高压下Ir_2P晶体结构预测与物理性质
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摘要
在压强为0～100 GPa范围内,运用CALYPSO结构搜索技术,结合基于密度泛函理论中的第一性原理方法,对Ir_2P晶体进行结构预测,并对预测出的晶体结构和物理性质进行细致的研究。在常压下,预测得出α-Ir_2P相具有立方结构,其空间群为Fm3m,与实验所得结构一致;压强为86.4 GPa时,发生结构相变,由α-Ir_2P相转变为β-Ir_2P相,为四方结构,其空间群为I4/mmm。在相变过程中,晶体体积发生坍塌,并且出现不连续变化的一级相变。电子性质计算表明,86.4 GPa时,预测的β-Ir_2P相中导带和价带在费米面附近发生交叠,表明其结构具有金属性质;电子局域函数计算表明,β-Ir_2P相具有丰富的化学键,包括极性共价键、金属键和离子键;Bader电荷转移计算得出,由于Ir原子具有较强的电负性,β-Ir_2P相中每个P原子向每个Ir原子电荷转移0.19e。
The crystals of Ir_2P were predicted under the pressure ranging from 0 to 100 GPa using the CALYPSO structure exploration technique with the first-principles method based on the density functional theory. The predicted physical properties and crystal structures were examined in detail. At ambient pressure,the predicted α-Ir_2P phase was found to have a cubic structure with Fm3 m space group, which is consistent with the experimental structure. The pressure-induced structural transformations were unraveled, from theα-Ir_2P phase to the β-Ir_2P phase at 86.4 GPa. The predicted β-Ir_2P phase has I4/mmm space group. In the process of phase transition, the volume of the crystal collapses and a discontinuous first order phase transition occurred. The calculation of the electronic properties showed that the predicted conduction bands and the valence bands of the β-Ir_2P phase overlap near the Fermi surface at 86.4 GPa, indicating that the structure of the β-Ir_2P phase has metallic properties. The electron localization function revealed that theβ-Ir_2P phase has a polar covalent bond, a metallic bond and an ionic bond. The Bader charge transfer calculations showed that each P atom transfers 0.19 e to Ir atom, mainly due to the strong electronegativity of the Ir atoms.
The crystals of Ir_2P were predicted under the pressure ranging from 0 to 100 GPa using the CALYPSO structure exploration technique with the first-principles method based on the density functional theory. The predicted physical properties and crystal structures were examined in detail. At ambient pressure,the predicted α-Ir_2P phase was found to have a cubic structure with Fm3 m space group, which is consistent with the experimental structure. The pressure-induced structural transformations were unraveled, from theα-Ir_2P phase to the β-Ir_2P phase at 86.4 GPa. The predicted β-Ir_2P phase has I4/mmm space group. In the process of phase transition, the volume of the crystal collapses and a discontinuous first order phase transition occurred. The calculation of the electronic properties showed that the predicted conduction bands and the valence bands of the β-Ir_2P phase overlap near the Fermi surface at 86.4 GPa, indicating that the structure of the β-Ir_2P phase has metallic properties. The electron localization function revealed that theβ-Ir_2P phase has a polar covalent bond, a metallic bond and an ionic bond. The Bader charge transfer calculations showed that each P atom transfers 0.19 e to Ir atom, mainly due to the strong electronegativity of the Ir atoms.
引文
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[5]HALL J W,MEMBRENO N,WU J,et al.Low-temperature synthesis of amorphous FeP2 and its use as anodes for Li ion batteries[J].Journal of the American Chemical Society,2012,134(12):5532-5535.
[6]BILTZ W,WEIBKE F,MAY E,et al.Alloyability of platinum and phosphorus[J].Zeitschrift fur Anorganische und Allgemeine Chemie,1935,223(2):129-143.
[7]ZHANG X,QIN J,SUN X,et al.First-principles structural design of superhard material of ZrB4[J].Physical Chemistry Chemical Physics,2013,15(48):20894-20899.
[8]KANER R B,GILMAN J J,TOLBERT S H.Designing superhard materials[J].Science,2005,308(5726):1268-1269.
[9]SHI Y,ZHANG B.Correction:Recent advances in transition metal phosphide nanomaterials:synthesis and applications in hydrogen evolution reaction[J].Chemical Society Reviews,2016,45(6):1781-1781.
[10]CARENCO S,PORTEHAULT D,BOISSIERE C,et al.Nanoscaled metal borides and phosphides:recent developments and perspectives[J].Chemical Reviews,2013,113(10):7981-8065.
[11]LI W,DHANDAPANI B,OYAMA S T.Molybdenum phosphide:a novel catalyst for hydrodenitrogenation[J].Chemistry Letters,1998,27(3):207-208.
[12]OYAMA S T,GOTT T,ZHAO H,et al.Transition metal phosphide hydroprocessing catalysts:a review[J].Catalysis Today,2009,143(1/2):94-107.
[13]ZUMBUSCH M.über die strukturen des uransubsulfids und der subphosphide des iridiums und rhodiums[J].Zeitschrift für Anorganische und Allgemeine Chemie,1940,243(4):322-329.
[14]RUNDQVIST S.Phosphides of the platinum metals[J].Nature,1960,185(4705):31.
[15]RAUB C J,ZACHARIASEN W H,GEBALLE T H,et al.Superconductivity of some new Pt-metal compounds[J].Journal of Physics and Chemistry of Solids,1963,24(9):1093-1100.
[16]WANG P,WANG Y,WANG L,et al.Elastic,magnetic and electronic properties of iridium phosphide Ir2P[J].Scientific Reports,2016,6(9):21787.
[17]SUN X W,BIOUD N,FU Z J,et al.High-pressure elastic properties of cubic Ir2P from ab initio calculations[J].Physics Letters A,2016,380(43):3672-3677.
[18]LIU Z J,SONG T,SUN X W,et al.Thermal expansion,heat capacity and Grüneisen parameter of iridium phosphide Ir2P from quasi-harmonic Debye model[J].Solid State Communications,2017,253:19-23.
[19]WANG Y,LV J,ZHU L,et al.Crystal structure prediction via particle-swarm optimization[J].Physical Review B,2010,82(9):094116.
[20]MONKHORST H J,PACK J D.Special points for Brillouin-zone integrations[J].Physical Review B,1976,13(12):5188.
[21]PERDEW J P,BURKE K,ERNZERHOF M.Generalized gradient approximation made simple[J].Physical Review Letters,1996,77(18):3865-3868.
[22]BORN M,HUANG K.Dynamical theory of crystal lattices[J].American Journal of Physics,1954,39(2):113-127.
[23]SAVIN A,NESPER R,WENGERT S,et al.ELF:the electron localization function[J].Angewandte Chemie International Edition in English,1997,36(17):1808-1832.