The effect of spectral resolution on the Raman spectra of polyaromatic hydrocarbons and beta‐carotene mixtures

The spectroscopic basis for extraterrestrial life‐detection through the molecular signatures of relevant biomaterials is dependent upon several instrumental facilities which could effect the diagnostic interpretation of key Raman bands from relevant substances occurring together in the geological record. To this effect, the Raman spectra of several polyaromatic hydrocarbons have been investigated under different conditions of spectral resolution using FT‐Raman‐spectroscopy operating at 1064 nm laser excitation wavelength. The observed Raman spectra are considerably altered under different conditions of spectral resolution; in particular, the discrimination between several polyaromatic hydrocarbons and beta‐carotene no longer becomes possible as the spectral resolution decreases. These results are relevant for the evaluation of miniaturised Raman spectrometers for space flight missions and incorporation into instrumentation for landers and rovers being proposed for future missions to Mars. Copyright © 2010 John Wiley & Sons, Ltd.     

核酸碱基的付立叶变换红外拉曼光谱特征

本文给出了核酸碱基付立叶变换红外（ＦＴ—ＩＲ）激光拉曼光谱特征，并与可见光激光拉曼光谱进行了比较。结果表明，付立叶变换红外激光拉曼获得较可见光激光拉曼光谱波数范围更宽（低波数）的谱带范围，所获谱图荧光干扰小，谱图质量明显高于普通激光拉曼光谱谱图。     

Relationship between the giant enhancement of the Raman scattering and luminescence on nanostructured metallic surfaces

The relationship between the factors of giant enhancement of luminescence and inelastic (Raman) scattering of light at planar silver nanostructures is investigated. For this purpose, the variation of the enhanced luminescence and Raman signals with the distance between the nanostructure surface and a layer of test molecules is examined. It is found that, for lines whose spectral position is close to the wavelength of the excitation laser, the enhancement factor for the Raman scattering is proportional to the square of that for the luminescence signal. As the spectral shift between the Raman lines and the laser position increases, the above dependence becomes subquadratic. It is established that the spatial scale on which the enhancement is manifested is the same for both effects and amounts to 25–30 nm.     

Wavelength‐dependent amplitude of Teflon Raman lines

Raman and other spectroscopy systems operating in the deep ultraviolet (DUV) spectral region below 250 nm lack scattering standards. Such standards are particularly important for experiments that use multiwavelength excitation and/or when results are compared across different experiment platforms. Teflon has been used as an external standard in the visible and near‐IR spectral regions and has been suggested for use in the ultraviolet (UV). Comparison of the relative amplitudes of prominent Teflon Raman lines indicates a significant effect on line ratios when the excitation wavelength is below 250 nm. This dependence on excitation wavelength has been commented on previously and attributed to pre‐resonance effects, but no detailed examination had been undertaken to date. We present the results of a study of Teflon Raman line ratios obtained from closely spaced excitation wavelengths in the DUV from 210 to 320 nm. The 731 cm⁻¹ line is identified as well suited for a standard. Electronic transition energies associated with resonance of principal Teflon Raman lines are obtained. Copyright © 2010 John Wiley & Sons, Ltd.     

Cascaded Raman shifting of high-peak-power nanosecond pulses in As₂S₃ and As₂Se₃ optical fibers

We report efficient cascaded Raman scattering of near-IR nanosecond pulses in large-core (65 μm diameter) As?S? and As?Se? optical fibers. Raman scattering dominates other spectral broadening mechanisms, such as four-wave mixing, modulation instability, and soliton dynamics, because the fibers have large normal group-velocity dispersion in the spectral range of interest. With ~2 ns pump pulses at a wavelength of 1.9 μm, four Stokes peaks, all with peak powers greater than 1 kW, have been measured.     

