BaBPO5晶体晶格振动光谱研究与第一性原理计算

通过偏振拉曼光谱和第一性原理计算对非线性光学晶体BaBPO₅的 晶格振动模式进行了研究. 实验得到了不同几何配置下、在100–1600 cm^-1范围内的晶体偏振拉曼光 谱与傅里叶变换红外吸收谱, 结合因子群分析方法研究了晶体的外振动与内振动模式特征. 分析表明拉曼振动主要来自于PO₄四面体和BO₄四面体的振动, 且PO₄基团振动具有较强的拉曼与红外活性. 此外,根据第一性原理对晶体拉曼振动进行了数值模拟, 进一步明确了拉曼峰与晶体中原子振动的对应关系, 计算表明拉曼光谱中位于672 cm^-1峰位来自晶体中B–O–P键的伸缩振动, 这是晶体中PO₄四面体和BO₄四面体共顶点连接的特征结构在光谱中的体现.     

P2O5-CuI-CuCl系统非晶态铜离子导体的EXAFS,IR,Raman光谱研究

本文用透射法EXAFS和IR,Raman光谱等手段研究了以P₂O₅,为基体的非晶态铜离子导体的微观结构,得出了非晶结构网络中存在[PO₄]^3-,[CuO₄]^6-,[CuO₃I]^5-,[PO₃I]^2-等四元骨架结构单元,Cu⁺在结构网络空隙中有两种不同的分布状况。并在此基础上对材料在50℃左右存在的二级相变及Cu⁺的其它传导性能进行了定性的描述。 关键词：     

铝硅酸盐Raman活性分子振动解析

分别测定了蓝晶石、红柱石和硅线石三种铝硅酸盐天然矿物晶体以及K₂O-Al₂O₃-SiO₂三元铝硅酸盐玻璃的Raman光谱。构建了一组硅铝四面体聚集体结构模型,采用量子化学自洽场分子轨道从头计算的方法计算了其Raman振动频率。分析研究了上述Raman光谱振动特征,确定了特征谱峰的归属,解析了铝对铝硅酸盐Raman活性分子振动特征的影响。结果表明,随四配位铝的增加,导致800～1 200 cm-1波数区间内谱峰频率降低,该区间的谱峰是Si—O_nb间非桥氧对称伸缩振动引起的,其中不含Al—O振动;700～800 cm-1区间内出现的谱峰归属于Al—O_nb间非桥氧的对称伸缩振动。     

碳酸铅在不同传压介质下的高压拉曼研究

为研究PbCO₃在高压下的稳定性,利用金刚石对顶砧技术,采用NaCl固体、甲醇-乙醇-水混合液体(16∶3∶1)和甲醇-乙醇混合液体(4∶1)做传压介质,开展了PbCO₃的高压拉曼实验,最高压强分别达到24.5、25.0和67.0 GPa。研究发现,PbCO₃在10、15和30 GPa左右发生相变,在静水压强条件下CO^2-₃基团的ν^2-外弯曲振动模出现了软化现象。通过对比得到不同传压介质中PbCO₃的Grüneisen参数γ,发现相变机制略有不同,并且压强对晶格振动的影响CO^2-₃基团的影响大,这是由Pb²⁺―O键的键长较大造成的。在所研究的压强范围内,PbCO₃没有发生分解或非晶化,30.0 GPa以上出现的PbCO₃-Ⅳ相直至67.0 GPa都很稳定。     

