Citation: Yufan ZHAO, Jinglin YOU, Shixiang WANG, Guopeng LIU, Xiang XIA, Yingfang XIE, Meiqin SHENG, Feiyan XU, Kai TANG, Liming LU. Raman spectroscopic quantitative study of the melt microstructure in binary Li₂O-GeO₂ functional crystals[J]. Chinese Journal of Inorganic Chemistry, ;2025, 41(8): 1533-1544. doi: 10.11862/CJIC.20250063 shu

Raman spectroscopic quantitative study of the melt microstructure in binary Li₂O-GeO₂ functional crystals

1.
State Key Laboratory of Advanced Special Steel, Shanghai Key Laboratory of Advanced Ferrometallurgy, School of Materials Science and Engineering, Shanghai University, Shanghai 200444, China
2.
Shanghai Technical Institute of Electronics & Information, Shanghai 201411, China
3.
SINTEF Industry, Trondheim 7094, Norway
4.
CSIRO Process Science and Engineering, Pullenvale 4069, Australia

Corresponding author: Jinglin YOU, jlyou@163.com
Received Date: 25 February 2025
Revised Date: 2 April 2025

Figures(7)

Four binary Li₂O-GeO₂ crystals, Li₄GeO₄, Li₆Ge₂O₇, Li₂GeO₃, and Li₂Ge₂O₅, were synthesized through solid-state sintering. In situ high-temperature Raman spectroscopy, combined with theoretical calculations, was employed to qualitatively and quantitatively analyze the structure evolution from the crystalline to the molten state, as well as the melt microstructure. The study reveals that the melts of Li₄GeO₄, Li₆Ge₂O₇, and Li₂GeO₃ are composed of [GeO₄]^4-, [Ge₂O₇]^6-, and [GeO₃]^2- units, respectively, along with Li⁺ ions. In contrast, Li₂Ge₂O₅ crystal undergoes a gradual transition from a three-dimensional network structure formed by [GeO₄]^4- tetrahedra to smaller [Ge₃O₉]^6- three-membered rings as the temperature increases towards the melting point. The microstructure units and a series of model clusters have been designed, optimized, and calculated by quantum chemistry ab initio calculations. The computational simulation, in conjunction with the experiments, presents a novel method for correcting the experimental Raman spectra of the melts. By introducing the concept of delicate structure and employing Gaussian functions to deconvolute the stretching vibration band of non-bridging oxygen in [GeO₄]^4- tetrahedra within Raman spectra, we quantitatively determined the distribution of structure units (Q_i, where i denotes the number of bridging oxygens in each [GeO₄]^4- tetrahedron, i=0-4) for these four crystals in their molten state.
- Li₂O-GeO₂ crystal,
- high-temperature Raman spectrum,
- quantum chemistry ab initio calculation,
- microstructure quantification
1. [1]
  HANNON A C, MARTINO D D, SANTOS L F, ALMEIDA R M. Ge-O coordination in cesium germanate glasses[J]. J. Phys. Chem. B, 2007, 111(13): 3342-3354
2. [2]
  XU Y W, LI Y D, LAN G X. Pressure-induced amorphization of Li₂GeO₃ and Li₆Ge₂O₇ crystals[J]. Spectroc. Acta Pt. A‒Molec. Biomolec. Spectr., 1996, 52: 1417-1422
3. [3]
  ZHANG S J, WAN S M, ZENY Y, JIANG S J, GONG X Y, YOU J L. In situ Raman spectroscopy and DFT studies of the Li₂GeO₃ melt structure[J]. Inorg. Chem., 2019, 58: 51-56
4. [4]
  LIU W J, DONG C J, ZHANG M X, LI F F, HE X Y, CHEN C, ZHAO C C, MENG S. The latest development of the germanate luminescent materials[J]. Rare Metals and Cemented Carbides, 2017, 45(1): 67-70
5. [5]
  EVANS J M, PETRICEVIC V, BYKOV A B, DELGADO A, ALFANO A A. Direct diode-pumped continuous-wave near-infrared tunable laser operation of Cr⁴⁺ forsterite and Cr⁴⁺ Ca₂GeO₄[J]. Opt. Lett., 1997, 22(15): 1171-1173
6. [6]
  IVANOV V A, MARYCHEV M O, ANDREEV P V, KOSEVA I, TZVETKOV P, NIKOLOV V. Novel solvents for the single crystal growth of germanate phases by the flux method[J]. J. Cryst. Growth, 2015, 426: 25-32
7. [7]
  SCHMIDT M W, CONNOLLY J A D, GUNTHER D, BOGAERTS M. Element partitioning: The role of melt structure and composition[J]. Science, 2006, 312: 1646-1650
8. [8]
9. [9]
  WANG Y Y, YOU J L, SIMON P, ZHENG S B. Temperature dependent structure evolutions of crystals and their melts and sodium germanates and germanium coordination study by Raman spectroscopy[J]. The Journal of Light Scattering, 2012, 24(4): 325-332
10. [10]
