Resonance Raman spectra of highly oriented trans polyacetylene

Resonant Raman spectra of highly oriented trans polyacetylene have been obtained for different scattering configurations at various exciting wavelengths. The polarization properties of the Raman active phonons have been determined for the first time. The changes in the Raman bandshapes observed upon changing the scattering configuration seem to imply that the dispersion of the Raman bands originates from a distribution of conjugation lengths.     

Studies on the resonance Raman spectra of polyaniline obtained with near‐IR excitation

The effects of near‐IR (NIR) laser power over the Raman spectra of poly(aniline) emeraldine salt (PANI‐ES) and base (PANI‐EB) were investigated. The reasons for the existence of several bands from 1324 to 1500 cm⁻¹ in the Raman spectra of poly(aniline) obtained at NIR region were also studied. The bands from 1324 to 1375 cm⁻¹ were associated to νC N of polarons with different conjugation lengths and the bands from 1450 to 1500 cm⁻¹ in Raman spectra of PANI emeraldine and pernigraniline base forms were correlated to νCN modes associated with quinoid units having different conjugation lengths. The increase of laser power at 1064.0 nm causes the deprotonation of PANI‐ES and the formation of cross‐linking segments having phenazine and/or oxazine rings. For PANI‐EB only a small spectral change is observed when the laser power is increased, owing to the low absorption of this form in the NIR region. Copyright © 2007 John Wiley & Sons, Ltd.     

针对水质监测的紫外-可见光谱双光程融合优化算法

紫外-可见光谱法多参数水质在线监测系统面对复杂水体时,常需要频繁改变探头光程以保持光谱较高的信噪比。然而,适合的光程往往需要大量实验才可确定,难以满足在线监测系统对实时性、精度、灵敏度、稳定性等的实际需求。研究了一种紫外-可见光谱双光程融合优化算法,将同时采集的长短两种光程光谱使用了滑窗法估计它们光谱噪声方差分布,确定光谱强噪声区间;由于长短光程光谱的信号强度不同,使用了遗传算法计算得到双光谱融合的最佳增益匹配倍率;最后,按噪声方差分布使用分段加权方式得到较高信噪比的双光程融合光谱。实验结果表明,利用该法对重庆长寿湖水样、嘉陵江某排污口及邻苯二甲酸氢钾标准溶液三种样本进行测试,其融合光谱在200～250 nm区域的强噪声得到抑制,零值干扰左推至220 nm之前,样本的峰值信噪比均有显著提高,证明了算法的有效性和普适性。该算法无需大量实验以获得最佳光程,对于拓宽紫外-可见光谱水质在线监测系统的应用范围具有较为重要的现实意义。     

六方晶型MgTiO3温致微结构变化及其原位拉曼光谱研究

采用固相烧结法制备了六方晶型结构的MgTiO₃粉体. 经高温原位X射线衍射分析(293-1473 K)进行了表征与确认,获得了晶胞参数及其随温度的变化,测量了高温原位拉曼光谱(273-1623 K),并运用第一性原理理论计算方法对应核实了拉曼谱峰的归属. 结果表明,随着温度升高,MgTiO₃晶面间距和晶格常数增大,从而反映对于拉曼光谱较为敏感的键长和键角的变化;温致拉曼位移可以反映Ti-O,Mg-O等键长以及Ti-O-Ti,Ti-O-Mg与Mg-O-Mg等键角随温度的细微变化,相关关系则独立于温度,有效提升了原位拉曼光谱微探针诊断技术的分析能力;拉曼谱峰随温度升高而展宽,表明原子瞬间运动振幅加剧,弥散性增加,稳定性有所下降,但仍维持六方晶型. 关键词： 3')" href="#">MgTiO₃ 微结构 拉曼光谱 高温     

