典型碱金属卤化物高压相变的第一性原理研究

刘雨诗 章龙 李文广 刘其军 刘正堂 刘福生

刘雨诗, 章龙, 李文广, 刘其军, 刘正堂, 刘福生. 典型碱金属卤化物高压相变的第一性原理研究[J]. 高压物理学报. doi: 10.11858/gywlxb.20240864
引用本文: 刘雨诗, 章龙, 李文广, 刘其军, 刘正堂, 刘福生. 典型碱金属卤化物高压相变的第一性原理研究[J]. 高压物理学报. doi: 10.11858/gywlxb.20240864
LIU Yushi, ZHANG Long, LI Wenguang, LIU Qijun, LIU Zhengtang, LIU Fusheng. First-Principles Investigation of the High-Pressure Phase Transition in Representative Alkali Metal Halides[J]. Chinese Journal of High Pressure Physics. doi: 10.11858/gywlxb.20240864
Citation: LIU Yushi, ZHANG Long, LI Wenguang, LIU Qijun, LIU Zhengtang, LIU Fusheng. First-Principles Investigation of the High-Pressure Phase Transition in Representative Alkali Metal Halides[J]. Chinese Journal of High Pressure Physics. doi: 10.11858/gywlxb.20240864

典型碱金属卤化物高压相变的第一性原理研究

doi: 10.11858/gywlxb.20240864
基金项目: 国家自然科学基金(12072299);中央高校基本科研业务费专项资金(2682024GF019)
详细信息
    作者简介:

    刘雨诗(2000-),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:3295107084@qq.com

    通讯作者:

    李文广(1998-),男,博士研究生,主要从事高压下凝聚态物质结构与物性的理论研究. E-mail:wenguangli1@163.com

    刘福生(1966-),男,博士,教授,主要从事高温高压下凝聚态物质结构与物性研究. E-mail:fusheng_l@163.com

  • 中图分类号: O521.2

First-Principles Investigation of the High-Pressure Phase Transition in Representative Alkali Metal Halides

  • 摘要: 基于密度泛函理论的第一性原理计算方法,研究了NaCl、KCl和KBr晶体在不同压力下相Ⅰ和相Ⅱ构型的几何、电子和力学性质,探讨了这些性质与相变点之间的关系,利用吉布斯自由能法对NaCl、KCl与KBr晶体的相变点进行判断。结果显示,对于NaCl的相Ⅰ结构,在0~30 GPa压力范围内,随着压力的升高,带隙不断增大;在30~50 GPa压力范围内,带隙随着压力的升高而下降,30 GPa正位于NaCl相Ⅰ结构的相变点。这表明根据电子结构判断金属卤化物在压力作用下的相变点具有一定的可行性。由高压下的晶体结构、声子谱以及力学稳定性无法对碱金属卤化物的相变点进行判断。通过吉布斯自由能法计算出了NaCl、KCl和KBr的相变点,分别为22.26、3.47和3.11 GPa。

     

  • 图  (a) NaCl型结构,(b) CsCl型结构

    Figure  1.  (a) NaCl-type structure; (b) CsCl-type structure

    图  6种结构在稳定压力区间的声子谱:(a) 零压下NaCl相Ⅰ,(b) 30.6 GPa下NaCl相Ⅱ,(c) 零压下KCl相Ⅰ,(d) 2.12 GPa下KCl相Ⅱ,(e) 零压下KBr相Ⅰ,(f) 2.20 GPa下KBr相Ⅱ

    Figure  2.  Phonon spectra for six structures in the stable pressure range: (a) NaCl phase Ⅰ at zero pressure; (b) NaCl phase Ⅱ at 30.6 GPa; (c) KCl phase Ⅰ at zero pressure; (d) KCl phase Ⅱ at 2.12 GPa; (e) KBr phase Ⅰ at zero pressure; (f) KBr phase Ⅱ at 2.20 GPa

    图  压力下6种结构的晶格常数a的变化:(a) 0~50 GPa下NaCl的相Ⅰ,(b) 0~50 GPa下NaCl的相Ⅱ,(c) 0~5 GPa下KCl的相Ⅰ,(d) 0~5 GPa下KCl的相Ⅱ,(e) 0~5 GPa下KBr的相Ⅰ,(f) 0~5 GPa下KBr的相Ⅱ

    Figure  3.  Lattice parameter a changes for six structures under pressure: (a) NaCl phase Ⅰ at 0−50 GPa; (b) NaCl phase Ⅱ at 0−50 GPa; (c) KCl phase Ⅰ at 0−5 GPa; (d) KCl phase Ⅱ at 0−5 GPa; (e) KBr phase Ⅰ at 0−5 GPa; (f) KBr phase Ⅱ at 0−5 GPa

