硝酸铷高压相变和物理性质的第一性原理研究

王晓雪; 丁雨晴; 王晖

doi:10.11858/gywlxb.20240776

硝酸铷高压相变和物理性质的第一性原理研究

doi: 10.11858/gywlxb.20240776

哈尔滨师范大学物理与电子工程学院, 黑龙江哈尔滨　150025

基金项目: 国家自然科学基金（11974135）

详细信息

作者简介:
王晓雪（1998－），女，硕士研究生，主要从事高压下凝聚态物质结构与物性的理论研究. E-mail：wx@fysik.cn

通讯作者:
王　晖（1981－），男，博士，教授，主要从事高压下凝聚态物质结构与物性的理论研究. E-mail：wh@fysik.cn

中图分类号: O521.2; O469
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出版历程
- 收稿日期: 2024-04-01
- 修回日期: 2024-04-09
- 录用日期: 2024-04-15
- 刊出日期: 2024-07-25

First-Principles Study of the High-Pressure Phase Transition and Physical Properties of Rubidium Nitrate

School of Physics and Electronic Engineering, Harbin Normal University, Harbin 150025, Heilongjiang, China

摘要

摘要: 采用基于密度泛函理论的第一性原理计算，并结合CALYPSO晶体结构预测软件，系统地探索了零温下RbNO₃的高压结构与物理性质。基于RbNO₃-Ⅳ相的实验数据，比较了4种不同泛函的准确性，发现PBEsol泛函的准确性最高。基于该泛函预测到RbNO₃在零温下的相变序列为R3m → Pnma → Pmmn （实验Ⅴ相），相变压强依次为1.7 和8.2 GPa，2次相变均为一级相变，体积坍塌率分别为3.73%和2.54%。研究结果表明，低压下RbNO₃可能存在有别于实验（常温常压下）给出的P3₁结构的低温新相。3个相在各自能量稳定的压强范围内均满足“伯恩-黄昆”弹性稳定性判据，且在整个布里渊区中均不存在声子虚频现象，表明它们均具有动力学稳定性。电子性质分析表明，3个相均为半导体，相变引起的带隙变化普遍较小，加压普遍地抑制了铷离子的电荷向硝酸根离子转移。所预测的高压相变序列及各个相的弹性、晶格动力学、电子结构性质可为后续实验与理论研究提供参考。
- 高压 /
- 相变 /
- 第一性原理 /
- RbNO₃
Abstract: The high-pressure structure and physical properties of RbNO₃ at zero temperature was systematically explored using first-principles calculations based on density generalized theory combined with CALYPSO crystal structure predictions. The accuracy of four different functionals was compared based on experimental data of the RbNO₃-Ⅳ phase, and the revised PBE for solids (PBEsol) functional was found to be the most reliable. The zero-temperature phase transition sequence of RbNO₃ predicted is R3m→Pnma→Pmmn (experimental phaseⅤ) based on the PBEsol functional, and the two phase transition pressures are 1.7 and 8.2 GPa. The two phase transitions are first-order phase transitions, and the volume collapse rates reach 3.73% and 2.54%, respectively. This suggests that RbNO₃ at low pressure may have new low-temperature phases those are different from P3₁ structure given by experiment in the room temperature and ambient pressure. In the energy-stabilized pressure interval, all three phases satisfy the “Born-Huangkun” elastic stability criteria, and there is no phonon virtual frequency phenomenon in the whole Brillouin zone, which indicates that they are dynamically stable structures. The electronic property analysis showed that the three phases are semiconductors, and the band gap changes caused by the phase transition are generally small, but the pressure generally inhibits the charge transfer from alkali metal ions to nitrate ions. The high-pressure phase transition sequence predicted in this paper and the elasticity, lattice dynamics, and electronic structure properties of the individual phases can provide a reference for subsequent experimental and theoretical studies.
- high pressure /
- phase transition /
- first principles /
- RbNO₃

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图 1 R3m、P3₁和Pmmn相相对于Pnma相的热力学焓差曲线

Figure 1. Calculated enthalpy difference of R3m, P3₁ and Pmmn phases relative to Pnma as a function of pressure

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图 2 R3m、Pnma、P3₁和Pmmn相的体积随压强的变化

Figure 2. Calculated volume of R3m, Pnma, P3₁ and Pmmn phases as a function of pressure

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图 3 R3m、Pnma和Pmmn相的晶体结构

Figure 3. Crystal structures of R3m, Pnma, and Pmmn phase

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图 4 R3m、Pnma和Pmmn相的声子色散曲线以及声子态密度

