R6G单分子表面增强共振拉曼散射光谱探测研究

以共焦显微系统为平台,研究了不同浓度的R6G银溶胶的表面增强共振拉曼散射(SERRS)光谱, 结果表明不同浓度溶液中的R6G分子表现出了不同的光谱特性。在浓度为10-13mol·L-1的R6G银溶胶中 得到了R6G单分子的表面增强共振拉曼散射光谱,观察到了一些光谱非均匀变化现象,如谱色散、谱线的 强度起伏、拉曼谱的偏振化以及分子的闪烁等,并对这些现象进行了分析,证明得到的是R6G单分子的 SERRS光谱。文章还对单分子检测中的一些关键问题进行了分析与讨论,确定了单分子SERRS光谱检测的 适当条件。     

蛋白质溶液小角散射方法和天线膜蛋白LH2的低分辨形状研究

应用溶液小角散射技术,测定了在清洁剂溶液中细菌捕光天线色素蛋白(LH2)的小角散射.使用椭球体形散射曲线进行直接的曲线拟合,并以球谐函数展开的ab initio 低分辨形状测定等方法来研究LH2的低分辨形状.结果表明LH2蛋白分子在清洁剂溶液中的单分子具有椭球结构.与环状9对称的晶态结构不同,变形的LH2的椭球偏心率与单分子光谱学对孤立的LH2单分子测量结果一致.     

瑞利散射和米氏散射现象的实验演示

硫代硫酸钠与稀盐酸反应时,会在溶液中缓慢产生不溶于水的固态硫分子,其直径小于可见光的波长;随着反应的进行,多个硫分子聚结形成较大颗粒,其直径接近并逐渐大于可见光波长.在上述反应过程中,利用白光照射溶液,可以分别观察到瑞利散射和米氏散射现象,并在文中研究和分析瑞利散射时光的偏振特性.     

小分子液体的高温布里渊散射研究

利用金刚石对顶砧技术,采用180°背向散射和60°前向对称散射两种几何配置,对水、氨、二水合氨和甲烷等含氢小分子液体进行了高温高压布里渊散射研究,计算了在室温(296K)和高温(410K)下的声速,比较了不同小分子液体中的声速及绝热体弹模量随压力的变化关系。在等温条件下,各体系中声速随着压力的增加逐渐增加;在相同温度下,甲烷液体的声速随着压力增加的速率明显高于水、氨及二水合氨液体;在相同的温度和压力条件下,水、氨及二水合氨液体的体弹模量明显高于甲烷液体的体弹模量,表明氢键的存在对于小分子液体弹性具有较大影响。二水合氨的体弹模量斜率在1.5GPa左右发生改变,表明液体结构可能发生了改变,并分析了氢键对该体系弹性性质的影响。研究有助于理解其他含氢小分子液体中压力和温度诱导的分子结构变化。     

富勒烯-PVP聚合物链团结构的中子小角散射实验研究

应用中子小角散射技术研究了水溶液中富勒烯-PVP聚合物的链团结构及其大小以及它们在不 同富勒烯含量下的变化.结果表明：当加入富勒烯后，不论是PVP单体分子链还是大分子链团 ，其相关长度与纯PVP溶液相比均变小，且大分子链团的变化更为明显；在不同富勒烯含量 情况下，高富勒烯含量的富勒烯-PVP分子链团的体积更小. 关键词： 中子小角散射 富勒烯 PVP聚合物     

聚集体分子的基频和高阶线性Raman散射研究

本文报道了2,2′菁染料的J聚集体吸附于银胶体的表面增强基频和高阶线性Raman散射效应,分析了基频和高阶线性Raman光谱随染料溶液浓度的变化关系。结果表明,J聚集体分子在银胶体表面具有一个稳定的吸附结构,且侧立吸附于表面,一些低波数振动模式起因于J聚集体分子。高阶线性Raman散射的增强与J聚集体分子的性质有关。 关键词：     