溶液中β胡萝卜素的共振拉曼光谱性质的研究

β胡萝卜素是一种重要的共轭多烯生物分子, 其在光电器件与功能材料等研制方面有重要应用。本文利用金刚石对顶砧技术, 在0～0.60 GPa的压强范围下, 分别对β胡萝卜素溶于水和二硫化碳溶液进行了原位拉曼光谱测量, 比较了二者的拉曼频移和半高宽等光谱特性。实验结果表明, 两种样品的拉曼频移均随着压强的增加而向高波数方向移动, 半高宽也随之增加。引用线性链状多烯分子的两种理论模型, 即 “相干弱阻尼电子-晶格振动模型”和 “有效共轭长度模型”等理论给予了解释。其机理是由于压力的增加, β胡萝卜素分子被压缩, 结构有序性下降, 有效共轭长度减小, 拉曼活性降低, 碳碳键的相干弱阻尼电子-晶格振动减弱。CC键的键长变短, 因此拉曼蓝移; CC键的键长差增加, 从而使半高宽增加。此外, 由于β胡萝卜素溶于非极性溶剂CS₂溶液中, 受到周围溶剂分子的作用, 使溶质与溶剂之间的色散力作用对压力更敏感一些, 从而使得其拉曼频移和半高宽随压强变化的斜率要比溶于水中的大。为研究共轭多烯分子在外场下的分子结构变化以及溶剂中分子的存在形式等具有一定的应用价值。     

Temperature-dependent photoreflectance of SnS crystals

The optical properties of single-crystal SnS were studied by photoreflectance (PR) spectroscopy. Temperature-dependent PR spectra were measured in the range 20–200 K. A room-temperature bandgap energy value of E_g=1.317 eV was estimated by fitting the temperature dependence of the bandgap energy obtained from the PR spectra. The vibrational properties of orthorhombic SnS were studied using Raman spectroscopy. Four vibrational modes were detected at 95, 163, 191, and 218 cm^–1.     

不同光程对山茶油掺假近红外检测精度的影响

利用近红外光谱在不同光程下对山茶油中掺杂大豆油的掺伪量进行定量检测研究,着重分析光程对掺伪量检测精度的影响。将大豆油按一定质量分数掺入山茶油获取实验样本,掺伪质量分数范围为1%～50%。利用QualitySpec型光谱仪采集样本在不同光程(1,2,4,10 mm)下的透射光谱,通过对比不同建模方法、预处理方法及建模波段范围所建立的掺伪量定量预测模型,分析光程对掺伪量检测精度的影响。研究结果表明,光程由1 mm增加到4 mm时,掺伪量定量预测模型性能随着光程的增加而逐渐变好,检测精度逐步提高;光程由 4 mm增加到10 mm时,掺伪量定量预测模型性能变差,检测精度下降,4 mm为较优的光程。在1,2,4和10 mm下所建立的较优掺伪量定量预测模型的预测集决定系数 (R2_P)和预测均方根误差(RMSEP)分别为0.923, 0.977, 0.989, 0.962和4.58%, 2.54%, 1.72%, 3.20%。     

Optical, electrical and photovoltaic properties of thermally annealed PPHT:DDE blend thin films

We have investigated the optical, electrical and photovoltaic properties of devices based on 1,2-diazoamino diphenyl ethane (DDE) and poly(3-phenyl hydrazone thiophene) (PPHT):DDE blend. It is observed from the J-V characteristics of the Al/DDE/ITO (ITO—indium tin oxide) device that the electron current injected from Al contact was shown to be space charge limited (SCL), indicating that Al forms nearly ohmic contact for electron injection into lowest unoccupied molecular orbital (LUMO) of DDE. The effect of thermal annealing and composition, on the optical, electrical and photovoltaic response of blend of PPHT and DDE sandwiched between a transparent ITO electrode and an Al back contact are investigated. The observed absorption quenching in the PPHT:DDE blend is attributed to the disordering of PPHT chains and charge transfer between PPHT and DDE as evidenced by FTIR spectra. The observed red shift in the absorption peak on thermal annealing is due to the improvement in the ordering and increases in conjugation length in PPHT. The observed dark current-voltage curves agree well with trap-controlled SCL transport theory. The photophysics of the blend material and influence of thermal annealing on the performance and morphology of these devices were discussed. Annealing process results in the formation of PPHT:DDE complex and increase in the ordering of polymer chain, that increases the incident photon to current efficiency (IPCE) and power conversion efficiency of the photovoltaic devices.     

