二元钠硅酸盐玻璃及其熔体微结构的高温拉曼光谱及核磁共振研究

本文采用拉曼光谱研究不同配比的二元钠硅酸盐玻璃,结果显示碱金属阳离子的浓度影响结构中桥氧的含量,且不同初级结构Qi具有不同的特征峰。对Na2O·3SiO2玻璃进行高温拉曼和核磁共振研究,分别采用精细结构Qjklmi(m1h,m2q,m3t)和Qjklmi取代初级结构Qi进行解谱拟合和结构分析得到得到初级微结构单元的实际分布,结合量化分析结果计算其拉曼散射截面,定量分析Na2O·3SiO2玻璃及熔体在升温状态下结构随温度的变化。从室温到到熔态,Qi结构之间存在动态平衡,Na2O·3SiO2玻璃随着温度的升高从玻璃态到高弹态,最后经历粘流态到熔态。     

硅酸盐熔体分子网络分数维值的高温拉曼光谱研究

采用高温拉曼光谱技术 ,对CaO Al2 O3 SiO2 (简称CAS)三元系硅酸盐熔体试样从 2 5℃ (淬火玻璃相 )～ 170 0℃ (高温熔融相 )的分子网络分数维值进行了系统研究 ,首次获得了该熔体在升温和淬火过程中网络分数维值的变化规律 ,也即在纳米尺度上描述了熔体网络构象的蠕变特征。这对深入研究熔体的粘度、密度和表面张力等物化性质具有重要意义 ,也将为进一步探索地幔岩浆上升速率及其迁移演化规律 ,完善冶金炉渣构成机理和改进低维非晶态材料与高分子材料的制备工艺和性能提供新的重要信息和理论依据。     

链状硅酸盐矿物的拉曼光谱研究

本文基于密度泛函理论(DFT)的平面波赝势法,利用CASTEP计算模块对四种典型链状(铝)硅酸盐矿物进行拉曼振动活性与拉曼光谱的模拟计算,同时测定了矿物的拉曼光谱,确定了四种矿物拉曼振动谱峰的归属,并结合硅氧四面体应力指数(SIT)进行了分析。结果表明,CASTEP计算模块可以有效获知(铝)硅酸盐矿物特征结构的拉曼振动模式的归属;链状(铝)硅酸盐矿物硅氧四面体局域环境与SiOT非桥氧对称伸缩振动波数之间的关系仍可用SIT指数描述。     

硅酸盐熔体团粒结构类声子振动的高温拉曼光谱研究

硅酸盐熔体是典型的近程有序,远程无序的准稳定态分数维体系,文章采用X射线小角散射(SAXS)、低波数拉曼光谱(LWRS)及高温拉曼光谱(HTRS)实时、原位分析等技术,对高温熔融法和溶胶凝胶法合成的CaO-Al₂O₃-SiO₂和Na₂O-Al₂O₃-SiO₂系列低维非晶硅酸盐试样进行了团粒结构粒度及其类声子振动频率的定量测定,获得了低温硅酸盐凝胶、高温硅酸盐熔体及其淬火玻璃相均具有纳米级(几个纳米至几十纳米)自相似团粒结构和类声子振动模的重要结论,进而建立了测定高温熔体介观团粒结构粒度的HTRS测定法,结果表明硅酸盐熔体的团粒结构粒度在高温下均会比其室温玻璃相的团粒尺度小,且高温熔体的网络结构基元也向桥氧数减少之基元转变。这些结论为探索自然界岩浆的地球化学特征、岩浆的结晶和演化以及低维硅酸盐材料结构性能的改进提供重要理论依据及信息。     

硅酸盐熔体高温Raman光谱定量分析中若干问题的探讨

根据Raman光谱定量分析的基本原理,分析了高温Raman光谱定量分析中存在的主要困难及可能的解决方法,得出高温Raman光谱定量分析的基本途径。     

枪晶石变温拉曼光谱及其固液相微结构研究

枪晶石在传统冶金连铸保护渣中起着十分重要的作用。采用紫外激光光源和电荷耦合器件(CCD)探测器,测定了枪晶石晶体和高温拉曼光谱(温度范围:298~1 723 K),观察了其在变温状态(升温和降温过程)下的特征谱变化。谱图结果显示,枪晶石熔态微结构单元与固态的相比更为多元化,表明熔体状态下多种团簇结构共存。同时,利用枪晶石晶胞结构模型,通过Dmol3密度泛函(DFT)理论计算了其分子振动频率,将其与实验值相结合,确定了特征谱峰的归属,为进一步采用拉曼光谱法原位研究保护渣中枪晶石的结构变化与行为特征提供了重要依据。     

