子	$ x $	$ y $	$ z $
相	压强/GPa	a	b	c	原子	$ x $	$ y $	$ z $
$P\bar {3}m1$	0	4.022	4.022	6.942	Th(2d)	0.667	0.333	0.712
					N(2d)	0.333	0.667	0.288
					S(1a)
I4/mmm	48.2	3.199	3.199	13.391	Th(4e)	0.500	0.500	0.362
					N(4e)			0.306
					S(2b)			0.500
Cmmm	156.2	3.604	9.875	2.852	Th(4j)		0.365	0.500
					N(4i)		0.175
					S(2a)	0.500	0.500

相	压强 /GPa	$C_{{11} }$	$C_{{12} }$	$C_{{13} }$	$C_{{14} }$	$C_{{22} }$	$C_{{23} }$	$C_{{33} }$	$C_{{44} }$	$C_{{55} }$	$C_{{66} }$
$P\bar {3 }m1$	0	214.7	107.1	74.2	–2.7			176.5	72.0		53.8
	48.2	411.4	243.9	208.0	–59.6			232.4	162.6		83.8
I4/mmm	48.2	409.6	125.9	163.3				374.1	82.9		111.7
	156.2	726.2	260.5	355.3				579.4	276.5		297.4
Cmmm	156.2	1009.3	263.8	450.1		1074.7	94.5	1025.4	117.1	438.9	231.5
	200.0	1191.5	271.1	521.4		1348.1	110.1	1214.7	141.8	535.0	263.8

相	压强/Gpa	B/GPa	G/GPa	$ \frac{B}{G} $	E/GPa	σ	${A}^{\rm{U}}$
P$\bar {\textit{\rm{3}} }$m1	0	122.6	62.2	1.971	159.6	0.283	0.142
I4/mmm	48.2	233.1	102.8	2.268	268.9	0.308	0.207
Cmmm	156.2	521.8	275.2	1.896	702.1	0.276	1.505

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高压下Th₂N₂S的结构相变: 第一性原理计算研究

Structural phase transitions of Th₂N₂S under high pressure: A first-principles calculation study

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