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1.
Leonardo Puppulin Masaya Kotaki Morimasa Nakamura Daisuke Iba Ichiro Moriwaki Giuseppe Pezzotti 《Journal of Raman spectroscopy : JRS》2012,43(12):1957-1963
The orientation dependence in space of Raman‐active vibrations in the hexagonal structure of polyoxymethylene (POM) is discussed in terms of Raman tensor elements as intrinsic physical parameters of the lattice. The variation of polarized intensity for the A1 and the E1 vibrational modes with respect to the POM molecular orientation is systematically studied, from both theoretical and experimental viewpoints, according to the symmetry assignments of each vibrational mode. A set of working equations including the Raman selection rules associated with the A1 and the E1 modes and the orientation distribution function are explicitly formulated and validated by means of a least‐square fitting procedure on experimental data. In addition, an approach based on the introduction of orientation distribution functions is applied to quantitatively assess and compare on a statistical base the molecular orientation of two different types of electrospun POM nanofibers. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
2.
V. Presser B.‐E. Schuster M. B. Casu U. Heinemeyer F. Schreiber K. G. Nickel T. Chass 《Journal of Raman spectroscopy : JRS》2009,40(12):2015-2022
In this work we report on the capability of polarized Raman spectroscopy to investigate the structure of thin organic films. Diindenoperylene (DIP) thin films on (1 × 1)‐rutile(110) were prepared via organic molecular beam deposition (OMBD). Raman spectra of DIP thin films showed several strong Raman modes in the wavenumber region from 1200 to 1650 cm−1. The Ag mode at 1284 cm−1 shows two contributions, thereby indicating the coexistence of at least two DIP film structures. Polarized Raman spectroscopy was applied to characterize the molecular orientation and the dominance of the σ‐configuration (i.e. upright standing DIP molecules) was found. Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
3.
Real‐time polarized Raman spectroscopy was used in this study to measure the molecular orientation evolution during blown film extrusion of low‐density polyethylene (LDPE). Spectra were obtained at different locations along the blown film line, starting from the molten state near the die and extending up to the solidified state near the nip rolls. The trans C C symmetrical stretching vibration of polyethylene (PE) at 1132 cm−1 was analyzed for films possessing uniaxial symmetry. For the given peak, the principal axis of the Raman tensor is coincident with the c‐axis of the orthorhombic crystal, and was used to solve a set of intensity ratio equations to obtain second (〈P2(cosθ)〉) and fourth (〈P4(cosθ)〉) moments of the orientation distribution function. The orientation parameters (P2, P4) were found to increase along the axial distance in the film line even past the frost‐line height (FLH). The P2 values also showed an increasing trend with crystalline evolution during extrusion, consistent with past observations that molecular orientation takes place even after the blown film diameter is locked into place. It was also found that the integral ratio (I1132/I1064) obtained from a single, ZZ‐back‐scattered mode can provide a reasonable estimate of molecular orientation. These results indicate the potential of real‐time Raman spectroscopy as a rapid microstructure monitoring tool for better process control during blown film extrusion. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
4.
Wenliang Zhu Jiliang Zhu Mingsong Wang Bo Zhu Xiaohong Zhu Giuseppe Pezzotti 《Journal of Raman spectroscopy : JRS》2012,43(9):1320-1328
A quantitative polarized Raman analysis of ferroelectric grain/domain orientation in LiSbO3 (LS‐modified) (K0.5Na0.5)NbO3 (KNN) ceramics is presented, based on the analysis of the complex orientation dependence in space of their Raman‐active modes. Complete sets of Raman tensor elements of Ag, and Eg phonon modes for orthorhombic/tetragonal structures of KNN have been determined. Through this spectroscopic algorithm, quantitative information could be extracted in terms of three Euler angles in space for KNN samples consisting of mixed phases, thus enabling quantitative visualization of the local distribution of grains/domains in the solid angle. As an application of the method, we quantitatively examined the unknown crystallographic grain orientation patterns on the surfaces of pure KNN and of KNN‐0.05LS ceramics. These two samples were useful to clarify a polymorphic phase transition from the orthorhombic to the tetragonal phase taking place in the LS‐modified KNN system. Thus, we demonstrated that polarized Raman spectroscopy is a valuable and efficient tool for nondestructive three‐dimensional assessments of grain/domain orientation in ferroelectric materials with complex polymorphic structures. We believe that the data shown here represent a typical scenario encountered in grain/domain orientation assessments of piezoelectric perovskites. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
5.
