Emission characteristics of hydrogen-oxygen flames

The emission spectra of hydrogen-oxygen flames are discussed. High temperature measurements of the radiative characteristics of the OH group in flames are described. The spectral absorption coefficients and the integral intensities of the hydroxyl bands are analyzed. A method for determining the nonequilibrium radiative cooling of hydrogen-oxygen flames using experimental data, their temperatures, and nonequilibrium coefficients is described and the results are examined.     

Air pressure broadening and shifting of high-J lines of (00011) ← (00001) band of CO2

The absorption spectra of carbon dioxide (isotope 626, natural abundance in air, ambient temperature) have been studied at total pressures 68-570 Torr with spectral resolution 0.003-0.005 cm⁻¹. The spectra were measured in the spectral domain of 2273-2393 cm⁻¹ by FTIR spectrometer Bruker IFS 125 HR equipped with White-type multipass cell (6.4-41.6 m) and with a cell having 10 cm optical path length. Pressure broadening and shift coefficients were obtained from a series of spectra by means of a nonlinear least-squares spectral fitting technique for the lines of the (00011)←(00001) band with rotational quantum number up to J=82. For fitting of the individual line shapes, we used the Voigt profile with pre-calculated Doppler broadening parameter. The experimental pressure broadening and shift coefficients are compared with the values available in spectroscopic databases HITRAN 2008 and Carbon Dioxide Spectroscopic Databank (CDSD-296) and with other experimental values reported in the literature.     

Measurements of O2-broadening and -shifting parameters of water vapor spectral lines in the second hexad region

Oxygen pressure induced broadening and shifting coefficients for water vapor absorption lines in the 8600–9010 cm⁻¹ region have been measured and calculated. The spectra were recorded with a Bruker IFS 125HR spectrometer at a spectral resolution of 0.01 cm⁻¹ for lines with angular moment of the upper states up to 10. Calculations of line broadening and shifting coefficients are performed using a semi-empirical approach. The method is based on the impact theory of broadening, and includes the correction factors whose parameters can be determined by fitting the broadening or shifting coefficients to the experimental data. The comparison of our calculations with the experimental values argues that the semi-empirical method is quite acceptable for the determination of the water vapor absorption line profile parameters.     

超高温FTIR光谱发射率测量系统的线性度分析

为研究航天领域特种材料高温区域的光谱辐射特性,建立了基于傅里叶光谱仪的超高温光谱发射率测量系统。系统线性度是发射率测量精度的保证,通过测量多温度点黑体辐射的光谱信号,采用多温度点线性拟合方法求得每个光谱点的光谱信号值与黑体光谱辐射亮度的函数关系式,并结合仪器线性度测量理论,建立了光谱发射率测量系统的线性度测量方法。实验测量了黑体温度范围1 000～2 000℃和光谱范围3～20μm的光谱辐射信号,求得波长λ=4μm的理论直线与测量光谱值的线性关系。实验表明,仪器在4～18μm光谱范围响应较好,除CO2强吸收光谱区域,仪器的光谱线性度均优于1%。当测量系统线性度一定时,温度越高,光谱误差对发射率的影响越小。评定光谱发射率测量系统的线性度有利于剔除个别温度点光谱扰动带来的误差。     

Absolute line intensity measurements in the ν2 bands of HDO and D2O using a tunable diode laser spectrometer

Absolute line intensities for several individual vibration-rotation transitions in the ν₂ bands of HDO and D₂O have been determined at room temperature from laboratory spectra recorded with a tunable diode laser spectrometer. Two tunable semiconductor diode lasers operating in the 1250- to 1350- and 1060- to 1140-cm⁻¹ spectral regions have been used in the recording of the data. Comparisons are made with previously published results where appropriate.     

基于TDLAS技术的水汽低温吸收光谱参数测量

精确的气体光谱参数对气体浓度、温度等的光谱精确反演测量具有十分重要的意义,针对当前主流光谱数据库(例如HITRAN)中数据与实际数值存在相当误差的问题,自主研制了一套基于静态冷却技术的低温光谱实验平台,用于精确测量低温下的气体吸收光谱参数.运用该低温光谱实验平台,采用可调谐二极管激光吸收光谱(TDLAS)技术测量了温度为230—340 K、压强为10—1000 Pa时7240—7246 cm~(-1)波段的纯水汽振转跃迁光谱.采用Voigt线型多峰拟合方法,获得了5条水汽振转跃迁谱在不同温度、不同压强下的积分吸光度值及洛伦兹展宽值,运用线性拟合的方法得到这5条吸收线的自展宽半峰全宽系数及参考温度下的线强值.运用不确定度传递公式,计算得到实验结果的不确定度,与HITRAN2012数据库中的线参数进行对比,所测的5条吸收线中实验结果与数据库值最大相差10.96%,且实验结果的不确定度为1.11%—2.98%(置信概率p=95%,包含因子k=2),小于HITRAN2012数据库值的不确定度.     

