Citation: Fuhong WAN, Zhaosheng LI, Jian CUI, Xin SU, Yi′neng HUANG. First-principles study of the cation size effect on birefringence in K₃RE(VO₄)₂ (RE=Sc, Y, La, Lu)[J]. Chinese Journal of Inorganic Chemistry, ;2026, 42(8): 1658-1668. doi: 10.11862/CJIC.20260009 shu

First-principles study of the cation size effect on birefringence in K₃RE(VO₄)₂ (RE=Sc, Y, La, Lu)

Fuhong WAN ^{1, 2, #} ,
Zhaosheng LI ^{1, 2, #} ,
Jian CUI ^{1, 2} ,
Xin SU ^{1, 2, 3,,} ,
Yi′neng HUANG ^{1, 2, 3,,}

1.
School of Physics Science and Technology, Yili Normal University, Yining, Xinjiang 835000, China
2.
Xinjiang Key Laboratory of Condensed Matter Phase Transition and Microstructure, Yili Normal University, Yining, Xinjiang 835000, China
3.
National Laboratory of Solid State Microstructures, Nanjing University, Nanjing 210093, China

Corresponding author: Xin SU, suxin_phy@sina.com Yi′neng HUANG,
Received Date: 8 January 2026
Revised Date: 18 June 2026

Figures(5)

In this work, the electronic structures and optical properties of a series of vanadate crystals, K₃RE(VO₄)₂ (RE=Sc, Y, La, Lu), are systematically investigated using first-principles calculations based on density functional theory (DFT). The generalized gradient approximation (GGA) with the Perdew-Burke-Ernzerhof (PBE) functional and norm-conserving pseudopotentials is employed to guarantee calculation precision. The results indicate that all compounds in this series crystallize in the trigonal system with the P3m1 space group, featuring a distinct layered structure composed of isolated [VO₄] tetrahedra and [REO₆] octahedra that do not share vertices. Electronic band structure calculations reveal that these materials are indirect band gap semiconductors with wide band gap values ranging from 3.286 to 3.701 eV, ensuring excellent transparency in the ultraviolet to near-infrared region. Quantitative analysis of the density of states (DOS), Mulliken populations, and electron localization functions (ELF) confirms a characteristic structural framework of "strong covalent [VO₄]^3- groups + weak ionic K/RE framework". Regarding optical properties, the birefringences (Δn) of K₃Sc(VO₄)₂, K₃Y(VO₄)₂, and K₃La(VO₄)₂ are primarily modulated by the cationic size effect, monotonically decreasing as the ionic radius increases. Crucially, K₃Lu(VO₄)₂ counterintuitively breaks this conventional evolutionary trend, exhibiting an exceptionally high birefringence (Δn=0.250 at 1 064 nm). This giant macroscopic enhancement is successfully achieved by the unique lanthanide contraction effect of Lu³⁺, which imposes rigorous spatial geometric constraints within the compact lattice, thereby optimizing the subtle balance between functional group distortion and spatial orientation. This effect successfully facilitates a "moderately low distortion + high consistency arrangement" of the core optical active units. Furthermore, quantitative regression analysis based on the relative electron density anisotropy (REDA) theory demonstrates a near-perfect linear correlation between the macroscopic Δn and the geometric distortion index (Δd) of [VO₄], as well as its REDA, identifying the [VO₄] tetrahedra as the absolute dominant source of optical anisotropy.
- rare-earth vanadates,
- first-principles calculations,
- electronic structures,
- birefringence
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First-principles study of the cation size effect on birefringence in K3RE(VO4)2 (RE=Sc, Y, La, Lu)

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First-principles study of the cation size effect on birefringence in K₃RE(VO₄)₂ (RE=Sc, Y, La, Lu)