Laser-induced Fluorescence Spectroscopy of NiS： Identification of a Low-lying Electronic State

Laser-induced fluorescence excitation spectra of jet-cooled NiS molecules were recorded in the energy range of 12200-13550 cm^-1. Four vibronic bands with rotational structure have been observed and assigned to the [12.4]^3∑-0-X^3∑0 transition progression. The relevant rotational constants, significant isotopic shifts, and （equilibrium） molecular parameters have been determined. In addition, the lifetimes of the observed bands have also been measured.

Laser-induced Fluorescence Spectroscopy of Uranium Monofluoride

The laser-induced fluorescence excitation spectra of uranium monofluoride have been recorded in the range of17000-19000 cm^(-1) using twodimensional spectroscopy.High resolution dispersed fluorescence spectra and time-resolved fluorescence spectroscopy were also recorded.Three rotationally resolved bands were intensively analyzed,and all bands were found to be derived from the ground state X(1)4.5 with a rotational constant of 0.23421 cm^(-1).The low-lying electronic states were observed near 435 and 651 cm^(-1) in the dispersed fluorescence spectra,which were assigned as?′=3.5 and 2.5,respectively.The vibrational constants for the X(1)4.5 and X(1)3.5 states were calculated.The branching ratios of the dispersed fluorescence spectra for the[18.62]3.5,[17.72]4.5,and[17.65]4.5 states were reported.Radiative lifetime of332(9)ns,825(49)ns,and 433(15)ns for the[18.62]3.5,[17.72]4.5,and[17.65]4.5 states were obtained by fitting the time-resolved fluorescence spectroscopy,respectively.Transition dipole moments were performed using the branching ratios and the radiative lifetimes.

Laser-induced Fluorescence Spectroscopy of CoS： Identification of a New Excited State Arising from the Ground State

Laser-induced fluorescence excitation spectra and dispersed fluorescence spectra of cobalt sulfide （COS） have been recorded in the energy range of 22400-24400 cm-1 （corresponding to 446-409 nm）. A new electronic transition progression with six vibronic bands, stemming from the X4AT/2 state of CoS, was identified and assigned to be [24.0014AT/2-X4A7/2. The new observed 4A state most probably originates from the core[10a2][47r3][lla2][153][57r3] electronic configuration. Strong perturbations are found to extensively exist in the transition bands of this new state. The rotational constants and lifetimes of these bands have been determined.

Laser-induced Fluorescence Spectroscopy of NiO between 510 and 650 nm

Laser-induced fluorescence excitation spectra of NiO have been recorded in the wavelength region of 510-650 nm under supersonic molecular beam conditions. More than fifty bands have been observed and rotationally analyzed to determine the molecular constants. The excited states exhibit highly irregular variations in terms of isotopic shifts, vibrational intervals, and rotational constants. Twenty-six bands attributed to [Ω=0, 1]-X3∑o transitions have been tentatively grouped into five vibrational progressions. Furthermore, dispersed fluorescence and lifetimes of the strong bands have also been measured.

Laser-induced Fluorescence Spectroscopy of NiCl in 12900-15000 cm-1

Laser-induced fluorescence excitation spectra of jet-cooled NiC1 molecules were recorded in the energy range of 12900-15000 cm-1. Six vibronic bands with rotational structure have been observed and assigned to the [13.0]2II3/2（v＇=0-5）-X2II3/2（v＂=0） transition progression. The relevant rotational constants, significant isotopic shifts, and （equilibrium） molecular parameters have been determined. In addition, the lifetimes of the observed bands have also been measured.