Calibration Procedure of Laser Confocal Micro-Raman SpectrometerSCIEI北大核心CSCD

As a common spectral characterization technique, Raman spectroscopy is widely used and has a specified calibration procedure. Based on laser confocal micro-Raman spectrometer, in this paper, we briefly introduced the principle, configuration and main components of Raman spectrometer. In addition, the calibration procedures were also presented, with an emphasis on the calibration of spectrometer (spectrograph) and that of excitation laser wavelength. On the basis of conventional calibration method, a novel and more accurate method was proposed to obtain the actual excitation wavelength, that is, calibration at the point of Raman shift Delta nu=0. Using this novel calibration method of excitation wavelength, Raman frequency shift values of sulfur were measured, and compared with the standard values from American Society Testing and Materials (ASTM). As a result, the measured values after calibration were consistent with those ASTM values, which indicated that the calibration method is accurate. Thus, a more reasonable calibration procedure of the laser confocal micro-Raman spectrometer was provided.     

飞秒受激拉曼光谱线形:基于泵浦及探测脉冲光的共振条件研究

Resonance enhancement has been increasingly employed in the emergent femtosecond stimulated Raman spectroscopy (FSRS) to selectively monitor molecular structure and dynamics with improved spectral and temporal resolutions and signal-to-noise ratios. Such joint efforts by the technique-and application-oriented scientists and engineers have laid the foundation for exploiting the tunable FSRS methodology to investigate a great variety of photosensitive systems and elucidate the underlying functional mechanisms on molecular time scales. During spectral analysis, peak line shapes remain a major concern with an intricate dependence on resonance conditions. Here, we present a comprehensive study of line shapes by tuning the Raman pump wavelength from red to blue side of the ground-state absorption band of the fluorescent dye rhodamine 6G in solution. Distinct line shape patterns in Stokes and anti-Stokes FSRS as well as from the low to high-frequency modes highlight the competition between multiple third-order and higher-order nonlinear pathways, governed by different resonance conditions achieved by Raman pump and probe pulses. In particular, the resonance condition of probe wavelength is revealed to play an important role in generating circular line shape changes through oppositely phased dispersion via hot luminescence (HL) pathways. Meanwhile, on-resonance conditions of the Raman pump could promote excited-state vibrational modes which are broadened and red-shifted from the coincident ground-state vibrational modes, posing challenges for spectral analysis. Certain strategies in tuning the Raman pump and probe to characteristic regions across an electronic transition band are discussed to improve the FSRS usability and versatility as a powerful structural dynamics toolset to advance chemical, physical, materials, and biological sciences.     

激光共聚焦显微拉曼光谱仪校准程序

作为一种常规光谱测量技术,拉曼光谱仪应用广泛并具有特定的校准方法。主要面向激光共聚焦显微拉曼光谱仪,概括介绍了激光共聚焦显微拉曼光谱仪的测量原理、结构及主要组成部分,重点介绍了激光共聚焦显微拉曼光谱仪的校准项目和校准过程,重点是分光计(摄谱仪)校准和激光器激发波长校准。在传统校准方法的基础上提出了一种更准确、新的获得实际激发波长的方法,即在Δν=0处校准的方法。根据此新的激发波长校准方法测量单质硫的拉曼频移,并将硫的拉曼频移值与美国材料与试验协会(ASTM)值比较。结果表明此校准步骤正确,从而进一步提出了一种更为合理的激光共聚焦显微拉曼光谱仪的校准程序。     

Nonlinear-optical transformation of nanosecond laser pulses and controlled supercontinuum generation in photonic-crystal fibers

Photonic-crystal fibers are shown to allow efficient spectral transformation of nanosecond laser pulses through parametric four-wave mixing and stimulated Raman scattering. Regimes providing highly efficient transformation of nanosecond laser pulses into white-light broadband radiation (supercontinuum) are identified. A strong parametric coupling between Stokes and anti-Stokes Raman sidebands around the wavelength of zero group-velocity dispersion is shown to increase the bandwidth and to improve the spectral quality of supercontinuum radiation.     