Figure 4. Phonon-dispersion curves and the PHDOS of R3m, Pnma and Pmmn phase

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图 5 R3m、Pnma和Pmmn相的电子局域函数

Figure 5. Electron localization function of R3m, Pnma and Pmmn phase

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图 6 R3m、Pnma和Pmmn相的COHP

Figure 6. Crystal orbital Hamilton populations of R3m, Pnma and Pmmn phase

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图 7 R3m、Pnma和Pmmn相的能带结构和电子态密度

Figure 7. Band structures and partial densities of states of R3m, Pnma and Pmmn phases

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表 1 RbNO₃-Ⅳ相的晶格常数的理论值与实验值的比较

Table 1. Comparison between experimental and calculated lattice parameters of RbNO₃-Ⅳ phase

Method	Condition	a/Å	c/Å	Volume/Å³
Simulation	PBE	10.68(+1.62%)	7.60(+1.88%)	867.56(+5.29%)
	vdW-DF	10.72(+2.00%)	7.62(+2.14%)	876.29(+6.35%)
	PBEsol	10.39(−1.14%)	7.39(−0.94%)	797.69(−3.19%)
	RPBE	11.14(+5.99%)	7.91(+6.03%)	982.63(+19.26%)
Experiment	T=296 K^[24]	10.47	7.44	815.58
	T=298 K^[25]	10.55	7.47	831.43
	Average	10.51	7.46	823.96

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表 2 高压下R3m、Pnma和Pmmn相的晶格参数和原子位置

Table 2. Lattice parameters and atomic coordinates of R3m, Pnma and Pmmn phases at different pressures

Phase	Pressure/GPa	Lattice parameters	Wyckoff positions
R3m	0	a=b=5.64 Å, c=9.48 Å, α=β=90°, γ=120°	Rb1: 3a(0.3333, 0.6667, 0.1699) N1: 3a(0.3333, 0.6667, 0.7275) O1: 9b(0.5373, 0.0746, 0.3953)
Pnma	4	a=7.18 Å, b=5.61 Å, c=6.77 Å, α=β=γ=90°	Rb1: 4c(0.483, 0.250, 0.686) N1: 4c(0.350, 0.250, 0.122) O1: 4c(0.448, 0.250, 0.275) O5: 8d(0.302, 0.444, 0.043)
Pmmn	12	a=4.67 Å, b=5.34 Å, c=4.63 Å, α=β=γ=90°	Rb1: 2b(0.500, 0, 0.400) N1: 2a(0, 0, 0.992) O1: 2a(0, 0, 0.721) O3: 4e(0, 0.204, 0.128)

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表 3 高压下R3m、Pnma和Pmmn相的弹性常数和弹性模量

Table 3. Elastic constant and elastic moduli of R3m, Pnma and Pmmn phase at high pressure GPa

Phase	Pressure	C₁₁	C₁₂	C₁₃	C₁₄	C₂₂	C₂₃	C₃₃	C₄₄	C₅₅	C₆₆	B	G	E
R3m	0	37	14	11	−4			13	7		12	15	7	19
	4	75	28	21	−8			39	6		23	35	11	29
	12	124	46	42	−15			94	12		39	66	19	52
Pnma	0	22	7	9		41	9	32	7	10	9	16	10	24
	4	50	19	30		73	19	69	12	17	19	36	17	44
	12	96	43	59		129	35	119	19	−5	34	69	−57	−236
Pmmn	0	26	9	9		50	16	54	15	5	5	21	10	26
	4	60	16	25		84	32	83	33	20	9	40	21	53
	12	113	25	53		143	59	129	60	37	16	72	35	91

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表 4 高压下R3m、Pnma和Pmmn相的元胞内的Bader电荷转移

Table 4. Calculated Bader charges within R3m, Pnma and Pmmn phases primitive cells at different pressures

Phase	Pressure/GPa	Atoms	Number	Charge/e	Charge transfer/e
R3m	0	Rb	1	8.10	0.90
		N	1	4.16	0.84
		O	3	6.58	−0.58
Pnma	4	Rb	4	8.13	0.87
		N	4	4.13	0.87
		O1	4	6.57	−0.57
		O2	4	6.58	−0.58
		O3	4	6.59	−0.59
Pmmn	12	Rb	2	8.14	0.86
		N	2	4.07	0.93
		O1	2	6.58	−0.58
		O2	2	6.59	−0.59
		O3	2	6.62	−0.62

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