Research on a deconvolution algorithm for laser-induced fluorescence diagnosis based on the maximum entropy principle

Laser-induced fluorescence(LIF)spectroscopy is employed for plasma diagnosis,necessitating the utilization of deconvolution algorithms to isolate the Doppler effect from the raw spectral signal.However,direct deconvolution becomes invalid in the presence of noise as it leads to infinite amplification of high-frequency noise components.To address this issue,we propose a deconvolution algorithm based on the maximum entropy principle.We validate the effectiveness of the proposed algorithm by utilizing simulated LIF spectra at various noise levels(signal-to-noise ratio,SNR=20–80 d B)and measured LIF spectra with Xe as the working fluid.In the typical measured spectrum(SNR=26.23 d B)experiment,compared with the Gaussian filter and the Richardson–Lucy(R-L)algorithm,the proposed algorithm demonstrates an increase in SNR of 1.39 d B and 4.66 d B,respectively,along with a reduction in the root-meansquare error(RMSE)of 35%and 64%,respectively.Additionally,there is a decrease in the spectral angle(SA)of 0.05 and 0.11,respectively.In the high-quality spectrum(SNR=43.96 d B)experiment,the results show that the running time of the proposed algorithm is reduced by about98%compared with the R-L iterative algorithm.Moreover,the maximum entropy algorithm avoids parameter optimization settings and is more suitable for automatic implementation.In conclusion,the proposed algorithm can accurately resolve Doppler spectrum details while effectively suppressing noise,thus highlighting its advantage in LIF spectral deconvolution applications.

Laser-induced Fluorescence and Dispersed Fluorescence Spectroscopy of NiB： Identification of a New 2П State in 19000-22100 cm^-1

The laser-induced fluorescence excitation spectra of jet-cooled NiB radicals have been recorded in the energy range of 19000-22100 cm-1. Eleven bands have been assigned to the [20.77]2П-X2∑＋ transition system for the first time. The dispersed fluorescence spectra related to most of these bands have been investigated. Vibrationally excited levels of the ground electronic state, with v＂ up to 6, have been observed. In addition, the lifetimes for almost all the observed bands have also been measured.

Quantitative measurement of hydroxyl radical(OH) concentration in premixed flat flame by combining laser-induced fluorescence and direct absorption spectroscopy

An accurate and reasonable technique combining direct absorption spectroscopy and laser-induced fluorescence（LIF）methods is developed to quantitatively measure the concentrations of hydroxyl in CH;/air flat laminar flame. In our approach, particular attention is paid to the linear laser-induced fluorescence and absorption processes, and experimental details as well. Through measuring the temperature, LIF signal distribution and integrated absorption, spatially absolute OH concentrations profiles are successfully resolved. These experimental results are then compared with the numerical simulation. It is proved that the good quality of the results implies that this method is suitable for calibrating the OH-PLIF measurement in a practical combustor.

Elemental and proximate analysis of coal by x-ray fluorescence assisted laser-induced breakdown spectroscopy

Although laser-induced breakdown spectroscopy(LIBS),as a fast on-line analysis technology,has great potential and competitiveness in the analysis of chemical composition and proximate analysis results of coal in thermal power plants,the measurement repeatability of LIBS needs to be further improved due to the difficulty in controlling the stability of the generated plasmas at present.In this paper,we propose a novel x-ray fluorescence(XRF) assisted LIBS method for high repeatability analysis of coal quality,which not only inherits the ability of LIBS to directly analyze organic elements such as C and H in coal,but also uses XRF to make up for the lack of stability of LIBS in determining other inorganic ash-forming elements.With the combination of elemental lines in LIBS and XRF spectra,the principal component analysis and the partial least squares are used to establish the prediction model and perform multi-elemental and proximate analysis of coal.Quantitative analysis results show that the relative standard deviation(RSD) of C is 0.15%,the RSDs of other elements are less than 4%,and the standard deviations of calorific value,ash content,sulfur content and volatile matter are 0.11 MJ kg,0.17%,0.79% and 0.41%respectively,indicating that the method has good repeatability in determination of coal quality.This work is helpful to accelerate the development of LIBS in the field of rapid measurement of coal entering the power plant and on-line monitoring of coal entering the furnace.