Florian Latteyer Sabine Savu Heiko Peisert Thomas Chass 《Journal of Raman spectroscopy : JRS》2012,43(9):1227-1236
This work presents an investigation of films prepared by doctor blade casting, the formation of self‐assembled microstructures of a liquid crystalline phthalocyanine with highly oriented molecules. Raman Spectroscopy in combination with atomic force microscopy is applied to study the structures within the films. By keeping the substrate at room temperature or at 353 K during coating, different geometric structures namely rods and islands form. Rod‐like structures are growing in coating direction, whereas directional growth of the islands is not observed. The distribution of the rod lengths varies widely, whereas the width appears more uniform. Annealing of the samples shows a different behavior of the two textures. Islands tend to melt, and rods smooth their structural form, which is extracted from Raman imaging in combination with atomic force microscopy. Additionally, Raman imaging gives insight into laterally different relative crystallinity. These observations are discussed in the context of the molecular orientation as probed by polarized Raman spectroscopy. These polarized Raman spectra indicate azimuthal alignment of the molecules within the rods (edge on alignment). This alignment occurs along and also perpendicular to the growth direction. In contrast to the alignment in the rods, the molecules inside the islands occurring at higher temperature do not show preferential molecular orientation. After annealing, no preferential molecular orientation is observed in rods because of the loss of anisotropy, too. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
6.
Toshihiro Mino Yuika Saito Hiroyuki Yoshida Satoshi Kawata Prabhat Verma 《Journal of Raman spectroscopy : JRS》2012,43(12):2029-2034
Polarization‐dependent Raman microscopy is a powerful technique to perform both structural and chemical analyses with submicron spatial resolution. In conventional Raman microscopy, the polarization measurements are limited only in the direction parallel to the sample plane. In this work, we overcome the limit of conventional measurements by controlling the incident polarization by a spatially modulated waveplate. In this method, the polarization perpendicular to the sample surface (z‐polarization) can be detected together with the parallel polarization (xy‐polarization). Because of this unique polarization control, our Raman microscope has the ability to image the molecular orientation, together with the molecular analysis. Here, we have investigated thin films of pentacene molecules that are widely studied as an organic semiconductor material. The orientations of pentacene molecules are imaged with a spatial resolution of 300 nm. Our results clearly indicate that the lamellar grains show the lower tilt angles compared to the neighboring islands, which has not been proved in conventional methods. The substrate effects and the thickness dependence of the film are also studied. These results provide knowledge about the relationship between the devise performance and the film structures, which is indispensable for future device exploitations. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
7.
Five sets of differently sterilised conventional ultra‐high molecular weight polyethylene (UHMWPE) and cross‐linked polyethylene (XLPE) acetabular cups were run for 5 million cycles on a hip joint simulator in order to evaluate their wear behaviour in relation to material properties (PE grade, conventional or cross‐linked) and sterilisation method (ethylene oxide (EtO) treatment or γ‐irradiation). Gravimetric measurements revealed that conventional UHMWPE wore significantly more than XLPE. The differences in wear behaviour could be partly related to the orthorhombic contents obtained by Raman spectroscopy in the unworn areas of the cups: XLPE cups showed a significantly higher crystallinity degree than the UHMWPE specimens. Raman analysis showed that wear testing did not significantly modify the orthorhombic content of any of the tested acetabular cups. However, the set of cups that showed the highest weight loss, i.e. γ‐sterilised PE GUR1020, appeared the most homogeneously polished upon wear testing; from a molecular point of view, only this set of cups showed a significant increase of the I1130/I1060 intensity ratio, suggesting the occurrence of chain orientation. On the other hand, XLPE cups, despite the lowest weight loss undergone, showed a decrease in the amorphous content upon wear testing as well as a limited orthorhombic → monoclinic transformation, which did not appear detrimental. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
8.