KTN晶体及其熔体结构的高温拉曼光谱研究

测量并研究了不同温度(室温—1573 K)范围内KTN晶体的拉曼光谱及其熔体的高温拉曼光谱,分析了KTN晶体结构随温度变化的规律及其熔体的结构特征.随着温度的升高,KTN晶体的拉曼光谱谱峰都不同程度地向低波数方向移动,同时存在不同程度的展宽,并伴随强度的减弱.观察并解释了温度353 K附近KTN晶体样品的四方—立方转相现象.研究了KTN晶体拉曼光谱中538cm^-1,585cm^-1,835cm^-1和877cm^-1谱峰及其 关键词： 高温拉曼光谱 熔体 KTN晶体     

磷硅酸盐微结构及其拉曼光谱的量子化学计算

构建了系列典型的磷硅酸盐团簇结构模型,应用量子化学从头计算方法研究了磷硅酸盐的精细结构,选用Restricted Hartree-Fock(RHF)方法以及6-31G(d)基组优化空间几何构型,并计算了其拉曼光谱,同时引入硅氧四面体应力指数(SIT)分析和讨论了磷氧四面体对硅氧四面体微环境的影响。研究表明,磷硅酸盐高频区硅氧四面体非桥氧的对称伸缩振动频率不仅与非桥氧所处的硅氧四面体本身的种类有关,同时也与其邻接四面体种类及成环状况有关;磷氧四面体具有较强的键角调节和应力传导能力,使得硅氧四面体的振动频率相对键角不敏感;硅氧四面体非桥氧的对称伸缩振动频率随硅氧四面体应力指数(SIT)的增加而增加,并呈线性关系。     

CaSiO_3及其熔体结构的高温拉曼光谱研究

采用铜蒸气脉冲激光光源和时间分辨探测技术,测定了CaSiO3晶体及其熔融态的常温及高温拉曼光谱(在298～2000K的温度范围),观察了其在高温下的相转变、升温过程及其熔体的特征光谱变化。通过谱图解析,研究分析了熔体微结构单元硅氧四面体Qn(n为单个硅氧四面体的桥氧数)分布、聚合状况及其与固态晶体的区别     

Bi4Ge3O12晶体及其熔体结构的高温拉曼光谱研究

研究了BGO晶体在不同温度下(在300-1323 K的温度范围)的拉曼光谱及其熔体的高温拉曼光谱,分析了BGO晶体结构随温度变化的规律及BGO熔体的结构特征.随着温度的升高,BGO晶体的拉曼光谱谱峰都不同程度地向低波数方向移动,也存在不同程度的展宽,同时强度减弱.另外,在BGO熔体中存在[GeO4]和[BiO6]的结构基团;但两种结构之间的联键消失,即在熔体中二者是相互独立的生长基元.     

Raman scattering in defect chalcopyrite crystals

Summary Raman-scattering measurements on the defect chalcopyrite compounds CdGa₂Se₄, CdGa₂S₄, ZnGa₂S₄ are reported. The phonon picture is consistent with the space group. A comparison between corresponding phonons suggests a simple model for the vibrational dynamics. Preliminary Raman results in the mixed compound Cd _x Zn_1−x Ga₂S₄ and in resonance conditions in CdGa₂Se₄ are presented. Paper presented at the ?V International Conference on Ternary and Multinary Compounds?, held in Cagliari, September 14–16, 1982.     

钠分子的共振喇曼散射

本文用80mW6238.2(?)的He-Ne激光激发钠蒸气,用一种新颖的棱镜反射光路,从后向首次观察到了56O0～8200(?)钠分子的共振喇曼谱.     

Raman scattering by hot polaritons in NaClO3

Summary By nonlinear mixing of IR and visible radiation,i.e. coherent Raman scattering by polaritons driven by a CO₂ laser, it has been possible to get high-resolution spectra for theF-modes of a NaClO₃ crystal in the region (907÷957) cm⁻¹, where several isotopic modes are present. The obtained independent measurement of the refractive index and absorbance allows an accurate determination of the polariton dispersion curve and its width inq-space. The experimental data confirm the existence of a localized isotopic mode at 931 cm⁻¹ and a strongly damped isotopic mode near 960 cm⁻¹. Finally, an accurate measurement of the dispersion of the second-order nonlinear polarizability in the same energy region has been obtained for the first time. This work was supported by the Italian Consiglio Nazionale delle Ricerche and Ministero della Pubblica Istruzione.     