Laser-induced Fluorescence Spectrum of CoS Between 15200 and 19000 cm^-1

Laser-induced fluorescence excitation spectra of jet-cooled CoS molecules have been recorded in the energy range of 15200-19000 cm^-1. Five transition progressions have been reported for the first time, the assignments of these progressions have been derived from a rotational analysis of vibronic bands and they are determined to be [15.58]^4△7/2-X^4△7/2, [16.02]^4△7/2- X^4△7/2, [16.50]^4△7/2-X^4△T/2, [17.80]^4II5/2-X^4△7/2, and [18.00]^4△7/2-X^4△7/2 transitions. In addition, under the supersonic jet condition the fluorescent lifetimes of these vibronic states were measured by exponentially fitting the fluorescence decay. Based on the observed spectra and the measured lifetimes of the vibronic states, the newly identified electronic states are discussed.

Laser-induced fluorescence experimental spectroscopy and theoretical calculations of uranium monoxide

As a model molecule of actinide chemistry,UO molecule plays an important role in understanding the electronic structure and chemical bonding of actinide-containing species.We report a study of the laser-induced fluorescence spectra of the U^(16)O and U^(18)O using two-dimensional spectroscopy.Several rotationally resolved excitation spectra were investigated.Accurate molecular rotational constants and equilibrium internuclear distances were reported.Low-lying electronic states information was extracted from high resolution dispersed fluorescence spectra and analyzed by the ligand field theory model.The configuration of the ground state was determined as U^(2+)(5 f^(3)7 s)O^(2-).The branching ratios,and the vibrational harmonic and anharmonic parameters were also obtained.Radiative lifetimes were determined by recording the timeresolved fluorescence spectroscopy.Transition dipole moments were calculated using the branching ratios and the radiative lifetimes.These findings were elucidated by using quantum-chemical calculations,and the chemical bonding was also analyzed.The findings presented in this work will enrich our understanding of actinide-containing molecules.

B-X and C-X Band Systems of CuCl Revisited： Laser-induced Fluorescence Study in 465-490 nm

We have reinvestigated the B-X and C-X band systems of CuCl by recording the laser- induced fluorescence excitation spectra in 20400-21800 cm^-1. The rotational analyses in Hund＇s case （a） revealed unambiguously a singlet-to-singlet transition nature. The radiative lifetimes were measured to be 4.670 and 4.667 μs, respectively, which are much longer than that expected for a pure singlet of CuCl. This implies that the fluorescence mechanism in the B or C band systems lies in the mixing of the singlets （^1II and ^1E^＋） and triplets （^3II0,1,2） and that the two excited states observed in our experiment might be the singlets that have been strongly ＂contaminated＂ by their triplet neighbors.

Incorporating empirical knowledge into data-driven variable selection for quantitative analysis of coal ash content by laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy(LIBS)has become a widely used atomic spectroscopic technique for rapid coal analysis.However,the vast amount of spectral information in LIBS contains signal uncertainty,which can affect its quantification performance.In this work,we propose a hybrid variable selection method to improve the performance of LIBS quantification.Important variables are first identified using Pearson's correlation coefficient,mutual information,least absolute shrinkage and selection operator(LASSO)and random forest,and then filtered and combined with empirical variables related to fingerprint elements of coal ash content.Subsequently,these variables are fed into a partial least squares regression(PLSR).Additionally,in some models,certain variables unrelated to ash content are removed manually to study the impact of variable deselection on model performance.The proposed hybrid strategy was tested on three LIBS datasets for quantitative analysis of coal ash content and compared with the corresponding data-driven baseline method.It is significantly better than the variable selection only method based on empirical knowledge and in most cases outperforms the baseline method.The results showed that on all three datasets the hybrid strategy for variable selection combining empirical knowledge and data-driven algorithms achieved the lowest root mean square error of prediction(RMSEP)values of 1.605,3.478 and 1.647,respectively,which were significantly lower than those obtained from multiple linear regression using only 12 empirical variables,which are 1.959,3.718 and 2.181,respectively.The LASSO-PLSR model with empirical support and 20 selected variables exhibited a significantly improved performance after variable deselection,with RMSEP values dropping from 1.635,3.962 and 1.647 to 1.483,3.086 and 1.567,respectively.Such results demonstrate that using empirical knowledge as a support for datadriven variable selection can be a viable approach to improve the accuracy and reliability of LIBS quantification.