温度对β胡萝卜素结构有序的影响

本文测量了全反式β胡萝卜素在二甲基亚砜中81–25 ℃ 范围的紫外–可见吸收和拉曼光谱. 结果表明, 随温度降低, 紫外–可见吸收光谱、拉曼光谱都发生红移, 拉曼光谱线型变窄, 散射截面增加这些现象的发生是由于随温度降低, β胡萝卜素分子的热无序降低、分子结构有序性增加、π电子离域扩展, 有效共轭长度增加, 分子的电子能隙变窄. 另外, 随着温度的降低, 溶剂密度增加, 由Lorentz-Lorenz 关系得知相伴的折射率增加, 从而引起吸收光谱的红移. CC键键长增加, 使CC 键拉曼光谱红移; 振动弛豫时间变长, 各CC 键之间的键长差减小, 线宽变窄; 但由于声子, π电子耦合加强使CC键拉曼线型不对称程度增加, 低频端"肩"扩展, CC键的弱阻尼相干振动增加, 使拉曼散射截面增加. 关键词： β胡萝卜素 分子结构有序 红移 拉曼散射截面     

β-胡萝卜素分子的黄琨因子的温度特性

β-胡萝卜素具有光采集、光防护功能, 又是重要的光电材料, 它在外场下的分子结构和性能变化既有理论意义也有应用价值。测量了β-胡萝卜素在环己醇中68～26 ℃温度范围内的紫外-可见吸收、拉曼光谱。实验结果表明随着温度的降低, 黄琨因子和碳碳键每个振动模的电子-声子耦合常数减小, 紫外-可见吸收光谱红移, 碳碳键拉曼散射截面增加。用线性链状多烯分子的“相干弱阻尼电子-晶格振动模型”、“有效共轭长度模型”等理论给予了解释。随着温度的降低,β-胡萝卜素分子的热无序减小,分子结构有序性增加,π电子离域扩展,有效共轭长度增加,导致紫外-可见吸收光谱红移和强的拉曼活性。相干弱阻尼电子-晶格振动增强,使碳碳键拉曼散射截面增加。引用带有量纲的电子-声子相互作用常数,既可以与黄昆因子建立关系式,计算出碳碳键每个振动模的数值,也可以表征分子的有效共轭长度,π电子离域程度及拉曼散射截面的大小等。     

塑化剂邻苯二甲酸二辛酯的拉曼光谱计算及分析

近几年,国内有关塑化剂的食品安全事件频发,迫切需求加强对于食品中塑化剂的检测研究工作。邻苯二甲酸二辛酯是塑化剂的一种。理论计算和实验测量了邻苯二甲酸二辛酯的拉曼光谱。利用密度泛函理论DFT(B3LYP)的三参数混合方法对其进行了空间结构优化;然后分别用(Hartree-Fock)HF/3-21G和DFT/3-21G两种算法计算了它的拉曼光谱和红外光谱,给出了光谱强度图。实验测量了分析纯级邻苯二甲酸二辛酯的拉曼光谱,并和理论计算结果进行了对比,显示了很好的一致性,与此同时由于计算方法的不同,从图中可以看出Gaussian计算的HF和DFT算法无论是峰的位置还是相对强度等都均存在差别。还给出了常用塑化剂邻苯二甲酸二辛酯的各个键长、键角等空间结构参数,并对邻苯二甲酸二辛酯分子在400～3 500 cm-1区间的振动谱做了指认。报道了常用塑化剂邻苯二甲酸二辛酯的拉曼光谱研究工作。这些工作将有助于拉曼光谱技术在食品检测领域的研究和应用。     

Raman and infrared spectroscopical investigation of the optical vibrational modes in GaSb/AlSb superlattices

The vibrational spectrum of ultra-thin layer GaSb/AlSb superlattices was investigated in detail by infrared (IR) and Raman spectroscopies. The effect of confinement of the transverse and longitudinal optical phonons in both types of the layers was studied. The dispersions of optical phonons of the GaSb and the AlSb obtained from the analysis of the Raman and IR spectra are in a good accordance with the theoretical data and results of neutron scattering experiments. First- and second-order Raman spectroscopy indicates the presence of intermixture of atoms at the interfaces in the GaSb/AlSb superlattices. Received: 11 May 1998 / Accepted: 21 July 1998     

Can Raman spectroscopy detect cumulenic structures of linear carbon chains?