    图  压力下6种结构的独立弹性常数:(a) 0~50 GPa下NaCl的相Ⅰ,(b) 0~50 GPa下NaCl的相Ⅱ,(c) 0~5 GPa下KCl的相Ⅰ,(d) 0~5 GPa下KCl的相Ⅱ,(e) 0~5 GPa下KBr的相Ⅰ,(f) 0~5 GPa下KBr的相Ⅱ

    Figure  4.  Independent elastic constants for six structures under pressure: (a) NaCl phase Ⅰ at 0−50 GPa; (b) NaCl phase Ⅱ at 0−50 GPa; (c) KCl phase Ⅰ at 0−5 GPa; (d) KCl phase Ⅱ at 0−5 GPa; (e) KBr phase Ⅰ at 0−5 GPa; (f) KBr phase Ⅱ at 0−5 GPa

    图  压力下6种结构的能带带隙:(a) NaCl相Ⅰ,(b) NaCl相Ⅱ,(c) KCl相Ⅰ,(d) KCl相Ⅱ,(e) KBr相Ⅰ,(f) KBr相Ⅱ

    Figure  5.  Band gaps of six structures under pressure: (a) NaCl phase Ⅰ; (b) NaCl phase Ⅱ; (c) KCl phase Ⅰ; (d) KCl phase Ⅱ; (e) KBr phase Ⅰ; (f) KBr phase Ⅱ

    图  NaCl、KCl和KBr的相Ⅰ与相Ⅱ的吉布斯自由能之差随压力的变化

    Figure  6.  Variations of Gibbs free energy difference of phase Ⅰ and phase Ⅱ structures of NaCl, KCl and KBr with pressure

    表  1  NaCl、KCl、KBr的相Ⅰ和相Ⅱ结构的晶格常数和原胞体积

    Table  1.   Lattice constant and cell volumes for phase Ⅰ and phase Ⅱ structures of NaCl, KCl and KBr

    Material Phase Space group p/GPa a V03 Method
    NaCl $Fm\overline 3 m $ 0 5.672 45.637 This work
    0 5.640 44.830 Experiment[18]
    NaCl $Pm\overline 3 m $ 30.6 3.043 28.186 This work
    30.6 3.010 27.271 Experiment[15]
    KCl $Fm\overline 3 m $ 0 6.325 63.274 This work
    0 6.294 62.333 Experiment[19]
    KCl $Pm\overline 3 m $ 2.12 3.681 49.864 This work
    2.12 3.670 49.431 Experiment[20]
    KBr $Fm\overline 3 m $ 0 6.598 71.826 This work
    0 6.586 71.418 Experiment[21]
    KBr $Pm\overline 3 m $ 2.20 3.833 56.293 This work
    2.20 3.740 52.314 Experiment[22]
    下载: 导出CSV

    表  2  NaCl、KCl、KBr的相Ⅰ(零压)和相Ⅱ(稳定压力)结构的独立弹性常数

    Table  2.   Independent elastic constants for phase Ⅰ (at zero pressure) and phase Ⅱ (at steady pressure) of NaCl, KCl and KBr

    MaterialPhaseC11/GPaC12/GPaC44/GPa
    NaCl78.6429.54810.509
    230.43179.37331.849
    KCl51.0875.1075.587
    67.76321.99319.573
    KBr49.3383.9594.636
    65.45122.26519.708
    下载: 导出CSV

    表  3  NaCl、KCl、KBr的相Ⅰ和相Ⅱ结构的声子谱虚频统计

    Table  3.   Statistics of imaginary frequencies in the phase Ⅰ and phase Ⅱ phonon spectra for NaCl, KCl and KBr

    Pressrue/GPa Imaginary frequency
    NaCl
    (Phase Ⅰ)
    NaCl
    (Phase Ⅱ)
    KCl
    (Phase Ⅰ)
    KCl
    (Phase Ⅱ)
    KBr
    (Phase Ⅰ)
    KBr
    (Phase Ⅱ)
    0 F F F F F F
    0.5 F F F F F F
    1.0 T F F F F F
    1.5 T F F F F F
    2.0 T F F F F F
    2.5 T F F F F F
    3.0 T F F F F F
    3.5 T F F F F F
    4.0 T F F F F F
    4.5 T F F F F F
    5.0 T F F F F F
    Note: “T” is imaginary frequency, while “F” is not imaginary frequency.
    下载: 导出CSV
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  • 收稿日期:  2024-08-05
  • 修回日期:  2024-09-03
  • 网络出版日期:  2024-10-27

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