碱金属阳离子对[B3O7]型非线性光学晶体结晶习性的影响

本文利用高温拉曼光谱技术和从头计算的方法, 研究了LiB₃O₅和CsB₃O₅晶体高温熔融体的结构, 分析了碱金属阳离子对熔体结构的影响, 以及熔体结构的差异与LiB₃O₅和CsB₃O₅晶体结晶习性的联系. 结果表明: LiB₃O₅和CsB₃O₅晶体高温熔融体中的结构基团 主要为B₃Ø₇和B₃Ø₆两种不同类型的硼氧六元环; 环内BØ₄ 四面体的数量影响了六元环呼吸振动峰的拉曼频率, 随BØ₄四面体数量的增加六元环呼吸振动峰向低频移动; LiB₃O₅晶体高温熔融体中, BØ₄四面体含量相对较多; 然而, 离子半径相对较大的Cs⁺离子却阻碍了熔体中BØ₄四面体的形成, 造成CsB₃O₅晶体高温熔融体中BØ₄/BØ₃比值的降低. 结合LiB₃O₅和CsB₃O₅晶体生长动力学过程的分析 (Wang D, Wan S M et al. 2011 Cryst. Eng. Comm. 13 5239), 阳离子的不同导致高温熔体中BØ₄四面体数量的差异, 被认为是影响LiB₃O₅和CsB₃O₅晶体结晶习性的重要因素, 有效降低高温熔体中BØ₄四面体的数量, 将是实现LiB₃O₅晶体生长的关键条件. 关键词： 硼酸盐晶体 熔体结构 拉曼光谱 结晶习性     

Raman光谱方法研究三氯甲烷与苯分子间的C/H…π相互作用

测量了不同浓度三氯甲烷（CHCl₃）与苯（C₆H₆）二元溶液的Raman光谱,随C₆H₆浓度的增加,受分子间C/H…π相互作用的影响,CHCl₃中C—H键伸缩振动频率向低波数移动;当CHCl₃体积分数小于40%,C—H键伸缩振动频率不变,分子间C/H…π相互作用达到饱和.分别以CHCl₃和C₆H₆体积分数为70%的CHCl₃-C₆H₆混合溶液为研究对象,测量了它们的高压和低温Raman光谱.根据CHCl₃中C—H键伸缩振动频率随压强和温度的变化关系,得出了分子间C/H…π相互作用对压强和温度的扰动表现出不稳定性.     

Sr3TaGa3Si2O14(STGS)单晶的晶格振动

根据空间群理论,预测了Sr3TaGa3Si2O14(STGS)单晶的振动模式,并分别计算了非极性和极性振动模式的Raman散射强度。测量了STGS晶体的Raman光谱,并对其振动模式进行了指认。实验结果表明STGS晶体具有6个A1对称类特征振动模式:波数为126cm-1的振动峰可指认为SiO4团簇、Sr原子和TaO6团簇间的相对平动;245cm-1的振动峰是SiO4团簇的扭曲振动和Sr—TaO6—Sr伸缩振动耦合的结果;特征峰557和604cm-1分别来源于O—Ta—O和O—Ga—O的伸缩振动;896cm-1谱带对应着两个SiO4四面体的O—Si—O伸缩振动;991cm-1的谱带对应着两个SiO4四面体的Si—O伸缩振动。实验结果和理论计算结果均确证了STGS晶体的层状结构,其弱的各项异性和压电模量归因于十面体结构单元的微弱形变。     

PbWO_4微晶高压结构相变的Raman光谱研究

本文利用溶剂热方法合成出具有锥形结构的四方白钨矿相PbWO4微晶,并结合金刚石对顶砧压机,利用Raman光谱手段研究了其在22GPa压力下的结构变化。结果发现,在大约4.2GPa,发生了向单斜结构PbWO4-Ш相的局部转变。随着压力继续增大至7GPa,又发现了向亚稳单斜结构的褐钇铌矿相的转变。大约13.2GPa后,亚稳相褐钇铌矿结构也转变为更为致密的PbWO4-Ш相。该相变过程为可逆相变,卸压后恢复为白钨矿结构。     

281—332nm SO+2的光碎片激发谱研究

在超声分子束条件下，利用380.85nm的电离激光使SO₂分子经由［３＋１］共 振增强多光 子电离(REMPI)制备纯净的分子离子SO⁺₂(²A ₁(000))，用另一束解离激光在281 —332nm扫描获得了光解碎片激发(PHOFEX)谱.获得的光碎片SO⁺激发谱基本可以 归属为SO ⁺₂(,)←SO⁺关键词： +₂')" href="#">SO⁺₂ 光解离 光碎片激发谱     

光促进温和条件非贵金属催化下卤代烃与二氧化碳的羰基化反应及ESR谱研究

研究了卤代烃在光促进温和条件（常温常压）非贵金属[Co(acac)₂,Co(OAc)₂或CoCl₂]催化下与二氧化碳的羰基化反应；同时对反应过程中的ESR谱进行了研究. ESR谱研究表明，在光促进下二氧化碳参与的羰基化反应中有二氧化碳游离基负离子（CO^·-₂）[用DMPO（5,5-二甲基-1-吡咯啉-N-氧化物）捕获］生成.     

