物理学报2025，Vol.74Issue(10)：85-94,10.DOI:10.7498/aps.74.20241631
基于第一性原理对碱金属钒酸盐AV3O8(A=Li,Na,K,Rb)大双折射率的机理研究
First-principles study of mechanism of high birefringence in alkali metal vanadates AV3O8(A=Li,Na,K,Rb)
摘要
Abstract
Birefringence,as a fundamental parameter of optical crystals,plays a vital role in numerous optical applications such as phase modulation,light splitting,and polarization,thereby making them key materials in laser science and technology.The significant birefringence of vanadate polyhedra provides a new approach for developing birefringent materials.In this study,first-principles calculations are used to investigate the band structures,density of states(DOS),electron localization functions(ELFs),and birefringence behaviors of four alkali metal vanadate crystals AV3O8(A=Li,Na,K,Rb).The computational results show that all AV3O8 crystals have indirect band gaps,whose values are 1.695,1.898,1.965,and 1.984 eV for LiV3O8,NaV3O8,KV3O8,and RbV3O8,respectively.The DOS analysis reveals that near the Fermi level,the conduction band minima(CBM)in these vanadates are predominantly occupied by the outermost orbitals of V atoms,while the valence band maxima(VBM)are primarily contributed by O-2p orbitals.The O-2p orbitals also exhibit strong localization near the Fermi level.Combined with highest occupied molecular orbital-lowest unoccupied molecular orbital(HOMO-LUMO)analysis and population analysis,the bonding interactions in all four crystals mainly arise from the hybridization between V-3p and O-2p orbitals,indicating strong covalent bonding in V-O bonds.Through the analysis of structure-property relationships,the large birefringence is primarily attributed to the pronounced structural anisotropy,high anisotropy index of responsive electron distribution,unique arrangement of anionic groups,and d-p orbital hybridization between V-3d and O-2p orbitals.The calculated birefringence values at a wavelength of 1064 nm for LiV3O8,NaV3O8,KV3O8,and RbV3O8 are 0.28,0.30,0.28,and 0.27,respectively.关键词
碱金属钒酸盐/第一性原理/电子结构/双折射率Key words
alkali metal vanadate/first principles/electronic structure/birefringence引用本文复制引用
万俯宏,丁家福,和志豪,王云杰,崔健,李佳郡,苏欣,黄以能..基于第一性原理对碱金属钒酸盐AV3O8(A=Li,Na,K,Rb)大双折射率的机理研究[J].物理学报,2025,74(10):85-94,10.基金项目
新疆维吾尔自治区重点实验室开放课题(批准号:2023D04074)、伊犁师范大学科研项目(批准号:22XKZZ21)和伊犁师范大学大学生创新训练项目(批准号:S202210764014,S202210764015,S202210764016)资助的课题. Project supported by the Open Project of Key Laboratory of Xinjiang Uygur Autonomous Region,China(Grant No.2023D04074),the Scientific Research Project of Yili Normal University,China(Grant No.22XKZZ21),and the Innovation Training Project for College Students of Yili Normal University,China(Grant Nos.S202210764014,S202210764015,S202210764016). （批准号:2023D04074）