The molecular and vibrational structures of cumulenic carbon chains are investigated by density functional theory calculations and compared with that of hydrogen‐capped polyynes. The small value of bond length alternation (BLA) along the CC bonds sequence obtained by geometry optimization of uncapped C_n chains and vinyl‐capped carbon chains confirms their cumulenic structure. It is demonstrated that for finite length chains the structural parameters are determined by end effects as far as the Peierls distortion, expected for very long molecules, does not occur. The Raman spectra of such molecules are calculated to verify the possibility of identifying markers of cumulenic chains by means of vibrational spectroscopy. As expected, the longitudinal mode consisting of the BLA oscillation, which is responsible for the strongest Raman transition of polyynes, becomes very weak for cumulenes; this behaviour is rationalized in terms of local polarizability derivatives. However, other longitudinal modes can be observed in the Raman spectra of C_n chains. The wavenumber behaviour and the optical activity of these modes are interpreted on the basis of the phonon dispersion branch of an ideally infinite cumulenic polymer. Raman intensities computed for chains of different lengths allow to conclude that cumulenic molecules could be detected and identified by means of Raman spectroscopy. Copyright © 2009 John Wiley & Sons, Ltd.     

Effect of nickel incorporation on the optical properties of diamond-like carbon (DLC) matrix

The present study investigates the optical behavior of composite nanostructured DLC based films and functional coatings. Diamond-like carbon (DLC) thin films were synthesized by electrodeposition method onto SnO₂-coated glass substrates using an electrolyte of a mixture of acetic acid and water. Nanoparticles of nickel were then introduced into the DLC matrix. Morphology of the metal incorporated thin films and distribution of nanoparticles were studied by SEM; continuous homogeneous distribution of the particles was observed. Raman spectroscopy showed additional peaks in addition to the peaks due to DLC matrix. FTIR spectra revealed new peaks in the lower wave number region due to metal inclusion. UV-vis transmittance studies were performed to calculate the band gap of the samples. The estimated band gap from the Tauc relation was found to vary from 2.63 eV for the virgin DLC to 1.48 eV for the metal incorporated DLC.     

Raman spectroscopy of a single ion coupled to a high-finesse cavity

We describe an ion-based cavity-QED system in which the internal dynamics of an atom is coupled to the modes of an optical cavity by vacuum-stimulated Raman transitions. We observe Raman spectra for different excitation polarizations and find quantitative agreement with theoretical simulations. Residual motion of the ion introduces motional sidebands in the Raman spectrum and leads to ion delocalization. The system offers prospects for cavity-assisted resolved-sideband ground-state cooling and coherent manipulation of ions and photons. C. Russo and H.G. Barros contributed equally to this work.     

Influence of vapor transport equilibration on Raman spectra of Er:LiNbO3 crystals

Raman spectra of as-grown and vapor transport equilibration (VTE) treated Er:LiNbO₃ crystals, which have different cut orientations (X-cut and Z-cut), different Er-doping levels (Er:(0.2, 0.4 and 2.0 mol%)LiNbO₃) and different VTE durations (80, 120, 150 and 180 h), were recorded at room temperature in the wavenumber range 50-1000 cm⁻¹ by using backward scattering geometry. The spectra were attributed on the basis of their spectral features and the previous experimental work and the most recent theoretical progress in lattice dynamics on pure LiNbO₃. In comparison with the pure crystal the most remarkable effect of Er-doping on the Raman spectrum is observed for the E(TO₉) mode. It does not appear at 610 cm⁻¹ as the pure crystal, but locates at 633 cm⁻¹. In addition, the doping also results in the lowering of the Raman phonon frequency, the broadening of the Raman linewidth and the changes of the relative Raman intensity of some peaks. The VTE treatment results in the narrowing of the linewidth, the recovery of the lowered phonon frequency and the further changes of relative Raman intensity. The narrowing of Raman linewidth indicates that the VTE processing has brought these crystals closer to stoichiometric composition. The VTE treatment has induced the formation of a precipitate ErNbO₄ in the high-doped Er(2.0%):LiNbO₃ crystals whether X- or Z-cut. For these precipitated crystals, besides above linewidth and phonon frequency features, they also display more significant Raman intensity changes compared with those not precipitated crystals. In addition, a slight mixing between A₁(TO) and E(TO) spectra is also observed for these precipitated crystals. Above doping and VTE effects on Raman spectra were quantitatively or qualitatively correlated with the characteristics of the crystal structure and phonon vibrational system.     

