Abstract:Quantum chemistry ab initio calculation was applied to study the hyperfine structure of ternary alkali phosphosilicates. Restricted Hartree-Fock method (RHF) with the basis sets of 6-31G(d) was employed to optimize geometric structure and calculate Raman spectra of a series of phosphosilicates model cluster structural units. Stress index of tetrahedron (SIT) was introduced to describe and classify the microstructure of ternary alkali phosphosilicates in order to investigate the effect of phosphorus-oxygen tetrahedron on the micro-environment of silicon-oxygen tetrahedron. It was suggested that the calculated vibrational wavenumbers of symmetric stretching vibration of non-bridging oxygen (NBO) depend not only on the species of the silicon-oxygen tetrahedron, which was called primary structure units, but also on the linkage of the neighboring tetrahedron and ring types. The phosphorus-oxygen tetrahedron exhibits regulative ability of bond angle and conductive ability of stress, so that the vibrational wavenumbers of silicon-oxygen tetrahedron are insensitive to the bond angle. It demonstrated that vibrational wavenumbers of NBO stretching vibration in the high frequency range show linear relationship with the value of SIT.
Key words:Phosphosilicates;Raman spectroscopy;ab initio calculation;Stress index
汪 磊,尤静林*,王媛媛 . 磷硅酸盐微结构及其拉曼光谱的量子化学计算[J]. 光谱学与光谱分析, 2010, 30(11): 2976-2980.
WANG Lei, YOU Jing-lin*, WANG Yuan-yuan . Quantum Chemistry ab initio Calculation Study on Microstructure and Raman Spectra of Phosphosilicates . SPECTROSCOPY AND SPECTRAL ANALYSIS, 2010, 30(11): 2976-2980.
[1] Tajima K, Ohashi M, Shiraki K, et al. J. Lightwave Technol., 1992, 10: 1532. [2] Kashyap R. Opt. Fiber Technol., 1994, 1: 17. [3] Dianov E M, Grekov M V, Bufetov I A, et al. Electorn. Lett.,1997, 33: 1542. [4] Grubb S G, Gannon P. Optical Society of America Technical Digest, 1991, 4: 7. [5] Dianov E M, Bubnov M M, Gurianov A N, et al. European Conference on Optical Communications (ECOC2000), 2000, 3: 135. [6] Gaponstev V P, Mtisin S M, Isineev A A, et al. Opt. & Laser Technol., 1989, 14(4): 188. [7] MO Xuan-xue(莫宣学). Geological Science and Technology Information(地质科技情报), 1985, 2: 21. [8] SUN Qiang, ZHENG Hai-fei, XIE Hong-sen, et al(孙 樯, 郑海飞, 谢鸿森,等). Acta Petrologica Sinica(岩石学报), 2001, 17(2): 332. [9] Ferraudi G, Arguello G A, Ali H, et al. Photochem. Photobiol., 1988, 47(5): 657. [10] Dearden S J. J. Chem. Soe., Faraday Trans. I, 1986, 82: 1627. [11] LI Di-en,PENG Ming-sheng(李迪恩,彭明生). Chinese Science Bulletin(科学通报), 1997, 22(4): 2405. [12] Dianov E M, Koltashev V V, Plotnichenko V G, et al. Journal of Non-Crystalline Solids, 1999, 249: 29. [13] YOU Jing-lin, JIANG Guo-chang, XU Kuang-di. Journal of Non-Crystalline Solids, 2001, 282(1): 125. [14] Izumitani Tetsuro(泉谷彻郎). Exploitation of Optics and Laser Glass(光学玻璃与激光玻璃开发). Translated by YANG Shu-qing(杨淑清, 译). Beijing: Weapon Industry Press(北京: 兵器工业出版社), 1993. 162. [15] Plotnichenko V G, Sokolov V O, Koltashev V V, et al. Journal of Non-Crystalline Solids, 2002, 306: 209. [16] YOU Jing-lin, JIANG Guo-chang, HOU Huai-yu, et al. J. Raman Spectrosc., 2005, 36(3): 237. [17] WANG Yuan-yuan, YOU Jing-lin, JIANG Guo-chang(王媛媛,尤静林,蒋国昌). Chinese Journal of Inorganic Chemistry(无机化学学报), 2008, 24(5): 765.