易解石族矿物的Raman光谱和光致发光谱研究

测定并讨论了中国白云鄂博矿区变生及退火晶态易解石族矿物Ｒａｍａｎ光谱和光致发光谱,与退火晶质矿物相比,变生态易解石的Ｒａｍａｎ光谱和光致发光谱的强度降低,谱线宽化弥散,说明在变生过程中,矿物的结构发生畸变,元素分布趋于无序。分析表明,易解石族矿物在５１４．５ｎｍ激光激发下的所有光致发光谱峰均出自Ｎｄ＾３＋的辐射跃迁。     

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     

基于离子注入技术的ZnMnO半导体材料的制备及光谱表征

通过离子注入技术制备了ZnMnO半导体材料，研究离子注入剂量与退火对材料光谱性质的影 响.Raman光谱研究发现，575cm^-1处声子模展宽是由高剂量Mn注入引起的缺陷所 致，退火样品528cm^-1振动模来自Mn相关的杂质振动.室温光致发光谱表明，退 火对高剂量注入样品的可见发光带有增强作用. 关键词： ZnMnO 离子注入 Raman光谱 室温光致发光     

Raman scattering studies on phase transition in barium sodium niobate at high pressure

Phase transition in barium sodium niobate at high pressure is investigated by Raman scattering experiments. Polarized Raman spectra from polished single domain crystal plates of definite orientation are obtained under pressure produced by a diamond anvil device. Anomalous hardening and intensity decrease of 32 cm^-1B₂ mode are found with increasing pressure. A remarkable pressure dependence of the frequencies of the bending modes of NbO₆ octahedrons is observed.     

Dehydration and recrystallization of radiation-damaged titanite under thermal annealing

Abstract

Dehydration of oriented sections of a radiation-damaged titanite crystal, CaTiSiO₅, at temperatures up to 1500K was analysed using infrared spectroscopy. The IR spectra of the untreated sample show only a very weak orientational dependence. The absence of sharp absorption peaks at wave number near 3486 cm^?1 in metamict titanite shows that the local environmental configurations of OH species in the metamict titanite differ strongly from that of crystalline titanite. The OH spectra of radiation-damaged titanite can be decomposed into two components: the first component shows anisotropic and sharp spectral features while the second component consists of a broad spectral feature like those observed in disordered silica glasses. It is proposed that the first component is related to the crystalline part of the titanite sample while the second is from the defected and disordered part which suffered strong radiation damage. With increasing annealing temperature, a decrease in the broad absorption between 2500 and 3200 cm^?1 is accompanied by a recovery of sharp IR bands near 3486 cm^?1 which display the same orientational dependence as undamaged single crystals. Annealing the sample at 1000K leads to the line profiles and orientational dependence of the main OH stretching bands near 3486cm^?1 that are virtually identical with those of crystalline, undamaged titanites. At temperatures above 1500 K, the crystal starts to melt and the orientational dependence of the IR absorption is destroyed. The recrystallization processes are quantified and discussed in terms of a percolation behaviour of amorphous and crystalline titanite. It is proposed that hydrogen transport is strongly enhanced during recrystallization.     

Infrared laser magnetic resonance detection of SD at 1885·76 cm-1

The visible and near infrared luminescence spectra of MoCl₆ ^3- in Cs₂NaMCl₆ (M=Sc, Y, In) and MoBr₆ ^3- in Cs₂NaYBr₆ have been measured between 15 000 cm^-1 and 3000 cm^-1 at liquid helium temperatures. Comparison with new electronic absorption, infrared and Raman spectra have enabled five luminescence transitions between the states derived from the t _2g ³ configuration to be assigned unambiguously. Each electronic transition shows extensive vibronic structure which can be analysed to yield the vibrational frequencies of the MoX ₆ ^3- ion in each state. The spectra are strongly influenced by resonant interactions between the MoX ₆ ^3- ion and the internal and lattice modes of the host lattices and there is an enormous variation in the intensities of the vibronic origins.     