Estimating the yield stress of soft materials via laser-induced breakdown spectroscopy

Taking three typical soft samples prepared respectively by loose packings of 77-,95-,and 109-μm copper grains as examples,we perform an experiment to investigate the energy-dependent laser-induced breakdown spectroscopy(LIBS)of soft materials.We discovered a reversal phenomenon in the trend of energy dependence of plasma emission intensity:increasing initially and then decreasing separated by a well-defined critical energy.The trend reversal is attributed to the laser-induced recoil pressure at the critical energy just matching the sample's yield strength.As a result,a one-to-one correspondence can be well established between the samples'yield stress and the critical energy that is easily obtainable from LIBS measurements.This allows us to propose an innovative method for estimating the yield stress of soft materials via LIBS with attractive advantages including in-situ remote detection,real-time data collection,and minimal destructive to sample.

Laser-induced breakdown spectroscopy as a method for millimeter-scale inspection of surface flatness

A non-contact method for millimeter-scale inspection of material surface flatness via Laser-Induced Breakdown Spectroscopy(LIBS)is investigated experimentally.The experiment is performed using a planished surface of an alloy steel sample to simulate its various flatness,ranging from 0 to 4.4 mm,by adjusting the laser focal plane to the surface distance with a step length of 0.2 mm.It is found that LIBS measurements are successful in inspecting the flatness differences among these simulated cases,implying that the method investigated here is feasible.It is also found that,for achieving the inspection of surface flatness within such a wide range,when univariate analysis is applied,a piecewise calibration model must be constructed.This is due to the complex dependence of plasma formation conditions on the surface flatness,which inevitably complicates the inspection procedure.To solve the problem,a multivariate analysis with the help of Back-Propagation Neural Network(BPNN)algorithms is applied to further construct the calibration model.By detailed analysis of the model performance,we demonstrate that a unified calibration model can be well established based on BPNN algorithms for unambiguous millimeter-scale range inspection of surface flatness with a resolution of about 0.2 mm.

Estimating the grain size of microgranular material using laser-induced breakdown spectroscopy combined with machine learning algorithms

Recent work has validated a new method for estimating the grain size of microgranular materials in the range of tens to hundreds of micrometers using laser-induced breakdown spectroscopy(LIBS).In this situation,a piecewise univariate model must be constructed to estimate grain size due to the complex dependence of the plasma formation environment on grain size.In the present work,we tentatively construct a unified calibration model suitable for LIBS-based estimation of those grain sizes.Specifically,two unified multivariate calibration models are constructed based on back-propagation neural network(BPNN)algorithms using feature selection strategies with and without considering prior information.By detailed analysis of the performances of the two multivariate models,it was found that a unified calibration model can be successfully constructed based on BPNN algorithms for estimating the grain size in the range of tens to hundreds of micrometers.It was also found that the model constructed with a priorguided feature selection strategy had better prediction performance.This study has practical significance in developing the technology for material analysis using LIBS,especially when the LIBS signal exhibits a complex dependence on the material parameter to be estimated.

