The laser-induced fluorescence spectroscopy of CoF in the ultra violet region

The laser-induced fluorescence (LIF) spectrum of jet-cooled CoF has been obtained in the wavelength region of 260-290 nm for the first time. Seventeen vibronic bands were observed and assigned to three types of transition from the ground state to upper states Ω′ = 3, 4, 5 by rotational analysis. A new vibrational transition with the 0-0 band at 34697.22 cm⁻¹ has been assigned as the [34.7]³Γ₅-X³Φ₄ transition and effective equilibrium molecular constants for the upper state have been determined. In addition, lifetime measurements have been carried out for most of the bands under collision-free conditions. On the basis of the spectroscopic data and lifetime measurements, the electronic structures of these possible high-lying electronic states are discussed.     

Laser-induced fluorescence spectroscopy of FeS in the visible region

The laser-induced fluorescence excitation spectra of jet-cooled FeS molecules have been recorded in the energy range of 18 900-21 600 cm⁻¹, in which four parallel and one perpendicular transitions were identified for the first time. Spectroscopic constants of the observed excited states of FeS were determined by analyzing their rotationally resolved spectra. In addition, the lifetimes of most observed bands were also measured.     

Gas phase electronic spectrum of the HSCCS radical by laser-induced fluorescence spectroscopy

In a discharged supersonic jet of a CS₂ and C₂H₂ mixture, a vibronic band system of a new radical species was observed in the energy region 21 800-23 000 cm⁻¹ by laser-induced fluorescence (LIF) spectroscopy. The LIF excitation spectrum shows progressions with 490 and 80 cm⁻¹ separations. The vibronic structure of a dispersed fluorescence (DF) spectrum, obtained by tuning a probe laser to the vibronic origin band, also consists of progressions with 520 and 100 cm⁻¹ separations. A high-resolution laser scan provided a rotationally resolved LIF excitation spectrum for the vibronic origin band, showing the rotational structure of a-type transitions of a near-prolate top. Several chemical tests indicate that the spectral carrier contains sulfur atom(s), one hydrogen atom and more than one carbon atoms. Electronic transition energy, vibrational frequencies, and rotational constants of this species are similar to those of SCCS⁻ [M. Nakajima, Y. Yoneda, Y. Sumiyoshi, T. Nagata, Y. Endo, J. Chem. Phys. 119(2003)7805-7813.], and the spectral carrier was assigned as an isoelectronic radical, bent HSCCS. Ab initio geometrical optimizations supported the spectral carrier to be HSCCS. The observed electronic transition was assigned to be the transition, which corresponds to the Π-Π transition in the limit of linear geometry. The observed vibrations in the excitation and DF spectra were assigned as the symmetric CS stretching (ν₅) and SCC bending (ν₇) modes by comparing the results of theoretical calculations.     

Simultaneous laser-induced fluorescence and sub-Doppler polarization spectroscopy of the CH radical

The first application of polarization spectroscopy (PS) to the CH radical is demonstrated. In particular, we report on the simultaneous application of laser-induced fluorescence (LIF) and sub-Doppler PS to CH. The conventional experimental setup for PS was supplemented with a second detection system in order to collect the LIF emission. At the same time a Fabry–Perot etalon and molecular iodine were utilized to obtain a precise relative and absolute frequency scale, respectively. CH was investigated in a low pressure methane–oxygen flame. The R₂(5) transition of the B–X (0, 0) band corresponding to a wavelength around 387.3 nm was scanned while fluorescence emission was collected in the spectral region around 431 nm from the B–X (0, 1), A–X (1, 1) and A–X (0, 0) bands. The saturation behavior of both techniques is investigated as well as line broadening effects due to the pump laser pulse energy or rather fluence. Saturation fluence for LIF was found to be more than one order of magnitude higher as compared to PS.     

A laser-induced fluorescence biosensor by using ellipsoidal reflector

A new and compact fluorescence biosensor is constructed. The distinguished feature of this setup is the use of an ellipsoidal reflector as an optical collector of the fluorescence light. A traditional collecting lens with numerical aperture of 0.5 can only collect a few percent of the available signal, while the incorporation of the ellipsoidal reflector enables the apparatus to provide a signal increase of at least 66 times. A very good linear relationship between the concentration of fluorescent dye and the fluorescence intensity is achieved with correlation coefficient R=0.99979. The 3σ detection limit is 5 nM for microliter volume sample. Meanwhile, it is found that laser light scattering by dirts and scratches on the sample cell's windows and by turbidity in the sample solutions is the dominant limitation to increase the detection sensitivity. Approach to solve this problem is suggested.     