A portable shifted excitation Raman difference spectroscopy system: device and field demonstration

In this paper, we present a portable shifted excitation Raman difference spectroscopy (SERDS) system applied in outdoor experiments. A dual‐wavelength diode laser emitting at 785 nm is used as excitation light source. The diode laser provides two individually controllable excitation lines at 785 nm with a spectral distance of about 10 cm⁻¹ for SERDS. This monolithic light source is implemented into a compact handheld Raman probe. Both components were developed and fabricated in‐house. SERDS measurements are performed in an apple orchard, and apples and green apple leafs are used as test samples. For each excitation wavelength, a single Raman spectrum is measured with 50 mW at the sample. Strong background interference from ambient daylight and laser‐induced fluorescence obscure the Raman signals. SERDS efficiently separates the wanted Raman signals from the disturbing background signals. For the Raman spectroscopic investigations of green leafs, one accumulation with an exposure time of 0.2 s was used for each excitation wavelength to avoid detector saturation. An 11‐fold improvement of the signal‐to‐background noise is achieved using SERDS. The results demonstrate the suitability of the portable SERDS system for rapid outdoor Raman investigations. Copyright © 2016 John Wiley & Sons, Ltd.     

金纳米空心半球壳膜的可调谐光学性质研究

以单层聚苯乙烯微球阵列为模板,通过控制其表面金膜蒸镀时间,制备了具有不同厚度的空心半球壳结构的金纳米膜.利用扫描电子显微镜和自制光谱仪分别测量了金膜表面形貌和其透射光谱,并分析了金膜形貌与其光学性质间的关系,同时以4-巯基苯胺为探针分子测定了金膜的表面增强喇曼散射效应.结果表明,该金纳米膜的表面等离子体共振波长随膜厚度增大而发生红移,在可见与近红外波段较宽范围内可调谐,并且,当金膜共振波长与入射激发光波长较近时,探针分子可产生出较强的表面增强喇曼信号.同时,对该现象的产生机制也进行了理论解释.     

Stimulated Raman hyperspectral imaging based on spectral filtering of broadband fiber laser pulses

We demonstrate a technique of hyperspectral imaging in stimulated Raman scattering (SRS) microscopy using a tunable optical filter, whose transmission wavelength can be varied quickly by a galvanometer mirror. Experimentally, broadband Yb fiber laser pulses are synchronized with picosecond Ti:sapphire pulses, and then spectrally filtered out by the filter. After amplification by fiber amplifiers, we obtain narrowband pulses with a spectral width of <3.3 cm(-1) and a wavelength tunability of >225 cm(-1). By using these pulses, we accomplish SRS imaging of polymer beads with spectral information.     

Super-Resolved Raman Spectra of Toluene and Toluene–Chlorobenzene Mixture

In this paper, we present a method for “super-resolved” Raman spectroscopy which improves the resolution of obtained spectra. Experimental investigations were carried out on the spectra of toluene and a toluene–chlorobenzene mixture. A tunable Fabry–Perot filter is added to the detection channel and by measuring the spectra for several states of the filter a spectrum of higher resolution can be obtained after a decoding process. We demonstrate both a reduced linewidth in the pure toluene spectra and partial separation of the two overlapping peaks in the mixture.     

Spectral power handling capability caused by stimulated Raman scattering effect in silica optical fibers

Spectral characteristics of the stimulated Raman scattering (SRS) in silica fibers was studied for the purpose of obtaining higher power transmission capability in single-mode silica optical fibers. When the input power exceeds a critical input power, which depends on the wavelength, nonlinear transmission loss caused by SRS gives rise to excess loss and signal waveform distortion. The SRS effect is reduced under the condition of sufficiently large spectral loss at the first Stokes wavelength.     