Different angle-resolved polarization configurations of Raman spectroscopy: A case on the basal and edge plane of two-dimensional materials
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Angle-resolved polarized Raman(ARPR) spectroscopy can be utilized to assign the Raman modes based on crystal symmetry and Raman selection rules and also to characterize the crystallographic orientation of anisotropic materials.However, polarized Raman measurements can be implemented by several different configurations and thus lead to different results. In this work, we systematically analyze three typical polarization configurations: 1) to change the polarization of the incident laser, 2) to rotate the sample, and 3) to set a half-wave plate in the common optical path of incident laser and scattered Raman signal to simultaneously vary their polarization directions. We provide a general approach of polarization analysis on the Raman intensity under the three polarization configurations and demonstrate that the latter two cases are equivalent to each other. Because the basal plane of highly ordered pyrolytic graphite(HOPG) exhibits isotropic feature and its edge plane is highly anisotropic, HOPG can be treated as a modelling system to study ARPR spectroscopy of twodimensional materials on their basal and edge planes. Therefore, we verify the ARPR behaviors of HOPG on its basal and edge planes at three different polarization configurations. The orientation direction of HOPG edge plane can be accurately determined by the angle-resolved polarization-dependent G mode intensity without rotating sample, which shows potential application for orientation determination of other anisotropic and vertically standing two-dimensional materials and other materials. 相似文献
9.
在准连续情况下, 通过求解低双折射光纤中含有拉曼效应的右旋与左旋圆偏振光所满足的耦合非线性薛定谔方程,着重研究了低输入功率和高输入功率情形在加入拉曼效应前后, 有效偏振拍长和输入功率的变化关系. 结果表明: 无论入射光的偏振是沿着慢轴或沿着快轴, 拉曼效应均改变了入射光偏振态演变的周期, 同时改变了入射光的传输距离. 相似文献
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The polarized Raman spectroscopy is capable of giving confirmation regarding the crystalline phase as well as the crystallographic orientation of the sample. In this context, apart from crystallographic X‐ray and electron diffraction tools, polarized Raman spectroscopy and corresponding spectral imaging can be a promising crystallographic tool for determining both crystalline phase and orientation. Sub‐micron sized hexagonal AlGaN crystallites are grown by a simple atmospheric pressure chemical vapor deposition technique using the self catalytic vapor–solid process under N‐rich condition. The crystallites are used for the polarized Raman spectra in different crystalline orientations along with spectral imaging studies. The results obtained from the polarized Raman spectral studies show single crystalline nature of sub‐micron sized hexagonal AlGaN crystallites. Optical properties of the crystallites for different crystalline orientations are also studied using polarized photoluminescence measurements. The influence of internal crystal field to the photoluminescence spectra is proposed to explain the distinctive observation of splitting of emission intensity reported, for the first time, in case of c‐plane oriented single crystalline AlGaN crystallite as compared with that of m‐plane oriented crystallite. Copyright © 2016 John Wiley & Sons, Ltd. 相似文献
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Aleksandr S. Oreshonkov Julia V. Gerasimova Alexandr A. Ershov Alexander S. Krylov Kirill A. Shaykhutdinov Aleksandr N. Vtyurin Maxim S. Molokeev Konstantin Y. Terent'ev Natalia V. Mihashenok 《Journal of Raman spectroscopy : JRS》2016,47(5):531-536
MnGeO3 single‐crystal samples have been synthesized by optical zonal melting and spontaneous crystallization. X‐ray crystal analysis showed the first sample to be a two‐phase one with phase ratio as follows: 17% – monoclinic C2/c, and 83% – orthorhombic Pbca; the phase ratio of the second sample was unknown. Raman spectra have been produced for these samples. Lattice dynamics has been simulated and polarization dependencies of lines' intensities have been analyzed to interpret experimental Raman spectra and to attribute lines to the spectra of monoclinic and orthorhombic phases. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
14.