Second-order Raman scattering and infra-red absorption in SnS2

Summary The second-order Raman scattering and infra-red absorption spectra of 2H−SnS₂ are reported. The temperature, excitation wavelength and polarization dependences of Raman spectra are studied; resonance effects are put in evidence. The assignment of the second-order bands is discussed on the basis of the appliable selection rules. The role of phonons of high symmetry points different from Γ in second-order spectra is also taken into account. Work partially supported by M.P.I.     

Raman scattering by hot and thermal polaritons in crystal quartz

Summary Nonlinear mixing of IR and visible radiation,i.e. coherent Raman scattering by polaritons driven by a CO₂ laser, has been used to obtain the dispersion curve and its width inq-space of the polariton associated to theE-phonon at 1065 cm⁻¹ in crystal quartz. It is shown in this paper that a direct method to determine indipendently, with high precision, the refractive index and absorbance of a crystal can be obtained in this way. The results are compared with accurate data obtained from Raman scattering by polaritions in thermal equilibrium and very good agreement is found between the two measurements. It is finally shown that nonlinear-mixing techniques turn out to be completely consistent with the simple picture of scattering of light by hot polaritons. This work was supported by the Italian Consiglio Nazionale delle Ricerche del Ministero della Pubblica Istruzione.     

Weak vibronic coupling in resonance Raman scattering: a unifying approach

Summary A unifying approach to the theory of Raman intensities including nonadiabatic coupling and vibronic coupling is presented and explicit equations of the resonant scattering tensor are obtained for weak vibronic coupling. Previous results reported in the literature are derived as special cases of the present treatment.

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Riassunto Si presenta un trattamento teorico delle intensità Raman comprendente sia l'accoppiamento non adiabatico che quello vibronico e si riportano le equazioni esplicite per il tensore di scattering risonante nel caso di accoppiamento vibronico debole. Vari risultati presentati in letteratura sono derivati come casi speciali di questo approccio unificante.

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Резюме Предлагается унифицировать подход к теоретическому описанию рамановских интенсивностей, включая неадиабатическую связь и колебательную связь. В случае слабой колебательной связи получаются точные уравнения для тензора резонансного рассеяния. Различные результаты опубликованные в литературе, получаются как частные случаи предложенного унифицированного подхода.

     

Local relaxation in lanthanum silicate oxyapatites by Raman scattering and MAS‐NMR

To characterize the local relaxation in the structure of lanthanum silicate oxyapatite materials, six compositions with different cation and oxygen stoichiometries (La₈Ba₂Si₆O₂₆, La₉BaSi₆O_26.5, La₁₀Si_5.5Mg_0.5O_26.5, La_9.33SiO₂₆, La_9.67SiO_26.5 and La_9.83Si_5.5Al_0.5O_26.5) were investigated by combining Raman scattering and ²⁹Si and ²⁷Al magic‐angle spinning nuclear magnetic resonance (MAS‐NMR) spectroscopies. Only [SiO₄]⁴⁻ species were evidenced and the hypotheses of [Si₂O₇]⁶⁻ and [Si₂O₉]⁸⁻ entities were ruled out. Both oxygen excess and cation vacancies induce local distortions in the structure, which leads to nonequivalent [SiO₄]⁴⁻ species, characterized by different ²⁹Si MAS‐NMR signals and by splitting of Raman signals. Copyright © 2011 John Wiley & Sons, Ltd.     

Raman scattering studies of sodalite for crystal structure and coloration mechanism

Summary Group-theoretical study of the vibrational modes of chlorosodalite [Na₄Al₃(SiO₄)₃]₂ has been carried out for theT _d ¹ space group. The Raman-active modes are evaluated and comparison is made with the experimental results on sodalite. It is shown that the experimental Raman spectrum does not support the structure of sodalite to beT _d ¹ but confirms it to beT _d ¹ . Raman scattering studies were performed on X-ray irradiated As-grown single crystal of chloro-sodalite to identify the coloration mechanism. Enhancement of oxygen twisting and stretching mode intensities on X-ray irradiation indicates the formation of neutral sodium colloidal aggregate during the coloration process. The authors of this paper have agreed to not receive the proofs for correction.     

KDP晶体受激拉曼散射特性

详细比较了磷酸二氢钾(KDP)晶体的自发拉曼散射和受激拉曼散射光谱,在受激拉曼散射(SRS)中观察到了自发拉曼散射中最强的振动模的三阶Stokes光(559.43,589.74,623.50nm),由于其他振动模的受激拉曼散射增益系数较小,其SRS光谱未观察到。另外,比较了传统生长的未退火和退火后的KDP晶体及快速生长的锥区和柱区KDP晶体的受激拉曼散射增益系数,结果表明生长方法和热退火对KDP晶体的受激拉曼散射增益系数无明显影响。