喇曼自由电子激光振荡器

本文报道喇曼自由电子激光振荡器的研究结果。脉冲加速器电子束能量０．４ＭｅＶ，束流８００Ａ。采用满足布喇格条件的分布反馈谐振腔，取代传统的激光器反射镜。理论上进行了分析和设计，采用正弦形波结构选择振荡模式。喇曼自由电子激光振荡器实验表明，输出光谱显著变窄。频率分布半高宽度，超辐射下范围为７．５ｍｍ～９．２ｍｍ，分布腔下范围为８．６ｍｍ～８．９ｍｍ。     

Spectral-temporal dynamics of ultrashort Raman solitons and their role in third-harmonic generation in photonic crystal fibers

We use cross-correlation frequency-resolved optical gating to obtain spectral-temporal portraits of ultrashort Raman solitons in photonic crystal fibers at telecommunication wavelengths. Power-dependent Raman frequency shifts of 200 nm in 63 mm of fiber are observed accompanied by spectral broadening and 2.5-times soliton compression. Complete time-frequency dynamics at the fundamental wavelength thus visualized enables us to explain the details of the intermodally phase-matched third harmonic generation by the propagating solitons.This revised version was published online in August 2005 with a corrected cover date.     

传统陶瓷中结构羟基的光谱学研究

烧结粘土产品可以吸收水分子发生再羟基化,生成结构羟基的量与产品保存时间存在一定关系,基于该理论可以利用热重分析方法对陶器制品进行测年研究.红外与拉曼光谱技术也可以用来分析结构羟基信息,因此人们希望探索利用光谱分析方法代替热重法进行传统陶瓷无损测年分析.为了验证可行性,收集了多种典型矿物原料和可溯源的传统陶瓷样品,利用红...     

Raman spectroscopy of automotive paints: Forensic analysis of variability and spectral quality

Raman spectroscopy was evaluated as a forensic technique for the analysis of automotive paints with the purpose to verify the measurement variability as well as to study the spectral quality by means of parameters and conditions. The objective lens, accumulation number, and laser (power, mode, and wavelength) were observed to significantly affect the spectral quality and thus should be taken into consideration during the development of a forensic database. On the other hand, exposure time, Raman shift range, and baseline correction had less influence on the features of the obtained spectra. Interestingly, samples collected from the bumper coating composed of a plastic substrate in comparison with fragments obtained from other parts of the same vehicle containing metallic substrate showed different absorption band patterns. In addition, less variability of data acquired directly onto the paint chip’s surface has demonstrated that direct analysis should be preferred during spectra library development as opposed to cross-section measurements. Sample homogeneity and distinction power of the technique combined with Principal Components Analysis were also investigated. The preliminary results showed that although Raman spectroscopy is extremely accurate in the identification of vehicles, it is necessary to pay particular attention to the spectral variability in order to avoid false database matching and misleading of forensic investigations. Therefore, we suggest that separated spectra library shall be developed for each laser wavelength as well as for each sample substrate. Further studies with a higher number of paint chips will enable the establishment of prediction models aimed to identify unknown samples involved in hit-and-run cases.     

岩心显微拉曼光谱成像方法的研究

虽然用激光拉曼光谱显微探针研究岩心中碳质物的工作已有很大进展,但是通常对诸如岩心等样品物性的光谱学(红外、拉曼和荧光等)微探针实验研究多是局限于对经过复杂处理分离出的微小样品或样品中个别点得到的结果,缺乏对复杂样品各组分(或基团)的空间分布及其相互关系的研究。近年来新发展起来的光谱成像分析系统将光谱技术与成像技术有机地结合起来融为一体,可在光谱和空间两个方面对目标样品进行分析和识别,但是用拉曼显微成像光谱研究岩心的工作则少有报道。文章报道了应用“串行-成像”(series-or indirect-imaging,Mapping)和“并行-成像”(parallel-or direct-imaging, Imaging)两种方式对含油岩心进行了显微拉曼光谱成像的研究。从光谱分辨率和空间分辨率以及工作效率等方面对两种方式所得试验结果进行了比较和评估。