The laser-induced fluorescence spectrum of CoS between 15 200 and 19 000 cm-1

测量了在15200～19000 cm^-1的超声射流冷却的CoS自由基的激光诱导荧光激发谱. 观测到[15.58]⁴Δ_7/2～X⁴Δ_7/2, [16.02]⁴Δ_7/2～X⁴Δ_7/2, [16.50]⁴Δ_7/2～X⁴Δ_7/2, [17.80]⁴П_5/2～X⁴Δ_7/2和[18.00]⁴Δ_7/2～X⁴Δ_7/2五个电子跃迁序列. 此外,还测量到了大多数观察的振动带的寿命. 并讨论了这些新的电子态的电子构型.     

Quantitative laser-induced fluorescence measurements of nitric oxide in a heavy-duty Diesel engine

We present quantitative, in-cylinder, UV-laser-induced fluorescence measurements of nitric oxide in a heavy-duty Diesel engine. Processing of the raw fluorescence signals includes a detailed correction, based on additional measurements, for the effect of laser beam and fluorescence attenuation, and for the pressure and temperature dependence of the fluorescence efficiency, based on numerical modelling. These corrections are largest early in the stroke, when quenching rates are high and UV transmission is low. Together, they vary over more than three orders of magnitude during the combustion stroke. Fully quantitative results are realised by an overall calibration using independent concentration measurements in the exhaust gas. The data provide evidence of NO formation during both the premixed and mixing-controlled combustion phases.     

Spectroscopic characterization of aluminum plasma using laser-induced breakdown spectroscopy

A detailed investigation of aluminum plasma induced by a 1064 nm Nd:YAG laser in air was performed. The emission of spectral lines arising from Al I transition at 396.07 nm, Al II transition at 358.46 nm, Al III transition at 360.72 nm and Al IV transition at 363.05 nm were well-resolved. The plasma parameters including electron temperature and electron density were determined through the Boltzmann plot method using the emission line intensities of the same ionized stages of aluminum atoms and the Stark-broadening profiles of Al II emission line, respectively. The temporal evolutions of the spectral lines belonging to atomic and ionic aluminum elements and the plasma parameters were investigated at three different laser pulse energies. Moreover, the validity of local thermodynamic equilibrium was elucidated in our experimental condition.     

基于激光诱导叶绿素荧光寿命成像技术的植物荧光特性研究

针对植物荧光遥感探测中信号易受干扰的问题, 提出了一种用于评估植物生长状况及环境监测的荧光寿命成像技术. 采用凹透镜对355 nm波长的激光扩束, 再照射植物激发叶绿素荧光, 由增强型电荷耦合器件接收荧光信号. 采用时间分辨测量法, 连续用相同激光脉冲照射植物以激发相同的荧光信号, 同时不断改变激光脉冲触发探测器启动的延时时间, 从而能够得到完整的离散荧光信号分布图像. 对植物特定位置点产生的离散荧光信号进行拟合, 再运用一种改进型的迭代解卷积法可反演高精度的荧光寿命; 进而反演图像各点的荧光寿命以生成植物的荧光寿命分布图. 该方法所绘制的荧光寿命图比荧光强度图能更准确地反映植物内部的叶绿素含量, 并对活体植物叶绿素荧光寿命的物理特性进行了初步研究, 证明叶绿素荧光寿命与植物生理状态存在一定关联; 并且叶绿素荧光寿命与活体植物所处环境存在着复杂的关系. 未来将与生物物理学家们合作, 继续探寻叶绿素荧光寿命与植物生存环境的关系.     

平面激光诱导荧光实验中激励激光的光束整形

分析了激励激光光强分布对平面激光诱导荧光（PLIF）实验中荧光强度的影响。基于柱面微透镜列阵设计了一套激光片状光束匀滑整形系统,并根据PLIF实验的具体要求,通过光线追迹方法优化了系统参数。建立了片状光束整形实验系统,对染料激光进行了匀滑整形,获得了不均匀性〈4%的均匀片状光束,满足了PLIF实验所需。在此基础上建立了PLIF实验系统,获得了酒精灯火焰和CH4/air预混火焰中OH的二维荧光分布。     

Investigation of four carbon monoxide isotopomers in natural abundance by laser-induced fluorescence in a supersonic jet