Development of diode laser absorption spectroscopy method for determining temperature and concentration of molecules in remote object

We develop a method of diode laser absorption spectroscopy for noncontact measurements of the temperature and pressure of a gas mixture under unsteady-state conditions at low signal-to-noise ratios. The method is based on the measurement of the absorption spectra of water molecules and approximation of experimental spectra by spectra simulated based on spectroscopic databases. Different approximation algorithms of experimental spectra are tested, such as fitting by individual contours and fitting by a part of the simulated spectrum. We reveal that, at small signal-to-noise ratios, the approximation of experimental data by a simulated spectrum yields more correct data on the temperature of the mixture compared to the fitting by individual contours. For the examined temperature range of 300–1300 K, the determination error of the gas temperature in the test cell proved to be approximately three times lower than upon fitting by individual contours. The developed method of recording and processing spectra is used to measure the temperature, water vapor concentration, and total pressure under the unsteady-state combustion conditions of an air-hydrogen mixture in a supersonic flow.     

Spectroscopic manifestations of orientational phase transition in adsorbate monolayer

In the framework of the virtual crystal approximation, the temperature dependences of frequencies and integral intensities of infrared absorption spectral lines are established for an adsorbate monolayer near the point of the order-to-disorder orientational phase transition. The results obtained are consistent with the experimentally observed temperature dependences of the vibrational spectra for the 2 × 1 monolayer CO/NaCl (100). For this system, the Davydov splitting does not vanish on the phase transition due to a nonzero value of the average dipole moment (unlike molecular crystals and orientationally planar monolayers in which the average dipole moment becomes zero at the phase transition temperature).     

基于非线性最小二乘法的多光谱拟合程序：应用于12CH4谱线参数分析

精确的甲烷分子实验光谱参数在大气科学和天文探测等领域有着广泛的应用,特别是谱线的展宽系数及其温度依赖系数对于甲烷分子浓度廓线的研究尤为重要。精密的实验测量是获得准确谱线参数的重要手段。采用实验测量获取谱线参数时,需要在已知实验条件（浓度,温度,总压力,吸收光程以及气体分子种类的混合比等）的情况下,多次扫描同一波段范围得到多组实验室吸收光谱,然后利用基于非线性最小二乘法的拟合程序处理这些光谱,反演获得所需要的光谱参数。然而,一般常用的单光谱拟合程序处理实验光谱既费时又容易引起拟合过程中的误差传递。针对此问题,采用最小二乘拟合技术和Levenberg-Marquardt迭代算法编写了一款适用于处理由可调谐半导体激光吸收光谱技术（TDLAS）所获得的吸收光谱的多光谱拟合程序。该程序可同时处理多张实验光谱,并基于全局拟合方法获得一套光谱参数。详细介绍了该程序的原理、使用方法及数据处理过程。利用多光谱拟合程序中的Voigt线型处理了2 958～2 959 cm-1波数内甲烷（12CH₄）分子6条跃迁谱线的实验光谱,获得了296.0,251.0,223.0,198.0和173.0 K共5组温度下12CH₄分子6条谱线的空气展宽系数。与之前文献报道的该波段内采用单光谱拟合程序得到的相应数据对比结果表明：获得的各温度下的空气展宽系数与参考文献中相应数据差值的百分比处在-4.97%~1.58%之间,两者数据整体符合较好,并且在30组对比数据中,有4组由单光谱拟合程序得到的空气展宽系数的误差值小于由多光谱拟合程序得到的相应数值,有2组数据显示由两种方法获得的误差值相等,其余24组由多光谱拟合程序获得的数据拟合误差小于由单光谱拟合程序获得的相应数值,表明多光谱拟合程序具有良好的可靠性,适用于气体分子吸收光谱的处理。     

An approach to gas sensors based on tunable diode laser incomplete saturated absorption spectra