海洋混合悬浮颗粒对蓝绿激光的散射特性研究

激光在水下的传输很大程度上会受到海水中悬浮颗粒物的影响,而目前对于海洋中悬浮颗粒物光散射的理论研究大多是针对单一成分的悬浮粒子而进行的,但是在真实海洋中悬浮颗粒物都是以多种成分混合的颗粒群形式而存在的,因此研究真实海洋中混合悬浮颗粒物对蓝绿激光的散射特性具有重要意义。该研究选取了对蓝绿激光传输产生较大影响的浮游藻类植物、悬浮泥沙、碎屑、悬浮气泡和矿物质这五种常见的悬浮颗粒物作为研究对象,充分考虑真实海况中这五种悬浮颗粒物的不同混合情况,构建了海水中混合球形悬浮颗粒物对蓝绿激光的散射特性模型。数值计算了海水中五种物质混合的球形悬浮颗粒物对532 nm蓝绿激光的统计平均光散射参量和平均散射相函数,分析不同混合悬浮颗粒物的混合比对平均散射、吸收和消光系数以及单次反照率随着粒子有效半径和粒子数浓度变化的影响,同时分析了不同粒子尺寸下的不同混合比对混合悬浮颗粒物的平均散射相函数随着角度变化的影响。数值结果表明,当悬浮泥沙在整个混合模型中占比越大时,平均散射系数越大,而当悬浮藻类粒子在整个混合模型中占比增大时,平均吸收系数增大,由此可知海洋中对光造成主要影响的五种常见悬浮颗粒物中,悬浮泥沙对光散射作用影响最大,悬浮藻类粒子对光吸收作用影响最大。随着悬浮颗粒物浓度的增大,混合粒子的单次反照率保持不变,由此可知混合悬浮颗粒物的平均光散射参量随着粒子浓度的增长速率是一致的。海洋中混合悬浮颗粒物的平均散射相函数随着粒子的有效半径的增大而增大,散射作用最大的混合比下的悬浮颗粒物其平均散射相函数最大,悬浮颗粒物的前向散射较强。该工作对蓝绿激光在海水中传输、信道建模,水下无线光通信的研究以及激光探测都具有重要的理论指导意义。     

液芯被导中受激动力学散射与受激拉曼散射的竞争

研究了液芯波导中受激拉曼散射和受激动力不散射的阈值随泵浦激光脉宽的变化，发现受激动力学散射的阈值随泵浦脉冲前沿增长率增大而下降。     

利用自发布里渊散射测量液体声速

为了克服共振干涉法在液体的热力学声速和高频声速测量方面精度不高的问题, 本文建立了一种基于自发布里渊散射原理的测定液体声速的实验装置. 利用法布里-珀罗干涉仪对散射光进行扫描滤波, 数据采集卡结合光子计数器对散射光进行探测, 设计了一种散射光信息采集分析方法. 该实验方法有效的解决了传统布里渊散射方法中信号失真的问题, 显著地提升了液体声速测量精度. 对308.6–906.2 MHz内298.15 K饱和液相CCl₄声速进行了测量, 测量结果与文献值具有较好一致性. 利用法布里-珀罗干涉仪周期性扫描的滤波原理, 通过在测量得到的布里渊频移上加减整数倍个自由波谱区, 得到了更大频率的波谱信息, 进而设计一种测定介质高频声速的方法. 对CCl₄在5406.1–5521.0 MHz频段内的声速进行了测量. 实验结果显示, CCl₄的热力学声速随频率无明显变化, 而高频声速随频率的增大呈增大趋势且远大于热力学声速, 证实CCl₄具有色散现象.     

布里渊散射及其在激光雷达中的应用

在简要介绍布里渊散射的基本性质的基础上,重点介绍了布里渊散射在激光雷达中的应用。主要分析了布里渊散射在水中声速测量、粘滞系数的测量和水中目标探测方面的原理和技术实现。     

CARS difference spectroscopy

Summary In this paper we present a vibrational-spectroscopy technique which combines the advantages of coherent anti-Stokes Raman spectroscopy (CARS) and linear Raman difference spectroscopy. The method which we call CARS difference spectroscopy can be applied for the study of small frequency shifts and/or bandwidth changes in the CARS spectra of liquid mixtures and solutions. First we develop the theory necessary for the interpretation of experimental data obtained from CARS difference measurements of mixtures of two Raman-active liquids and present some model calculations for benzene-toluene mixtures of different concentrations. Then the experimental arrangement used for CARS difference measurements as well as some examples of recorded spectra are described. We show that it is possible to observe the effects of dilution on CARS spectra with high accuracy by applying the discussed technique. Paper presented at the “XI European CARS Workshop”, Florence, Italy, 23–25 March, 1992.     

