First Principles Study on the Structure-Property Relationship of Alkali Metal Molybdates

Abstract

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

CLC Number:

TB34
O469

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.

References

[1] BARINOVA O P, DANEVICH F A, DEGODA V Y, et al. First test of crystal as a cryogenic scintillating bolometer[J]. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2010, 613(1): 54-57.
[2] BARINOVA O P, CAPPELLA F, CERULLI R, et al. Intrinsic radiopurity of a crystal[J]. Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, 2009, 607(3): 573-575.
[3] SOMANI M, SALEEM M, MITTAL M, et al. Structural, photoluminescent and thermoluminescent studies of rare earth ion (RE=Eu³⁺) doped Sr₂SiO₄ phosphor[J]. Optik, 2019, 182: 839-847.
[4] 赵小杨, 王佳, 温慧霞, 等. 稀土掺杂钼酸盐发光材料的研究进展[J]. 稀土, 2022, 43(1): 25-38.
ZHAO X Y, WANG J, WEN H X, et al. Research progress of rare earth doped molybdate luminescent materials[J]. Chinese Rare Earths, 2022, 43(1): 25-38 (in Chinese).
[5] YANG Y Q, YANG H, WANG Q, et al. Study of the supported K₂MoO₄ catalyst for methanethiol synthesis by one step from high H₂S-containing syngas[J]. Catalysis Letters, 2001, 74(3): 221-225.
[6] HAO Y J, ZHANG Y H, CHEN A P, et al. Study on methanethiol synthesis from H₂S-rich syngas over K₂MoO₄ catalyst supported on electrolessly Ni-plated SiO₂[J]. Catalysis Letters, 2009, 129(3): 486-492.
[7] YANG X L, ZHANG J Q, HOU Q H, et al. Regulation of kinetic properties of chemical hydrogen absorption and desorption by cubic K₂MoO₄ on magnesium hydride[J]. Nanomaterials, 2022, 12(14): 2468.
[8] ZHANG L, CAO X F, MA Y L, et al. Pancake-like Fe₂(MoO₄)₃ microstructures: microwave-assisted hydrothermal synthesis, magnetic and photocatalytic properties[J]. New Journal of Chemistry, 2010, 34(9): 2027-2033.
[9] HU J Y, CHEN L, ZHONG X, et al. Corrosion inhibition of titanium in hydrochloric acid containing Na₂MoO₄[J]. International Journal of Electrochemical Science, 2017, 12(10): 8878-8891.
[10] SHAHRYARI Z, GHEISARI K, YEGANEH M, et al. Corrosion mitigation ability of differently synthesized polypyrrole (PPy-FeCl₃ & PPy-APS) conductive polymers modified with Na₂MoO₄ on mild steel in 3.5% NaCl solution: comparative study and optimization[J]. Corrosion Science, 2021, 193: 109894.
[11] 王平, 郭小阳, 梁奇. ZL108铝合金微弧氧化膜的Na₂MoO₄改性机理[J]. 稀有金属材料与工程, 2015, 44(5): 1191-1196.
WANG P, GUO X Y, LIANG Q. Na₂MoO₄ modifying mechanism of micro-arc oxidation coating on ZL108 aluminum alloy[J]. Rare Metal Materials and Engineering, 2015, 44(5): 1191-1196 (in Chinese).
[12] 车顺爱, 林海明, 段瑛滢. 手性钼酸盐介观结构膜的制备方法: CN113136572A[P]. 2021-07-20.
CHE S A, LIN H M, DUAN Y Y. Preparation of chiral molybdate mesostructured membranes: CN113136572A[P]. 2021-07-20 (in Chinese).
[13] 林海明. 手性介观结构钼酸盐的组装及其在手性分子检测中的应用[D]. 上海: 同济大学, 2020.
LIN H M. Assembly of chiral mesoscopic molybdate and its application in chiral molecular detection[D].Shanghai: Tongji University, 2020 (in Chinese).
[14] KOLITSCH U. The crystal structures of Phenacite-type Li₂(MoO₄), and Scheelite-type LiY(MoO₄)₂ and LiNd(MoO₄)₂[J]. Zeitschrift für Kristallographie-Crystalline Materials, 2001, 216(8): 449-454.
[15] BECKA L N, POLJAK R J. Crystal structure of Na₂MoO₄ and Na₂WO₄. Anales Asoc Quim Arg, 1958, 46: 204-209.
[16] GATEHOUSE B M, LEVERETT P. Crystal structure of potassium molybdate, K₂MoO₄[J]. Journal of the Chemical Society A: Inorganic, Physical, Theoretical, 1969: 849.
[17] KOOLS F X N M, KOSTER A S, RIECK G D. The structures of potassium, rubidium and caesium molybdate and tungstate[J]. Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry, 1970, 26(12): 1974-1977.
[18] CHEN X, CHEN P, JIANG L W, et al. Luminescence properties of large-size Li₂MoO₄ single crystal grown by Czochralski method[J]. Journal of Crystal Growth, 2021, 558: 126022.