A spectral profile reconstruction method that can be applied to incomplete saturated-absorption spectra is proposed and demonstrated. Through simulation and theoretical calculation, it is proved that compared with the traditional wholeprofile fitting method, this new method can increase the concentration detection upper limit of a single absorption line by about 8.7 times. High-concentration water vapor is measured using TDLAS technology, the total water vapor pressure and the self-broadened half-width coefficient of the spectrum were simultaneously measured from incomplete saturatedabsorption spectra and compared with high-precision pressure sensors and the HITRAN databases. Their maximum relative deviations were about 4.63% and 9.10%, respectively. These results show that the spectral profile reconstruction method has great application potential for expanding the dynamic range of single-line measurements to higher concentrations,especially for in-situ online measurements under complex conditions, such as over large temperature and concentration dynamic ranges.     

Curve of growth analysis laboratory absorption spectra for a random exponential band of Voigt lines,with application to ultraviolet spectra of HNO3

A computerized method for optimal fitting of experimental absorption data to curves of growth based on a statistical band model with Voigt line shape and an exponential distribution of line intensities is described. The general method is applied to ultraviolet absorption spectra of HNO₃ vapor.     

Temperature dependence of the self-broadening coefficients of ethane

Using a diode-laser spectrometer, self-broadening coefficients have been measured at three temperatures (246.2, 226.2 and 150.2 K) for 11 spectral lines in the ν₉ fundamental band of ¹²C₂H₆. The collisional widths have been obtained by fitting each experimental absorption profile with a Rautian model. The temperature dependence exponent n was also determined for each line, and found to be constant within experimental uncertainties. The mean value is equal to n = 0.676.     

The absorption spectrum of D<Subscript>2</Subscript>O in the region of 0.97 μm: the 3ν<Subscript>1</Subscript> + ν<Subscript>3</Subscript> vibrational–rotational band

The vibrational–rotational absorption spectrum of D₂O in the range from 10 120 to 10 450 cm^–1 is recorded on a Fourier transform spectrometer with a resolution of 0.05 cm^–1. The measurements were performed using a multipass White cell with an optical path length of 24 m. A light-emitting diode with brightness higher than that of other devices was used as a radiation source. The signal-to-noise ratio was about 10⁴. The spectrum is interpreted as consisting of lines of more than 400 transitions. The spectral characteristics of lines (centers, intensities, and half widths) are determined by fitting the Voigt profile parameters to experimental data by the least-squares method. The intensities of lines and the experimental rotational energy levels of the (301) vibrational state of the D₂ ¹⁶O molecule with high rotational quantum numbers are determined for the first time.     

Diagnostic and characterization of the VCSEL diodes based on GaSb

Vertical-Cavity Surface-Emitting Laser (VCSEL) diodes are among the youngest members of the semiconductor laser diode family. The main aim of our work focuses on the measurement of the basic properties (the spectral range of the laser emission, temperature and current tunability) of experimental VCSEL diode lasers based on GaSb operating in the infrared region around 4250 cm^?1. A high-resolution FTIR Bruker IFS 120 HR spectrometer with a maximum resolution of 0.0035 cm^?1 was used in the emission setup for the laser diagnostic research. The absorption spectra of atmospheric pollutants like methane, carbon monoxide and ammonia have been measured using these VCSELs for the first time.     

Experimental Line Parameters of the Oxygen A Band at 760 nm

To support atmospheric remote sensing applications, line positions, intensities, self- and nitrogen-broadened linewidths and their temperature dependences and pressure-induced shifts in line positions at room temperature were measured up to J' and N' = 22 for the oxygen A band at 13 122 cm(-1). Line intensities were obtained with 1% precisions and 2% absolute accuracies using absorption spectra recorded at Doppler-limited (0.02 cm(-1)) resolution with the McMath Fourier transform spectrometer (FTS) located at Kitt Peak National Observatory/National Solar Observatory in Arizona. The oxygen line positions were calibrated using near-infrared transitions of the 2-0 and 3-0 bands of CO as secondary standards. The intensities and positions of seven H(2)O lines near 13 900 cm(-1) were also remeasured to validate the FTS performance. The O(2) intensities fell within 1% of the values currently assumed for the molecular databases, but it was found that broadening coefficients and line positions should be revised for the A band of molecular oxygen. Copyright 2000 Academic Press.     