介绍喇曼感生克尔效应光谱(RIKES)的琼斯(Jones)矩阵分析方法.探测光束的传输强度不仅由所经过的每一个光学器件的琼斯矩阵所决定,而且还受到强的泵波在非线性介质样品中感生依赖于强度的二向色性和双折射(克尔效应)对琼斯矩阵的影响.同时计及样品和光学器件由强泵波作用下感生应力和其他外部产生的线双折射对喇曼感生克尔效应光谱观察的不利影响,导出测量系统的功率传输函数的完整表达式和喇曼感生克尔效应光谱的实现观察条件,最后简述以甲笨(C_7H_8)液体为试样的喇曼感生克尔效应光谱实验结果分析. 相似文献
15.
Josefine Enman Kerstin Ramser Ulrika Rova Kris Arvid Berglund 《Journal of Raman spectroscopy : JRS》2008,39(10):1464-1468
Eritadenine, 2(R),3(R)‐dihydroxy‐4‐(9‐adenyl)‐butyric acid, is a cholesterol‐reducing compound naturally occurring in the shitake mushroom (Lentinus edodes). To identify the unknown Raman spectrum of this compound, pure synthetic eritadenine was examined and the vibrational modes were assigned by following the synthesis pathway. This was accomplished by comparing the known spectra of the starting compounds adenine and D ‐ribose with the spectra of a synthesis intermediate, methyl 5‐(6‐Aminopurin‐9H‐9‐yl)‐2,3‐O‐isopropylidene‐5‐deoxy‐β‐D ‐ribofuranoside (MAIR) and eritadenine. In the Raman spectrum of eritadenine, a distinctive vibrational mode at 773 cm−1 was detected and ascribed to vibrations in the carbon chain, ν(C C). A Raman line that arose at 1212 cm−1, both in the Raman spectrum of MAIR and eritadenine, was also assigned to ν(C C). Additional Raman lines detected at 1526 and at 1583 cm−1 in the Raman spectrum of MAIR and eritadenine were assigned to ν(N C) and a deformation of the purine ring structure. In these cases the vibrational modes are due to the linkage between adenine and the ribofuranoside moiety for MAIR, and between adenine and the carbon chain for eritadenine. This link is also the cause for the disappearance of adenine specific Raman lines in the spectrum of both MAIR and eritadenine. Several vibrations observed in the spectrum of D ‐ribose were not observed in the Raman spectrum of eritadenine due to the absence of the ribose ring structure. In the Raman spectrum of MAIR some of the D ‐ribose specific Raman lines disappeared due to the introduction of methyl and isopropylidene moieties to the ribose unit. With the approach presented in this study the so far unknown Raman spectrum of eritadenine could be successfully identified and is presented here for the first time. Copyright © 2008 John Wiley & Sons, Ltd. 相似文献
16.
Zhaodong Liu Mingguang Yao Ye Yuan Shuanglong Chen Ran Liu Shuangchen Lu Bo Zou Tian Cui Bingbing Liu 《Journal of Raman spectroscopy : JRS》2015,46(4):413-417
Raman spectroscopy of the one‐dimensional atomic or molecular chains, which are the attractive building blocks of advanced nanoscale materials, is crucial in understanding the physical properties of the one‐dimensional atomic or molecular chains. Here, we introduce the bromine into the one‐dimensional channels of AlPO4‐5 single crystals through a physical vapor diffusion method. Raman spectroscopy indicates that the confined bromine structures mainly exist as (Br2)n chains, individual Br2 molecules, and a small amount of Br3− chains inside the channels of AlPO4‐5 single crystals. Polarized Raman spectra demonstrate that the bromine molecular chains are approximately parallel to the channel direction of AlPO4‐5 single crystals. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
17.