Characteristics of laser-induced breakdown spectroscopy of liquid slag

Rapid online analysis of liquid slag is essential for optimizing the quality and energy efficiency of steel production. To investigate the key factors that affect the online measurement of refined slag using laser-induced breakdown spectroscopy(LIBS), this study examined the effects of slag composition and temperature on the intensity and stability of the LIBS spectra. The experimental temperature was controlled at three levels: 1350℃, 1400℃, and 1450℃. The results showed that slag composition and temperature significantly affected the intensity and stability of the LIBS spectra. Increasing the Fe content and temperature in the slag reduces its viscosity, resulting in an enhanced intensity and stability of the LIBS spectra. Additionally, 42 refined slag samples were quantitatively analyzed for Fe, Si, Ca, Mg, Al, and Mn at 1350℃, 1400℃, and 1450℃.The normalized full spectrum combined with partial least squares(PLS) quantification modeling was used, using the Ca Ⅱ 317.91 nm spectral line as an internal standard. The results show that using the internal standard normalization method can significantly reduce the influence of spectral fluctuations. Meanwhile, a temperature of 1450℃ has been found to yield superior results compared to both 1350℃ and 1400℃, and it is advantageous to conduct a quantitative analysis of the slag when it is in a “water-like” state with low viscosity.

Quantitative measurements of one-dimensional OH absolute concentration profiles in a methane/air flat flame by bi-directional laser-induced fluorescence

The one-dimensional （1D） spatial distributions of OH absolute concentration in methane/air laminar premixed flat flame under different equivalence ratios at atmospheric pressure are investigated by using bi-directional laser-induced flu- orescence （LIF） detection scheme combined with the direct absorption spectroscopy. The effective peak absorption cross section and the average temperature at a height of 2 mm above the burner are obtained by exciting absorption on the Q1（8） rotational line in the A2∑＋ （Dt = 0） ←- X2∏ （v = 0） at 309.240 nm. The measured values are 1.86×10-15 cm2 and 1719 K, respectively. Spatial filtering and frequency filtering methods of reducing noise are used to deal with the experi- mental data, and the smoothing effects are also compared using the two methods. The spatial distribution regularities of OH concentration are obtained with the equivalence ratios ranging from 0.8 to 1.3. The spatial resolution of the measured result is 84μm. Finally, a comparison is made between the experimental result of this paper and other relevant study results.

Absorption,quenching,and enhancement by tracer in acetone/toluene laser-induced fluorescence

To measure the equivalent ratio distribution of the two-stage lean premixed(DLP)flame,we propose using acetone/toluene planar laser-induced fluorescence(PLIF)technology to simultaneously measure the concentrations of the two components.Appropriate excitation laser wavelength and filters are used to assess the influence of acetone and toluene on each other’s fluorescence signal at room temperature.Experimental results show that acetone has a strong absorption effect on toluene’s fluorescence signal,the effective absorption cross-section is 5.77×10-20 cm-2.Acetone has an obvious quenching effect on the toluene fluorescence signal,and the Stern–Volmer coefficient is 0.50 kPa-1.The collisions between the molecules of toluene and acetone will lead to the enhancement of the fluorescence signal of acetone,and the enhancement coefficient is exponential with the acetone’s concentration.The quantitative relationship between the fluorescence intensity and the concentrations of the two tracers is obtained by establishing the photophysical model of toluene and acetone’s fluorescence signals.

Numerical analysis of quantitative measurement of hydroxyl radical concentration using laser-induced fluorescence in flame

The aim of the present work is to quantitatively measure the hydroxyl radical concentration by using LIF（laserinduced fluorescence） in flame.The detailed physical models of spectral absorption lineshape broadening,collisional transition and quenching at elevated pressure are built.The fine energy level structure of the OH molecule is illustrated to understand the process with laser-induced fluorescence emission and others in the case without radiation,which include collisional quenching,rotational energy transfer（RET）,and vibrational energy transfer（VET）.Based on these,some numerical results are achieved by simulations in order to evaluate the fluorescence yield at elevated pressure.These results are useful for understanding the real physical processes in OH-LIF technique and finding a way to calibrate the signal for quantitative measurement of OH concentration in a practical combustor.