一种危险液体混合物的拉曼光谱定性定量识别方法

危险液体混合物的拉曼光谱定性定量分析一直是现场应用难点，为解决该问题，分析了多种物质混合后拉曼光谱的峰位、峰值、峰型变化情况，选取拉曼光谱关键特征峰进行数学简化，构建了从混合物物质成分到混合物拉曼光谱的映射关系，该映射关系描述多种物质成分混合的混合物拉曼特征峰响应只和混合物中各成分本身拉曼特征峰响应以及各物质成分混合比例有关，各物质成分按混合比例贡献拉曼特征谱峰，共同形成最终的混合物拉曼光谱。由该映射关系求逆，可实现从采集到的混合物拉曼光谱计算出各物质成分的混合比例。基于此，设计了危险液体混合物成分定性定量识别方法，主要方法步骤包括，首先进行拉曼光谱数据采集，然后进行拉曼光谱数据处理并获得拉曼特征峰，再进行测试样品与数据谱库标准品的正反向特征峰匹配，如果正反向特征峰匹配系数都比较高，在满足一定阈值条件下，可认定测试样品是某种纯净物，如果不是纯净物，则进入混合物分析，通过拉曼光谱特征峰反向匹配系数筛选，确定混合物成分构成，混合物成分确定后再进行混合物成分比例计算，最终实现危险液体混合物定性定量分析。实验部分，选定丙酮、甲苯、三氯甲烷、乙醇及其混合物进行实验验证，当混合物样品是丙酮、乙醇两种成分按3∶7比例混合时，经拉曼光谱识别方法计算，混合成分计算值是丙酮占比0.245 7，乙醇占比0.706 0；当混合物样品是甲苯、三氯甲烷两种成分按3∶7比例混合时，经拉曼光谱识别方法计算，混合成分计算值是甲苯占比0.323 4，三氯甲烷占比0.763 0；当混合物样品是丙酮、甲苯、乙醇三种成分按4∶3∶3比例混合时，经拉曼光谱识别方法计算，混合成分计算值是丙酮占比0.795 9、甲苯占比0.303 5、乙醇占比0.287 5，实验结果表明，当危险液体混合物成分是两种或三种成分混合时，混合成分计算值基本和实际值吻合，应用危险液体混合物的拉曼光谱定性定量识别方法，可较准确的从拉曼混合光谱中解析出各混合物成分以及各成分在混合物中的比例，可以判断混合物每个拉曼特征谱峰都来自于哪个成分或哪些成分拉曼特征谱峰的混合，谱图解析结果良好，对危险液体混合物现场分析鉴别有较大应用价值。     

Nonlinearity in Intensity versus Concentration Dependence for the Deep UV Resonance Raman Spectra of Toluene and Heptane

Abstract: The relation between Raman scattering, resonance Raman scattering, and absorption is reviewed to determine to what extent quantitative analysis can be applied in resonance Raman spectroscopy. In addition, it is demonstrated experimentally that normal Raman spectra can be dramatically inhibited by absorption and resonance Raman effects. Raman spectra of toluene and heptane mixtures—with progressively increasing concentrations of heptane—were measured using 229-nm laser excitation. The results show that the characteristic band intensities are not directly proportional to the relative concentrations of the compounds and deviate due to absorption resonance effects. An approximated mathematical model is developed to demonstrate that the intensities of the normal Raman scattering bands are suppressed. An inhibition coefficient K_i is introduced to describe the situation and determine the penetration depth. Most remarkably, it is shown that the intensity of the resonance Raman scattering bands can be constant even when the concentration ratios differ substantially in the sampled mixtures.     

Solvent dependent study of carbonyl vibrations of 3‐phenoxybenzaldehyde and 4‐ethoxybenzaldehyde by Raman spectroscopy and ab initio calculations

A Raman spectroscopy investigation of the carbonyl stretching vibrations of 3‐phenoxybenzaldehye (3Phbz) and 4‐ethoxybenzaldeheyde (4Etob) was carried out in binary mixtures with different polar and nonpolar solvents. The purpose of this study was twofold: firstly, to describe the interaction of the carbonyl groups of two solute molecules in terms of a splitting in the isotropic and anisotropic components and secondly, to analyze their spectroscopic signatures in a binary mixture. Changes in wavenumber position, variation in the anisotropic shift and full width half maximum were investigated for binary mixtures with different mole fractions of the reference systems. In binary mixtures, the observed increase in wavenumber with solvent concentration does not show linearity, indicating the significant role of molecular interactions on the occurrence of breaking of the self‐association of the solute. In all the solvents, a gradual decrease in the anisotropic shift reflects the progressive separation of the coupled oscillators with dilution. Γ_i(η_c), 3Phbz—solvent mixtures, exhibit a gradual decrease with decrease in the concentration of the solute which is an evidence on the influence of micro viscosity on linewidth. For 4Etob, the carbonyl stretching vibration shows two well‐resolved components in the Raman spectra, attributed to the presence of two distinct carbonyl groups: hydrogen‐bonded and free carbonyl groups. The intensity ratio of the carbonyl stretching vibration of these two types of carbonyl groups is studied to understand the dynamics of solute/solvent molecules owing to hydrogen bond interactions. Ab initio calculations were employed for predicting relevant molecular structures in the binary mixtures arising from intermolecular interactions, and are related to the experimental results. Copyright © 2009 John Wiley & Sons, Ltd.     