在准连续情况下, 通过求解低双折射光纤中含有拉曼效应的右旋与左旋圆偏振光所满足的耦合非线性薛定谔方程, 得到了归一化功率以及相位差的解析解. 利用解析解,推导出了椭圆率和方位角的表达式, 研究了拉曼效应和传输距离对偏振态演化的影响, 并用相平面法对椭圆率和方位角随着输入功率的变化进行了直观描述. 结果表明: 低双折射光纤在传输的过程中, 拉曼效应和传输距离都是影响其偏振态稳定性的因素, 均改变了椭圆率和方位角的演变周期以及振荡幅度. 相似文献
18.
Sameer V. Naik Jungyu Hwang Robert P. Lucht Normand M. Laurendeau 《Journal of Raman spectroscopy : JRS》2008,39(1):68-78
The techniques of inverse Raman spectroscopy, Raman‐induced polarization spectroscopy (RIPS), and optical heterodyne RIPS (OHD‐RIPS) are compared by probing the Q‐branch of the nitrogen molecule. The signal is measured employing either a photomultiplier tube (low background level–RIPS) or a photodetector (high background level–IRS and OHD‐RIPS). The measurements are performed using atmospheric mixtures of N2 Ar with concentrations varying from 0 to 79% N2. This strategy permits estimation of detection limits using the different techniques. Pump and probe energy levels are varied independently to study signal dependence on laser irradiance. A theoretical treatment is presented on the basis of the Raman susceptibility equations, which permits the calculation of spectra for all three techniques. Calculated Q‐branch spectra are compared with the measured spectra for the interactions of a linearly polarized probe beam with a linearly or circularly polarized pump beam. The polarizer angle in the detection path for OHD‐RIPS has a dramatic effect on the shape of the spectrum. The calculated and experimental OHD‐RIPS spectra are in good agreement over the entire range of investigated polarizer angles. Detection limits using these techniques are analyzed to suggest their applicability for measuring other species of importance in combustion and plasma systems. Copyright © 2007 John Wiley & Sons, Ltd. 相似文献
19.
The vibrational molecular excitation by strong laser fields have been studied. Starting with the molecular Hamiltonian, we derive the vibrational excitation rate due to a gradient of laser field and show that the rate can be two to three orders of magnitude larger than the regular Raman rates. The developed theory contributes to understanding of interaction of powerful laser pulses with molecular systems, and it might be used in developing quantitative coherent Raman spectroscopy. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
20.
Raman spectroscopy (RS) for selective quantification of protein species in mixed solutions holds enormous potential for advancing protein detection technology to significantly faster, cheaper, and less technically demanding platforms. However, even with powerful computational methods such as nonlinear least squares regression, protein quantification in such complex systems suffers from relatively poor accuracy, especially in comparison with established methods. In this work, a combination of the expanded set of spectral information provided by polarized Raman spectroscopy (PRS) that is otherwise unavailable in conventional RS was, to our knowledge, explored to enhance the quantitative accuracy and robustness of protein quantification for the first time. A mixture containing two proteins, lysozyme and α‐amylase, was used as a model system to demonstrate enhanced quantitative accuracy and robustness of selective protein quantification using PRS. The concentrations of lysozyme and α‐amylase in mixtures were estimated using data obtained from both traditional RS and PRS. A new method was developed to select highly sensitive peaks for accurate concentration estimation to take advantage of additional spectra offered by PRS. The root‐mean squared errors (RMSE) of estimation using traditional RS and PRS were compared. A drastic improvement in RMSE was observed from traditional RS to PRS, where the RMSEs of α‐amylase and lysozyme concentrations decreased by 11 and 7 times, respectively. Therefore, this technique is a successful demonstration in achieving greater accuracy and reproducibility in the estimation of protein concentration in a mixture, and it could play a significant role in future multiplexed protein quantification platforms. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献