碱金属钼酸盐结构与性能关系的第一性原理研究

摘要/Abstract

摘要： 基于第一性原理比较研究Li₂MoO₄、Na₂MoO₄、K₂MoO₄和Rb₂MoO₄四种晶体的晶体结构、电子结构、原子布居、电荷密度分布和双折射率。研究结果表明四种晶体的带隙为直接带隙,禁带宽度相差不大,均在4.3 eV附近。随着碱金属原子半径增加,其电子轨道对能带的贡献会向高能侧靠近。键布居数和电子密度分布情况表明, Mo与O之间形成共价键,碱金属原子与O形成离子键。四种晶体中双折射率最高者为Rb₂MoO₄,其在1 064 nm处的双折射率为0.022 5。晶体折射率数据表明碱金属原子半径与双折射率正相关。本文研究可为钼酸盐在非线性光学晶体方面的应用提供一定的参考。

关键词: 碱金属钼酸盐, 光学性质, 双折射率, 能带结构, 第一性原理, 密度泛函理论

Abstract: The crystal structures, electronic structures, atomic populations, charge density distributions and birefringence of Li₂MoO₄, Na₂MoO₄, K₂MoO₄ and Rb₂MoO₄ were compared by first principles. The results show that the bandgaps of the four crystals are direct band gaps, the differences of the bandgap between them are not large, and they are all around 4.3 eV. As the radius of alkali metal atoms increases, the contribution of their electronic orbitals to the energy bands moves closer to the high-energy side. The distribution of the bonding boule number and electron density suggests that covalent bonds are formed between Mo and O, and the alkali metal atoms form ionic bonds with O. Rb₂MoO₄ has the highest birefringence of 0.022 5 among the four crystals at 1 064 nm. The refractive indices of the four crystals show that the radius is positively correlated with the birefringence. The study in this paper provides some references for the application of molybdate in nonlinear optical crystals.

Key words: alkali metal molybdate, optical property, birefringence, bandgap structure, first principle, density functional theory

中图分类号:

TB34
O469

张博, 王云杰, 齐亚杰, 丁家福, 和志豪, 苏欣. 碱金属钼酸盐结构与性能关系的第一性原理研究[J]. 人工晶体学报, 2024, 53(6): 999-1007.

ZHANG Bo, WANG Yunjie, QI Yajie, DING Jiafu, HE Zhihao, SU Xin. First Principles Study on the Structure-Property Relationship of Alkali Metal Molybdates[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2024, 53(6): 999-1007.

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