[19] SHIGEMATSU H, NOMURA K, NISHIYAMA K, et al. Structures and phase transitions in Rb₂MoO₄ and Rb₂WO₄[J]. Ferroelectrics, 2011, 414(1): 195-200.
[20] BRˇEZINA B, HAVRÁNKOVÁ M. Growth of KH₂PO₄ single crystals in gel[J]. Materials Research Bulletin, 1971, 6(7): 537-543.
[21] BORDUI P F, JACCO J C, LOIACONO G M, et al. Growth of large single crystals of KTiOPO₄ (KTP) from high-temperature solution using heat pipe based furnace system[J]. Journal of Crystal Growth, 1987, 84(3): 403-408.
[22] CHEN C T, WU B C, JIANG A D, et a1. A new type ultraviolet SHG crystal β-BaB₂O₄[J]. Science China Chemistry, 1985, 28: 235-243.
[23] SHEN D Z, HUANG C E. A new nonlinear optical crystal KTP[J]. Progress in Crystal Growth and Characterization, 1985, 11(4): 269-274.
[24] CHEN C T, WU Y C, JIANG A, et al. New nonlinear-optical crystal: LiB₃O₅[J]. Journal of the Optical Society of America b-Optical Physics, 1989, 6: 616-621.
[25] LIU L L, YANG Y, YANG Z H, et al. The enhancement of birefringence resulted from anionic dimensionality changes through adjusting cationic density[J]. Journal of Alloys and Compounds, 2017, 717: 317-325.
[26] SHI T T, ZHANG F F, LI Y H, et al. Structural diversity of molybdate iodate and fluoromolybdate: syntheses, structures, and calculations on Na₃(MoO₄)(IO₃) and Na₃Cs(MoO₂F₄)₂[J]. Inorganic Chemistry, 2020, 59(5): 3034-3041.
[27] 潘世烈, 王颖. 化合物磷钼酸铷和磷钼酸铷非线性光学晶体及制备方法和用途: CN103628135A[P]. 2014-03-12.
PAN S L, WANG Y. Compounds rubidium phosphomolybdate and rubidium phosphomolybdate nonlinear optical crystals and methods of preparation and uses thereof: CN103628135A[P]. 2014-03-12 (in Chinese).
[28] 安海艳, 侯玉姣. 一种手性杂多钼酸盐、制备方法及非线性光学应用: CN106544736A[P]. 2017-03-29.
AN H Y, HOU Y J. A chiral heteropolymolybdate, preparation method and nonlinear optical applications: CN106544736A[P]. 2017-03-29 (in Chinese).
[29] ZHANG X Y, LI D N, YANG Z H, et al. Synthesis, crystal structure, and properties of the sodium molybdate fluoride Na₃MoO₄F[J]. Zeitschrift Für Anorganische und Allgemeine Chemie, 2015, 641(5): 922-926.
[30] LV J S, LIU X N, ZHANG X T, et al. Experimental and DFT study of peapod-like Fe₂(MoO₄)₃ nanofibers for photodegradation of ciprofloxacin[J]. Materials Letters, 2021, 290: 129456.
[31] ZHU R, JIA K, BI Z, et al. Realizing white emission in Sc₂(MoO₄)₃:Eu³⁺/Dy³⁺/Ce³⁺ phosphors through computation and experiment[J]. Journal of Solid State Chemistry, 2020, 290: 121592.
[32] HIZHNYI Y, BORYSYUK V, CHORNII V, et al. Role of native and impurity defects in optical absorption and luminescence of Li₂MoO₄ scintillation crystals[J]. Journal of Alloys and Compounds, 2021, 867: 159148.
[33] WAN S M, ZHANG B, YAO Y N, et al. Raman and density functional theory studies of Li₂Mo₄O₁₃ structures in crystalline and molten states[J]. Inorganic Chemistry, 2017, 56(22): 14129-14134.
[34] ANANDKUMAR B, KRISHNA N G, SOLOMON R V, et al. Synergistic enhancement of corrosion protection of carbon steels using corrosion inhibitors and biocides: molecular adsorption studies, DFT calculations and long-term corrosion performance evaluation[J]. Journal of Environmental Chemical Engineering, 2023, 11(3): 109842.
[35] SEGALL M D, LINDAN P J D, PROBERT M J, et al. First-principles simulation: ideas, illustrations and the CASTEP code[J]. Journal of Physics: Condensed Matter, 2002, 14(11): 2717-2744.
[36] YIP T W S, CUSSEN E J, WILSON C. Spontaneous formation of crystalline lithium molybdate from solid reagents at room temperature[J]. Dalton Transactions, 2010(2): 411-417.
[37] FORTES A D. Crystal structures of spinel-type Na₂MoO₄ and Na₂WO₄ revisited using neutron powder diffraction[J]. Acta Crystallographica Section E, Crystallographic Communications, 2015, 71(6): 592-596.
[38] ABBAS S A, MAHMOOD I, SAJJAD M, et al. Spinel-type Na₂MoO₄ and Na₂WO₄ as promising optoelectronic materials: first-principle DFT calculations[J]. Chemical Physics, 2020, 538: 110902.