光谱学与光谱分析 |
|
|
|
|
|
Theoretical Investigation of the Electron Paramagnetic Resonance Parameters and Local Structures for Zinc Phosphate Glass Doped with VO2+ |
LI Chao-ying, HUANG Xian-kai, TU Qiu, WANG Wei-yang, ZHENG Xue-mei |
School of Physics and Electronic Information, Shangrao Normal University, Shangrao 334000, China |
|
|
Abstract As an important model system, 3d1 ions (VO2+, V4+ et al) have been extensively investigated by means of electron paramagnetic resonance (EPR), and many experimental results of EPR parameters were also measured. The optical absorption and EPR parameters (g factors g‖, g⊥ and hyperfine structure constants A‖, A⊥) of a tetragonal V4+ center in zinc phosphate glass are theoretically investigated, using the perturbation formulas for a 3d1 ion in tetragonally compressed octahedra. Since the spin-orbit coupling parameter ζ0p(≈150 cm-1) of ligand O2- is close to that ζ0d(≈248 cm-1) of the central 3d1 ion in zinc phosphate glass doped VO2+, the effect of the spin-orbit coupling parameter ζp0 on the EPR spectra and optical absorption spectra should be taken into account. In this work, the relationship between the EPR parameters as well as the optical absorption spectra and the local structure of the impurity center are established based on the superposition model. By fitting the calculated EPR parameters and optical absorption spectra for V4+ center in zinc phosphate glass to the experimental data, the local structure parameters of [VO6]8- cluster are obtained. According to the investigation, the magnitudes of the metal-ligand distances parallel and perpendicular to the C4-axis of [VO6]8- cluster are, respectively, R‖≈0.175 nm and R⊥≈0.197 nm, the local structure around the V4+ ions possesses a compressed tetragonal distortion along C4 axis. Theoretical results of EPR parameters and optical absorption spectra are in good agreement with experimental data, the validity of the calculated results has also been discussed. Thus,perturbation method is effective to the studies the EPR parameters and optical spectra of transition-metal 3d1 ions in crystals. In addition, based on the studies of the hyperfine structure constants (A‖ and A⊥), one can found that the large value of κ indicates a large contribution to the hyperfine constant bv the unpaired s-electron.
|
Received: 2014-05-20
Accepted: 2014-08-19
|
|
Corresponding Authors:
LI Chao-ying
E-mail: cyli1962@gmail.com
|
|
[1] Fletcher L B, Witcher J J, Troy N, et al. Opt. Lett., 2012, 37(7): 1148. [2] Rao R B, Veeraiah N. Physica B, 2004, 348(1-4): 256. [3] Ravikumar R V S S N, Jamalaiah B C, Chandrasekhar A V, et al. J. Alloy. Compd., 1999, 287(1-2): 84. [4] Kripal R, Shukla S. Spectrosc. Lett., 2011, 44(4): 235. [5] Zhang H M, Xiao W B, Wan X. J. Alloy. Compd., 2014, 583: 244. [6] Griffith J S. The Theory of Transition-Metal Ions. London, Cambridge University Press, 1964. [7] Newman D J, Ng B. Rep. Prog. Phys., 1989, 52(6): 699. [8] Song B T, Wu S Y, Kuang M Q, et al. Optik, 2013, 124(16): 2493. [9] Vainshtein B K, Fridkin V M, Indenbom V L. Modern Crystallography Ⅱ-Structure of Crystals, Springer-Verlag Berlin Heidelberg, New York, 1982. [10] Xie L H, Yeung Y Y. Appl. Magn. Reson., 2011, 40(4): 441. [11] Kalfaolu E, Karabulut B. Magn. Magn. Mater., 2012, 324(8): 1593. [12] Zhang H M, Xiao W B, Wan X. Physica B, 2014, 449(15): 225. [13] Zhang H M, Wan X. J Non-Cryst. Solids, 2013, 361: 43. |
[1] |
ZHANG Quan-zhe1, ZOU Sheng1, ZHANG Hong1, 2*. Application and Progress of Residual Magnetometry Based on Electron Paramagnetic Resonance Spectroscopy[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2024, 44(01): 22-28. |
[2] |
SUN Kai-yue1, 2, CHEN Xiao-ming2, HAN Wen2*, HE Ming-yue1*, LU Tai-jin2. Study on Color Formation and Identification Characteristics of Blood Amber Produced by Irradiation[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2023, 43(05): 1459-1464. |
[3] |
YAN Xiao-xu1, YUE Su-wei1, 2*, SU Lü-man1, WANG Zhi-wen1. Gemological and Spectroscopic Characteristics of Natural White Sodalite With Tenebrescence[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2021, 41(12): 3936-3941. |
[4] |
Enas Aljuhani1, Amnah M. A. Alsuhaibani2, A. M. El-Didamony3, N. Hassan4, Sameh Abo Taleb4, Moamen S. Refat4,5*. Preparation and Spectroscopic of Vanadyl(Ⅱ) Vitamin D3 Amino Acid Mixed Complexes as Insulin Mimetic Drug[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2019, 39(07): 2316-2324. |
[5] |
WU Xiao-xuan1,4,FENG Wen-lin2,3,ZHENG Wen-chen3,4. Studies of the g Factor and Optical Spectra for CaZrO3∶Mn4+ Crystal[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2008, 28(08): 1705-1707. |
[6] |
FENG Wen-lin1,3, WU Xiao-xuan2,3,4, ZHENG Wen-chen3,4. Investigation of Optical and EPR Spectra of ZnO∶V3+ Crystal[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2007, 27(09): 1689-1691. |
[7] |
WU Xiao-xuan1, 2, 3,ZHENG Wen-chen2, 3,LIU Hong-gang2. Study on the Optical and EPR Spectra of CuAlS2∶Ni+[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2007, 27(03): 417-419. |
[8] |
WU Xiao-xuan1, 2, 3,ZHENG Wen-chen2, 3 . Study on the Contribution of the Charge Transfer Excited States in Ba2MgGe2O7∶Cr4+ Crystal to g Factor [J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2007, 27(01): 8-11. |
[9] |
XU Chang-tan. Investigation of Electron Paramagnetic Resonance Spectrum in Ni2+:RbMgF3[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2004, 24(12): 1594-1596. |
[10] |
MENG Yu-fei1,PENG Ming-sheng1,CHEN Wen-xuan2. Spectroscopic Studies on Transition Metal Ions in Colored Diamonds[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2004, 24(07): 769-774. |
|
|
|
|