The four carbon monoxide (CO) isotopomers ¹²C¹⁶O, ¹³C¹⁶O, ¹²C¹⁸O and ¹²C¹⁷O have been detected simultaneously in a CO gas sample of natural isotopic abundance by measuring rovibronic excitation spectra of six vibronic bands in the Fourth Positive System. The CO sample was flow cooled by adiabatic expansion in a pulsed supersonic jet. The rovibronic excitation spectra were obtained using a novel pulsed laser source (pulse duration ∼25 ns, spectral bandwidth ∼5 GHz) continuously tunable in the 139-155 nm vacuum ultraviolet wavelength region for excitation and recording the total fluorescence. In the present paper we report on the spectroscopic results obtained, including transition wavelengths of three forbidden rovibronic bands (e³Σ⁻ −  X¹Σ⁺(1, 0), d³Δ  − X¹Σ⁺(5, 0), a′³Σ⁺ −  X¹Σ⁺(14, 0)) of ¹²C¹⁶O and band origins of six rovibronic bands (A¹Π(v′ = 0-5) −  X¹Σ⁺(v″ = 0)) of the rare isotopomer ¹²C¹⁷O, and on the experimental conditions facilitating the high sensitivity of the measurements. The exceptional sensitivity demonstrated by the results has been achieved by fine tuning experimental conditions including the conditions in the supersonic expansion, the jet pulse duration and the laser pulse timing.     

Detection of multiple elements in coal samples from Bangladesh by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) was used to analyze the coal samples from the Barapukuria coal mine of Bangladesh and coal from eastern India. Besides the major elements carbon and silicon, a number of minor and trace elements, such as iron, titanium, aluminum, calcium, sodium, copper, zirconium, neodymium, ytterbium, cerium, samarium, dysprosium and gadolinium were identified. In earlier work some researchers identified the lines around 279 and 280 nm as due to Mg II rather than Yb III. The reasons for identifying these two lines as due to ytterbium in the present work are explained. The detection of multiple elements in one experiment in a commonly used fuel demonstrated the versatility and multi-elemental capability of LIBS.     

Fourier transform emission spectroscopy of the TiF radical in the 407 nm region

Ultraviolet emission spectra of the TiF radical in the 407 nm region have been observed at a resolution of 0.04 cm⁻¹ using a Fourier transform spectrometer. A new electronic assignment of ⁴Γ–X⁴Φ has been proposed. Rotational analysis has been obtained for the 0–0 and 1–1 vibrational bands of the ⁴Γ_5/2–X⁴Φ_3/2, ⁴Γ_9/2–X⁴Φ_7/2, and ⁴Γ_11/2–X⁴Φ_9/2 subbands and the 0–0 band of ⁴Γ_7/2–X⁴Φ_5/2. The lower state rotational and centrifugal distortion constants are consistent with the previous results [J. Mol. Spectrosc. 184 (1997) 186; J. Chem. Phys. 119 (2003) 9496], to the conformation that the lower state of the 407 nm band is the ⁴Φ ground electronic state. Rough estimates of the vibrational interval ΔG(1/2) and the spin–orbit coupling constant A in the ⁴Γ state were also obtained.     

不同物理形态复合肥的激光诱导击穿光谱特性分析

为深入了解激光诱导击穿光谱技术应用于复合肥成分的检测机制,选用不同物理形态(粉状和颗粒状)的复合肥样品,在不同压力下制得片状样品进行实验,以分析不同物理形态复合肥样品的激光诱导击穿光谱特性。实验分别对比了0,0.5,2,4,6MPa下粉末和颗粒的N,P,K的等离子体光谱特性。研究结果表明,在压力较小时,两种形态样品的光谱特性存在较大差别,且颗粒状样品的谱线强度明显高于粉末状样品。而随着压力的增加,两者的光谱特性的差别逐渐减小。对于同一形态样品,随着压力的增加,各主要元素的特征谱线强度均呈现先增加后减小的变化趋势。     

Effects of experimental parameters on elemental analysis of coal by laser-induced breakdown spectroscopy

The purpose of this work is to improve the precision of the elemental analysis of coal using laser-induced breakdown spectroscopy (LIBS). The LIBS technique has the ability to allow simultaneous elemental analysis and on-line determination, so it could be used in the elemental analysis of coal. Organic components such as C, H, O, N and inorganic components such as Ca, Mg, Fe, Al, Si, Ti, Na, and K of coal have been identified. The precision of the LIBS technique depends strongly on the experimental conditions, and the choice of experimental parameters should be aimed at optimizing the repeatability of the measurements. The dependences of the relative standard deviation (RSD) of the LIBS measurements on the experimental parameters including the sample preparation parameters, lens-to-sample distance, sample operation mode, and ambient gas have been investigated. The results indicate that the precision of LIBS measurements for the coal sample can be improved by using the optimum experimental parameters.     