Determination of SWCNT diameters from the Raman response of the radial breathing mode

We report on the evaluation of the distribution of diameters for nanotube samples with a wide variation of mean diameters. Such results were obtained from a detailed analysis of the radial breathing mode Raman response and compared to results obtained from an evaluation of optical spectra and X-ray diffraction pattern. The evaluation of the Raman data needs a well refined analysis as the experimental analysis exhibits a rather complicated and oscillating relation between response and exciting laser. Both, an exact calculation where the density of states was considered explicitly and an approximate calculation were applied. Both models used for the analysis are able to explain several unexpected results from the experiment such as the oscillating behavior of the spectral moments, unusual discontinuities in the first moments of the Raman response for excitation in the IR, a fine structure for the response in optics and Raman, and an up shift of the RBM frequency as compared to qualified ab initio calculations. In detail the first moment and the variance of the spectra were used for the evaluation of the diameter distribution. To obtain good results between experimental and theoretical oscillation pattern the transition energy between the first two van Hove singularities had to be scaled up which is considered as a result from coulomb interaction of the electrons in the tubular material. On the other hand the analysis does not only allow to determine the mean value and the width of the diameter distribution but yields also a value for the average bundle diameters or, alternatively, the strength of the tube-tube interaction. The model used for the analysis of the Raman data is also appropriate to analyze the optical response, at least for the spectral range from 0.5 eV to 3.5 eV. The fine structure in the response for the transitions between the three lowest van Hove singularities is well reproduced and the mean tube diameters and their distribution is obtained in very good agreement with the results from the Raman analysis. From the X-ray analysis the same mean values and comparable distributions for the tube diameters were received whereas the bundle diameters could not be retained with high precision in this case. Received 18 February 2001 and Received in final form 3 April 2001     

Vibrational spectroscopy of structural defects in oligothiophenes

Vibrational spectra of oligothiophenes with structural defects are calculated within the density-functional-theory methodology. The effects of the defective αβ linkages on the infrared (IR) and Raman spectra are characterized from calculations of all isomers up to the hexamer. The signatures of αβ linked monomers can be found in IR spectra from broken symmetry arguments which result in absorptions localized in the defective region. The positions of the absorption peaks in the Raman spectra seem to be unaffected by the presence of such defects; however, strong reductions in the intensities are observed because of the shortening of the conjugation length.     

Spatially resolved Raman spectroscopy evaluation of residual stresses in 3C-SiC layer deposited on Si substrates with different crystallographic orientations

Raman scattering studies were performed on hot-wall chemical vapor deposited (heteroepitaxial) silicon carbide (SiC) films grown on Si substrates with orientations of (1 0 0), (1 1 1), (1 1 0) and (2 1 1), respectively. Raman spectra suggested that good quality cubic SiC single crystals could be obtained on the Si substrate, independent of its crystallographic orientation. Average residual stresses in the epitaxially grown 3C-SiC films were measured with the laser waist focused on the epilayer surface. Tensile and compressive residual stresses were found to be stored within the SiC film and in the Si substrate, respectively. The residual stress exhibited a marked dependence on the orientation of the substrate. The measured stresses were comparable to the thermal stress deduced from elastic deformation theory, which demonstrates that the large lattice mismatch between cubic SiC and Si is effectively relieved by initial carbonization. The confocal configuration of the optical probe enabled a stress evaluation along the cross-section of the sample, which showed maximum tensile stress magnitude at the SiC/Si interface from the SiC side, decreasing away from the interface in varied rate for different crystallographic orientations. Defocusing experiments were used to precisely characterize the geometry of the laser probe in 3C-SiC single crystal. Based on this knowledge, a theoretical convolution of the in-depth stress distribution could be obtained, which showed a satisfactory agreement with stress values obtained by experiments performed on the 3C-SiC surface.     

Structural and optical properties of porous iron oxide

The structural and optical properties of the novel porous iron oxide fabricated by wood template have been investigated. The obtained porous iron oxide was characterized to be α- Fe₂O₃ by Fourier transform infrared and Raman spectroscopy. X-ray absorption fine structure measurement revealed that the bond length of Fe-O₁ of the porous iron oxide has good agreement with that reported for the α- Fe₂O₃ crystal structure while the bond lengths for Fe-O₂ and Fe-Fe deviate slightly from those of the α- Fe₂O₃ crystal structure. Photoluminescence from the porous iron oxide exhibited broad emission bands around 760 and 890 nm, which are believed to be due to the unique nanoscale structure of the porous iron oxide.