  WAN S M, ZHANG S J, GONG X Y, ZENG Y, JIANG S J, YOU J L. Structural investigations on two typical lithium germanate melts by in situ Raman spectroscopy and density functional theory calculations[J]. CrystEngComm, 2020, 22: 701-707
11. [11]
  WAN S M, ZHANG S J, LI B, ZHANG X, GONG X Y, YOU J L. Threefold coordinated germanium in a GeO₂ melt[J]. Nat. Commun., 2023, 14(1): 7008
12. [12]
  LIU S S, ZHANG G C, FENG K, HAN Y Y, HE T, YOU J L, WU Y C. In-situ Raman spectroscopy studies on La₂CaB₁₀O₁₉ crystal growth[J]. Cryst. Growth Des., 2020, 20(10): 6604-6609
13. [13]
  WANG M, YOU J L, SOBOL A A, WANG J, WU J, LV X M. Temperature-dependent Raman spectroscopic studies of microstructure present in dipotassium molybdate crystals and their melts[J]. J. Raman Spectrosc., 2016, 47(10): 1259-1265
14. [14]
  FARBER D L, WILLIAMS Q. Pressure-induced coordination changes in alkali-germanate melts: An in situ spectroscopic investigation[J]. Sci., 1992, 256: 1427-1430
15. [15]
  YOU J L, JIANG G C, HOU H Y, CHEN H, WU Y Q, XU K D. Quantum chemistry study on superstructure and Raman spectra of binary sodium silicates[J]. J. Raman Spectrosc., 2005, 36: 237-249
16. [16]
  TANG X H, YOU J L, WANG J, WANG M, GONG X Y, ZHANG F, TANG K. Quantitative study on microstructure of (CaO-SiO₂)-xAl₂O₃ ternary glass by Raman spectroscopy[J]. The Journal of Light Scattering, 2022, 34(1): 22-29
17. [17]
  LEE T J, JAYATILAKA D. An open-shell restricted Hartree-Fock perturbation theory based on symmetric spin orbitals[J]. Chem. Phys. Lett., 1993, 201: 1-10
18. [18]
  NOWAK M J, ROSTKOWSKA H, LAPINSKI L, KWIATKOWSKI J S, LESZCZYNSKI J. Experimental matrix isolation and theoretical ab initio HF/6-31G(d, p) studies of infrared spectra of purine, adenine and 2-chloroadenine[J]. Spectroc. Acta Pt. A‒Molec. Biomolec. Spectr., 1994, 50: 1081-1094
19. [19]
  WANG C, LIU Z G, LIN P P, XU X, LU F G, XU J J, SHI Y H, HE P, LIN T S. Impacts of 3Li₂O-2GeO₂ melt on fabrication and electrical performance of novel LLZTO@Li₄GeO₄/Li₂O composite electrolytes[J]. J. Eur. Ceram. Soc., 2022, 42(5): 2290-2298
20. [20]
  HENDERSON G S, WANG H M. Germanium coordination and the germanate anomaly[J]. Eur. J. Mineral., 2002, 14: 733-744
21. [21]
  ZHAO Y F, YOU J L, WANG J, WANG M, TANG K LU L M, ZHANG Q L, WAN S M, GONG X Y, LIU G P. Quantitative studies on local structure of molten binary potassium germanates[J]. Inorg. Chem., 2023, 62(28): 10905-10915
22. [22]
  SCOTT A P, RADOM L. Harmonic vibrational frequencies: An evaluation of Hartree-Fock, Mller-Plesset, quadratic configuration interaction, density functional theory, and semiempirical scale factors[J]. J. Phys. Chem., 1996, 100: 16502-16513
23. [23]
  POLAVARAPU P. Ab initio vibrational Raman and Raman optical activity spectra[J]. J. Phys. Chem., 1990, 94(21): 8106-8112
1. [1]
  Xueli Mu , Lingli Han , Tao Liu . Quantum Chemical Calculation Study on the E2 Elimination Reaction of Halohydrocarbon: Designing a Computational Chemistry Experiment. University Chemistry, 2025, 40(3): 68-75. doi: 10.12461/PKU.DXHX202404057
2. [2]
  Liang MA , Honghua ZHANG , Weilu ZHENG , Aoqi YOU , Zhiyong OUYANG , Junjiang CAO . Construction of highly ordered ZIF-8/Au nanocomposite structure arrays and application of surface-enhanced Raman spectroscopy. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1743-1754. doi: 10.11862/CJIC.20240075
3. [3]
  Yanan Jiang , Yuchen Ma . Brief Discussion on the Electronic Exchange Interaction in Quantum Chemistry Computations. University Chemistry, 2025, 40(3): 10-15. doi: 10.12461/PKU.DXHX202402058
4. [4]
  Yaqin Zheng , Lian Zhuo , Meng Li , Chunying Rong . Enhancing Understanding of the Electronic Effect of Substituents on Benzene Rings Using Quantum Chemistry Calculations. University Chemistry, 2025, 40(3): 193-198. doi: 10.12461/PKU.DXHX202406119
5. [5]
  Jiabo Huang , Quanxin Li , Zhongyan Cao , Li Dang , Shaofei Ni . Elucidating the Mechanism of Beckmann Rearrangement Reaction Using Quantum Chemical Calculations. University Chemistry, 2025, 40(3): 153-159. doi: 10.12461/PKU.DXHX202405172
6. [6]