Determination of transition probabilities by laser-induced breakdown spectroscopy with curve-of-growth measurements

A method for the measurement of transition probabilities using laser-induced plasmas as spectroscopic sources is presented. To check its validity, the method is applied to 19 Ni II lines, most of them with known A_ki values. The method is based on the measurement of curves of growth using samples with varying concentrations of the element of interest (here, nickel-copper alloys with nickel contents in the range 0.11-27 at%). The plasma is characterized by a reduced set of parameters, obtained by usual techniques (Boltzmann plot and Stark shift) combined with the curve-of-growth methodology. The transition probabilities are determined by fitting experimental curves of growth to calculations based on the plasma parameters. The use of curves of growth allows eliminating the systematic error due to the self-absorption in the measurement of transition probabilities, and is applicable to intense as well as very weak lines.     

Classification of recyclables using laser-induced breakdown spectroscopy for waste management

With the ever-increasing amount of generated waste governments around the world are looking for, and implementing, ways to minimize waste output and maximize waste recovery. The main difficulties are sorting waste items, identifying the different types of plastics, and the time taken to sort them manually. Bioplastics such as polylactic acid and Novatein thermoplastic protein can be incorporated into the recycling stream to minimize waste. Laser-induced breakdown spectroscopy spectra analyzed by k-nearest neighbor and soft independent modeling by class analogy were investigated as methods that can rapidly identify recyclables. Raw, peak normalized, and total intensity normalized spectra were used to identify which would improve classification. Laser-induced breakdown spectroscopy spectra were generated by single laser shots to different locations on nine samples, glass (brown, green, and clear), tin, aluminum, polylactic acid, Novatein, polyethylene terephthalate, and high-density polyethylene. To prove that the system has the potential to be used on a waste sorting stream an autofocus unit was developed to move the laser-induced breakdown spectroscopy beam into focus on the different sample geometries. Two classification methods were investigated, soft independent modeling by class analogy and the k-nearest neighbors algorithm. k-Nearest neighbors on raw spectra produced the best results. Discrimination between bioplastics and plastics were 100%. Glass samples could not be reliably distinguished from each other. Surface contamination produced three misclassifications from 450 spectra. Similar results were obtained when the spectral range was reduced from 182.26–908.07?nm to 313.20–495.12?nm.     

A review of laser-induced breakdown spectroscopy signal enhancement

A review of the methods of signal enhancement in laser-induced breakdown spectroscopy (LIBS) is presented. Conventional LIBS suffers from disadvantages of low sensitivity and high limits of detection compared with other analytical techniques, such as inductively coupled plasma mass spectrometry. During the last two decades, various methods have been applied to LIBS in order to realize highly quantitative and qualitative analysis. Current approaches include double-pulse excitation, spatial or magnetic confinement, spark discharge, etc. Different configurations of experimental setups and conditions are suggested for the realization of these improved techniques, while various parameters influence significantly on the enhancement effect. With the aim to study the laser ablation process and characterize the effectiveness of each method, several parameters such as plasma volume and emission intensity are reviewed. Several suggestions are proposed to explain the mechanism of each enhancement method. These modified techniques have been applied on various materials and fields.     

第十五届全国原子与分子物理学术会议: 用激光诱导击穿光谱技术定量分析油漆中的有害重金属

很多轻工业产品需要用到油性油漆，其中的重金属元素的含量是否超标将会直接影响到产品质量及其安全性。因此发展轻工产品中重金属含量的快速检测技术，对促进国民经济的发展和保障消费者生命安全具有重要的意义。我们利用激光诱导击穿光谱技术实现了对油漆中有害重金属含量的快速定性和定量分析。通过观测激光等离子体中重金属原子辐射强度可以定性测量重金属含量的大体水平。然后，在相同检测条件下，将已知浓度的标准样品作为参考，制定出各元素的校正曲线，使用外标法，就能够实现定量分析。对Pb、Cr、Cd三种有害重金属元素，目前检出限分别达到9、3.5和23ppm的水平，分析相对误差小于10%，单次测量时间短于2分钟。汞的结果不太理想，检测灵敏度相对偏低，与其原子辐射寿命较短有关。我们将采取脉冲放电延长汞原子辐射弛豫时间的措施来改进汞元素的分析灵敏度，使其达到较高水平。     

自由定标激光诱导击穿光谱技术在炉渣成分定量分析中的应用

采用自由定标激光诱导光谱技术(CF-LIBS)对炉渣中几种主要成分(CaO,SiO2,Al2O3,MgO)进行了定量分析.利用Nd:YAG激光脉冲在空气中烧蚀炉渣样品产生等离子体,等离子体光谱由中阶梯光栅光谱仪记录.通过几种主要元素的原子谱线和离子谱线的玻尔兹曼图,计算了等离子体的温度.利用Ca的一条谱线Stark展宽...