Optical absorption spectra of synthetic CoCO3 single crystal

New results have been obtained on absorption spectra of synthetic CoCO₃ single crystal in the spectral range from the 11,500 to 34,500 cm^-1. Some vibration frequencies of the (CO₃)^2- ions have deduced from the absorption spectrum and zero-phonon lines have been identified. In the regions 22,900 and 24,500 cm^-1, a shift is observed of absorption frequencies with antiferromagnetic order for temperatures increasing from 4.2 to 20°K.     

Raman microscopy of haidingerite Ca(AsO3OH)·H2O and brassite Mg(AsO3OH)·4H2O

Raman spectroscopy has been used to study the arsenate minerals haidingerite Ca(AsO₃OH)·H₂O and brassite Mg(AsO₃OH)·4H₂O. Intense Raman bands in the haidingerite spectrum observed at 745 and 855 cm⁻¹ are assigned to the (AsO₃OH)²⁻ν₃ antisymmetric stretching and ν₁ symmetric stretching vibrational modes. For brassite, two similarly assigned intense bands are found at 809 and 862 cm⁻¹. The observation of multiple Raman bands in the (AsO₃OH)²⁻ stretching and bending regions suggests that the arsenate tetrahedrons in the crystal structures of both minerals studied are strongly distorted. Broad Raman bands observed at 2842 cm⁻¹ for haidingerite and 3035 cm⁻¹ for brassite indicate strong hydrogen bonding of water molecules in the structure of these minerals. OH···O hydrogen‐bond lengths were calculated from the Raman spectra based on empirical relations. Copyright © 2009 John Wiley & Sons, Ltd.     

Raman and mid‐IR spectroscopic study of the magnesium carbonate minerals—brugnatellite and coalingite

Two hydrated hydroxy magnesium carbonate minerals brugnatellite and coalingite with a hydrotalcite‐like structure were studied by Raman spectroscopy. Intense bands are observed at 1094 cm⁻¹ for brugnatellite and at 1093 cm⁻¹ for coalingite attributed to the CO₃²⁻ν₁ symmetric stretching mode. Additional low intensity bands are observed at 1064 cm⁻¹. The existence of two symmetric stretching modes is accounted for in terms of different anion structural arrangements. Very low intensity bands at 1377 and 1451 cm⁻¹ are observed for brugnatellite, and the Raman spectrum of coalingite displays two bands at 1420 and 1465 cm⁻¹ attributed to the (CO₃)²⁻ν₃ antisymmetric stretching modes. Very low intensity bands at 792 cm⁻¹ for brugnatellite and 797 cm⁻¹ for coalingite are assigned to the CO₃²⁻ out‐of‐plane bend (ν₂). X‐ray diffraction studies by other researchers have shown that these minerals are disordered. This is reflected in the difficulty of obtaining Raman spectra of reasonable quality and explains why the Raman spectra of these minerals have not been previously or sufficiently described. A comparison is made with the Raman spectra of other hydrated magnesium carbonate minerals. Copyright © 2008 John Wiley & Sons, Ltd.     

Raman spectroscopy of selected borate minerals of the pinakiolité group

The Raman spectra of a series of related minerals of the pinakiolité group have been collected and the spectra related to the mineral structure. These minerals are based upon an isolated BO₃³⁻ ion. The site symmetry is reduced from D_3h to C₁. Intense Raman bands are observed for the minerals takeuchiité, pinakiolité, fredrikssonité and azoproité at 1084, 1086, 1086 and 1086 cm⁻¹. These bands are assigned to the ν₁ BO₃³⁻ symmetric stretching mode. Low‐intensity Raman bands are observed for the minerals at 1345, 1748; 1435, 1748; 1435, 1750; and 1436, 1749 cm⁻¹, respectively. One probable assignment is to ν₃ BO₃³⁻ antisymmetric stretching mode. Intense Raman bands of the studied minerals at 712 cm⁻¹ are attributed to the ν₂ out‐of‐plane bending mode. Importantly, through the comparison of the Raman spectra, the molecular structure of borate minerals with ill‐defined structures can be obtained. Copyright © 2010 John Wiley & Sons, Ltd.