Abnormal characteristics of binary molecular clusters in DMSO–ethanol mixtures under external electric fields

For the nonlinearly phenomena on the dielectric properties of dimethyl sulfoxide (DMSO)–ethanol mixtures under a low intensity microwave field, we propose a conjecture that there exist some abnormal molecular clusters. To interpret the mechanism of abnormal phenomena and confirm our conjecture about the existence of abnormal molecular clusters, an in-depth investigation about the structure evolutions of (DMSO)_m(C₂H₅OH)_n (m = 0–4; n = 0–4; m + n ≤ 4) molecular clusters induced by external electric fields has been given by using density functional theory. The results show that there exist some binary molecular clusters with large cluster radii in mixtures, and some of them are unstable under exposure of electric fields. It implies that the existence of certain abnormal molecular clusters in DMSO-ethanol mixtures results in their abnormality of dielectric properties.     

基于分子对接的类二恶英类多氯联苯的拉曼光谱增强

为了从分子结构角度找到可以增强类二恶英类多氯联苯（PCBs）的拉曼光谱振动强度的结构变量，利用密度泛函理论（DFT）在B3LYP/6-31G（d）水平下对13种类PCBs结构进行优化，通过分子对接技术提取13种PCBs与联苯双加氧酶（Bpha，PDB：3GZX）对接后的PCBs分子结构，并计算了气态环境下对接前后PCBs分子的拉曼光谱振动强度和频率。研究结果表明：13种PCBs的拉曼振动归属为苯环变形、C-C伸缩、C-H摇摆、C-H伸缩以及各种形式的耦合，其中拉曼光谱频率在1 632.77~1 652.06 cm^-1之间的振动最强，苯环变形为特征振动；对接后PCBs的二面角大小有明显的改变，导致拉曼振动强度提高2.9%~213.98%，频率在1 631.57~1 651.94 cm^-1之间的拉曼峰整体发生蓝移，二面角大小与拉曼振动强度呈现一定程度的线性关系，随二面角逐渐减小，拉曼振动增强。实验结果表明，可通过调整PCBs的二面角大小达到提升PCBs辨识灵敏度的目的，并为PCBs拉曼光谱检测提供理论依据。     

Measurement of Raman scattering in simple liquids under the influence of high quasi-static electric fields

The vibrational Raman bands of some simple liquids are investigated on the influence of an external electric dc field. Thereby the electric field strength is varied in the range of 0.1 to 1 MV/cm. The experiments demonstrate that Raman intensities and depolarization ratios increase with increasing field strength and — after passing a maximum — decrease with even higher field strengths. In mixtures the field dependence of Raman intensity takes a different course than in pure liquids.     

Quantitative speciation of manganese oxide mixtures by RIXS/RRS spectroscopy

Resonant inelastic X‐ray scattering, also named X‐ray resonant Raman scattering, was recently used to discriminate local chemical environments. By means of this novel technique, the speciation of samples could be attained in a variety of samples and experimental conditions. Until now, this discrimination methodology had been applied only to pure compounds, being the speciation possible by two different mathematical treatments. Nevertheless, the effectiveness/sensitivity of this technique has not been tested yet in samples containing mixtures of oxides of the same element. In this work, the first results of quantitative speciation of mixtures of manganese compounds, using resonant inelastic X‐ray scattering/X‐ray resonant Raman scattering spectroscopy, are presented. The results show that it is possible to discriminate and quantify oxide mixtures of the same element in slightly different proportions, allowing a quantitative speciation of compound mixtures in a variety of experimental conditions, presenting also several advantages over conventional spectroscopic techniques. Copyright © 2017 John Wiley & Sons, Ltd.     

Deconvolution of Raman spectra for the quantification of ternary high‐pressure phase equilibria composed of carbon dioxide,water and organic solvent

The paper reports on a routine to extract the composition of multi‐component mixtures from their Raman spectra at elevated pressures. The strategy is based on fitting weighted Raman spectra of the pure compounds to the measured Raman spectrum of the mixture, also considering the effects of intermolecular interactions onto the Raman spectra by applying Gaussian and Voigt profile deconvolution of the Raman peaks. Thereby, an improved accuracy compared to previous evaluation strategies could be obtained. The more accurate data of the ternary mixtures of carbon dioxide, water and organic solvents are presented. Copyright © 2014 John Wiley & Sons, Ltd.     

Isotropic Raman spectra of liquid (isotope) mixtures: Intermolecular coupling of vibrational modes

The theory presented in this paper investigates the isotropic Raman spectra of liquid binary mixtures. It is found that the collective vibrational modes of different molecular species can be significantly coupled. This is a consequence of the (nearly) resonant vibrational transfer processes, which give rise to distinct vibrational correlations (i.e. correlations between adjacent molecules). The coupling, however, occurs only with weakly-separated or overlapping bands. The more general results of the theory are applied to isotope mixtures. The spectral information available from relevant dilution experiments is interpreted. In particular it is shown that the spectral properties of the vibrational self-correlation part can be concluded from the observed collective correlation function. The significance of the distinct vibrational correlations with respect to the infrared and depolarized Raman spectra is discussed.