  Huiying Xu , Minghui Liang , Zhi Zhou , Hui Gao , Wei Yi . Application of Quantum Chemistry Computation and Visual Analysis in Teaching of Weak Interactions. University Chemistry, 2025, 40(3): 199-205. doi: 10.12461/PKU.DXHX202407011
7. [7]
  Wenkai Chen , Yunjia Shen , Xiangmeng Kong , Yanli Zeng . Quantum Chemistry Calculation of Key Physical Quantity in Circularly Polarized Luminescence: Introducing an Exploratory Computational Chemistry Experiment. University Chemistry, 2025, 40(3): 83-91. doi: 10.12461/PKU.DXHX202405018
8. [8]
  Jia Zhou . Constructing Potential Energy Surface of Water Molecule by Quantum Chemistry and Machine Learning: Introduction to a Comprehensive Computational Chemistry Experiment. University Chemistry, 2024, 39(3): 351-358. doi: 10.3866/PKU.DXHX202309060
9. [9]
  Zhuomin Zhang , Hanbing Huang , Liangqiu Lin , Jingsong Liu , Gongke Li . Course Construction of Instrumental Analysis Experiment: Surface-Enhanced Raman Spectroscopy for Rapid Detection of Edible Pigments. University Chemistry, 2024, 39(2): 133-139. doi: 10.3866/PKU.DXHX202308034
10. [10]
  Jingyi Chen , Fu Liu , Tiejun Zhu , Kui Cheng . Practice of Integrating Ideological and Political Education into Raman Spectroscopy Analysis Experiment Course. University Chemistry, 2024, 39(2): 140-146. doi: 10.3866/PKU.DXHX202310111
11. [11]
  Wei Peng , Baoying Wen , Huamin Li , Yiru Wang , Jianfeng Li . Exploration and Practice on Raman Scattering Spectroscopy Experimental Teaching. University Chemistry, 2024, 39(8): 230-240. doi: 10.3866/PKU.DXHX202312062
12. [12]
  Zhaoyue Lü , Zhehao Chen , Yi Ni , Duanbin Luo , Xianfeng Hong . Multi-Level Teaching Design and Practice Exploration of Raman Spectroscopy Experiment. University Chemistry, 2024, 39(11): 304-312. doi: 10.12461/PKU.DXHX202402047
13. [13]
  Jiajie Li , Xiaocong Ma , Jufang Zheng , Qiang Wan , Xiaoshun Zhou , Yahao Wang . Recent Advances in In-Situ Raman Spectroscopy for Investigating Electrocatalytic Organic Reaction Mechanisms. University Chemistry, 2025, 40(4): 261-276. doi: 10.12461/PKU.DXHX202406117
14. [14]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
15. [15]
  Dongju Zhang , Rongxiu Zhu . Construction of Ideological and Political Education in Quantum Chemistry Course: Several Teaching Cases to Reveal the Universal Connection of Things. University Chemistry, 2024, 39(7): 272-277. doi: 10.3866/PKU.DXHX202311032
16. [16]
  Xinpeng LIU , Liuyang ZHAO , Hongyi LI , Yatu CHEN , Aimin WU , Aikui LI , Hao HUANG . Ga₂O₃ coated modification and electrochemical performance of Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ cathode material. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1105-1113. doi: 10.11862/CJIC.20230488
17. [17]
  Pei Li , Yuenan Zheng , Zhankai Liu , An-Hui Lu . Boron-Containing MFI Zeolite: Microstructure Control and Its Performance of Propane Oxidative Dehydrogenation. Acta Physico-Chimica Sinica, 2025, 41(4): 2406012-0. doi: 10.3866/PKU.WHXB202406012
18. [18]
  Yan Liu , Yuexiang Zhu , Luhua Lai . Introduction to Blended and Small-Class Teaching in Structural Chemistry: Exploring the Structure and Properties of Crystals. University Chemistry, 2024, 39(3): 1-4. doi: 10.3866/PKU.DXHX202306084
19. [19]
  Ruiqin Feng , Ye Fan , Yun Fang , Yongmei Xia . Strategy for Regulating Surface Protrusion of Gold Nanoflowers and Their Surface-Enhanced Raman Scattering. Acta Physico-Chimica Sinica, 2024, 40(4): 2304020-0. doi: 10.3866/PKU.WHXB202304020
20. [20]
  Hongyi LI , Aimin WU , Liuyang ZHAO , Xinpeng LIU , Fengqin CHEN , Aikui LI , Hao HUANG . Effect of Y(PO₃)₃ double-coating modification on the electrochemical properties of Li[Ni_0.8Co_0.15Al_0.05]O₂. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1320-1328. doi: 10.11862/CJIC.20230480

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(6)
HTML views(2)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Raman spectroscopic quantitative study of the melt microstructure in binary Li2O-GeO2 functional crystals

Metrics

通讯作者: 陈斌, bchen63@163.com

Raman spectroscopic quantitative study of the melt microstructure in binary Li₂O-GeO₂ functional crystals