An experimental method for making spectral emittance and surface temperature measurements of opaque surfaces

An experimental procedure has been developed to make spectral emittance and temperature measurements. The spectral emittance of an object is calculated using measurements of the spectral emissive power and of the surface temperature of the object obtained using a Fourier transform infrared (FTIR) spectrometer. A calibration procedure is described in detail which accounts for the temperature dependence of the detector. The methods used to extract the spectral emissive power and surface temperature from measured infrared spectra were validated using a blackbody radiator at known temperatures. The average error in the measured spectral emittance was 2.1% and the average difference between the temperature inferred from the recorded spectra and the temperature indicated on the blackbody radiator was 1.2%. The method was used to measure the spectral emittance of oxidized copper at various temperatures.     

基于FTIR光谱辐射测量分析大气透过率

提出了一种利用FTIR光谱仪进行大气透过率测量的方法。通过黑体对系统的光谱响应进行标定,由两点温度校准得到测量光谱的辐射亮度谱。在一定的距离内实测并分析计算出了CO2红外吸收波段的大气透过率谱。采用非线性最小二乘方法将测量的CO2透过率谱与HITRAN数据库中的光谱拟合得到了干洁大气中的CO2浓度值。实验结果表明,该方法是测量大气透过率和定量分析气体组分的可行性方法。     

电激励DF化学激光器光腔流场荧光光谱测量与分析

 观察并记录了增大D₂流量时DF激光光腔流场可见光荧光的变化现象,对光轴处的可见光荧光进行了光谱测量,使用波长为632.8 nm和543.5 nm的He-Ne激光器对光谱仪进行标定。对激光器光腔内介质成分进行了理论分析,并理论计算了DF高次泛频谱线及D原子谱线,通过比对荧光的实验测量光谱与光腔内介质成分谱线,发现荧光是由F,He,D,N,DF及其它激发态介质共同形成的,对光轴处荧光的颜色构成作出了解释。     

Spectral Intensity and Lineshape Measurements in the First Overtone Band of HF Using Tunable Diode Lasers

High-resolution absorption lineshapes for the P(3) and P(6) transitions of the first overtone (v = 2-0) band of HF at 296 K have been measured using a pair of distributed feedback diode lasers operating near 1.31 and 1.34 μm, respectively. Spectral line intensities and self-broadening parameters were determined by fitting the measured spectra with Voigt, Galatry, and Rautian lineshape models. Voigt profiles fit the low-pressure (<10 Torr) spectra of the P(3) transition reasonably well due to the relatively strong collisional broadening effect. Lineshape measurements of the P(6) transition (for pressures ranging from 5 to 60 Torr) show significant variation from the Voigt lineshape model due to velocity-changing collisions that effectively reduce the Doppler component of the spectral line. Lineshape models that include motional (Dicke) narrowing effects, Galatry (soft collision) and Rautian (hard collision) profiles yield significant improvements in the spectral lineshape fits compared with Voigt profiles. The collisional broadening coefficient (gamma) of the P(6) transition obtained from a Voigt fit is approximately 4% lower than those found with either Galatry or Rautian profile fits. The measured intensities and self-broadening coefficients are compared with values in the HITRAN database and previous measurements. Copyright 1999 Academic Press.     

Determination of Self-, Air-, and Oxygen-Broadening Coefficients of Pure Rotational Absorption Lines of Ozone and of Their Temperature Dependencies

Room temperature measurements of self-, air-, and oxygen-broadening coefficients are reported for 101 pure rotational absorption lines for ¹⁶O₃ covering a range of 7≤J″≤34 and 3≤K₋₁″≤11 in the spectral region 50 to 90 cm⁻. In addition, the temperature dependence of the coefficients has been determined for most of these lines. A total of 14 high-resolution Fourier transform far-IR spectra (0.004 cm⁻ resolution) of ozone/air/dioxygen mixtures were recorded at various temperatures (212, 252, and 296 K). The broadening coefficients and corresponding temperature exponents were deduced by analyzing all of the 14 spectra simultaneously for each absorption line using a nonlinear least-squares fitting technique. Several sources of systematic errors were taken into account: the values of the partial pressures of the species involved, the value of the total optical path length, the sample temperature, thermal emission from sources other than the spectrometer source (e.g., sample emission), the effect of convolution with the instrument function, and intensity contributions from weak and neighbouring absorption lines. The variation of the determined broadening coefficients and temperature exponents with the rotational quantum numbers J″ and K₋₁″ has been examined. Furthermore the determined pressure-broadening parameters have been compared to the data reported in the 2000 edition of the HITRAN compilation.