钠钛硅酸盐精细结构及其拉曼活性分子振动的量子化学从头计算研究

doi:10.13883/j.issn1004-5929.20190106

光散射学报 ›› 2019, Vol. 31 ›› Issue (1) : 38-44. DOI: 10.13883/j.issn1004-5929.20190106

材料研究中的应用

钠钛硅酸盐精细结构及其拉曼活性分子振动的量子化学从头计算研究

何莹霞, 尤静林^*, 王建, 马楠, 吴志东, 杨冶金

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Quantum Chemistry ab initio Study on Fine Structure and Raman-Active Molecular Vibration of Sodium Titanosilicates

HE Yingxia, YOU Jinglin^*, WANG Jian, MA Nan, WU Zhidong, YANG Yejin

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摘要

本文选取了Na₂O-TiO₂-SiO₂体系不同成分的团簇模型,采用量子化学从头计算方法计算其拉曼振动频率和相对散射活性。本文分析了钛硅酸盐中硅氧四面体([SiO₄])的局域环境变化对特征拉曼振动频率的影响,对硅氧四面体应力指数进行了拓展与修正,研究表明钠钛硅酸盐拉曼光谱高波数区硅氧四面体非桥氧对称伸缩振动频率随相应的硅氧四面体应力指数的增加而增加,并表现出良好的线性相关性。采用拉曼光谱和²⁹Si NMR对Na₂TiSiO₅玻璃进行解谱、定量分析和比较,并认为869 cm^-1处的谱峰归属为Q_1(Si)中非桥氧的对称伸缩振动。

Abstract

Raman vibrational wavenumber and scattering activity of the sodium titanosilicates with various compositions were calculated by quantum chemistry ab initio calculation method.The effect of the local microscopic environment of the silicon-oxygen tetrahedron (SiO₄) on the vibrational Raman wavenumbers was studied.Stress index of tetrahedron (SIT) was promoted and modifieded to analyze the symmetric stretching vibrational wavenumber of NBO (non-bridging oxygen),which appeared to increase linearly with the corresponding SIT in the high wavenumber range.Raman spectroscopy and ²⁹Si NMR were applied to make the quantitative analysis of Na₂TiSiO₅ glass,and the spectral peak around 869 cm^-1 was assigned to the symmetric stretching vibration of NBO of Q₁ species of silicon-oxygen tetrahedron.

导出引用

何莹霞, 尤静林, 王建, 马楠, 吴志东, 杨冶金. 钠钛硅酸盐精细结构及其拉曼活性分子振动的量子化学从头计算研究. 光散射学报. 2019, 31(1): 38-44 https://doi.org/10.13883/j.issn1004-5929.20190106

HE Yingxia, YOU Jinglin, WANG Jian, MA Nan, WU Zhidong, YANG Yejin. Quantum Chemistry ab initio Study on Fine Structure and Raman-Active Molecular Vibration of Sodium Titanosilicates. Chinese Journal of Light Scattering. 2019, 31(1): 38-44 https://doi.org/10.13883/j.issn1004-5929.20190106

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基金

国家自然科学基金(21773152);上海市科学技术委员会项目(12520709200);111引智项目(D17002);省部共建高品质特殊钢冶金与制备国家重点实验室开放课题(SKLASS2015-01,SKLASS2017-02);省部共建高品质特殊钢冶金与制备国家重点实验室自主课题(SKLASS2016-Z01)和科技部中央引导基金(YDZX20173100001316)资助

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Received	Revised	Published
2018-09-20	2018-11-06	2019-03-10
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2022-08-29

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