基于可调谐半导体激光吸收光谱技术的气体浓度测量温度影响修正方法研究

可调谐二极管激光吸收光谱技术测量气体浓度时,由于测量氛围温度变化的影响引起解调的二次谐波信号发生变化,最终导致浓度测量的较大误差. 为了修正温度变化对浓度反演结果的影响,适应工业测量、燃烧诊断的需要,采用通过实验所得温度关系的数值拟合修正方法即经验公式修正和根据HITRAN数据库参数的理论关系即理论公式修正两种方法进行分析与讨论. 实验中采用在50 cm长的高温管式炉中通入高温安全的21%浓度的 氧气为目标测定气体,选定760.77 nm的中心吸收波长,测量了温度变化范围为300–900 K,间隔50 K的情况下所得到的谐波信号,并利用一次谐波比值消元法消除光强波动影响后的结果,得出了不同温度下未修正的原始浓度值和通过修正方法后的修正值. 实验结果表明所述的经验公式和理论公式两种修正方法对温度影响都有一定的抑制作用,可以应用到温度变化引起的气体浓度误差修正监测中,为下一步开展燃烧诊断实时在线监测提供了依据. 关键词： 可调谐二极管激光吸收光谱 (TDLAS) 温度修正 经验公式 理论公式     

CO2-laser-induced multiphoton absorption of CF2Cl2

Energy absorption by CF₂Cl₂ from an intense TEA CO₂ laser pulse is measured as a function of the pressure of CF₂Cl₂ and the pressure of Ar bath gas for different laser energy fluences. The fraction of the molecules excited by the laser field and the average energy of the molecular ensemble are determined by a simple experimental method.     

Infrared diode laser spectroscopy of the CF radical

The fundamental bands of the CF radical in the $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and $\text{X}{}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ electronic states were observed by using an infrared tunable diode laser as a source. Zeeman modulation could be used in detecting lines not only in the ${}^2\text{Π}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ state, but also in ${}^2\text{Π}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$, because the CF radical deviates considerably from Hund's case (a). From the least-squares analysis of the observed spectra, the following molecular constants were obtained: B_e = 1.416 704 (37) cm^?1, α_e = 0.018 419 (50) cm^?1, $\text{r}{}_{\mathrm{e}}\text{= 1.271 977 (17)}\text{A}\text{?}$, D_e = 6.68 (15) × 10^?6cm^?1, p₀ = 0.008 580 (21) cm^?1, p₁ = 0.008 52 (11) cm^?1, and $\text{ν}{}_0\text{= 1286.1281 (5)}\text{cm}{}^{\mathrm{?1}}$, with three standard errors in parentheses.     

Cavity-enhanced absorption spectroscopy with a rapidly swept diode laser

Cavity-enhanced absorption spectroscopy is explained in terms of the transmission function of a rapidly swept interferometer, and the integrated transmission is shown to be proportional to the cavity ringdown time. The technique is demonstrated on the b¹Σ_g ⁺-X³Σ_g ^-  (1,0) band in molecular oxygen at 687 nm using a tunable diode laser and a relative-ly high-Q optical cavity (finesse ≈4000). A detection limit of 3×10^-8 cm^-1 s^1/2 is achieved for a 0.8 cm^-1 scanning range. Received: 24 June 2002 / Revised version: 5 August 2002 / Published online: 15 November 2002 RID="*" ID="*"Corresponding author. Fax: +44-1865/275410, E-mail: peverall@physchem.ox.ac.uk     

Diode-laser radiation absorption of CF2Cl2 around 921 cm−1 in a supersonic jet

With a diode laser we have studied the spectral region around 921 cm^–1 of the CF₂Cl₂ molecule cooled in a free jet. Accurate studies of the intensity of two vibrorotational bands have enabled us to determine their assignment. In addition, the rotational structure has been partially resolved, and approximate fitting parameters have been deduced. The simultaneous use of a diode laser and a free jet has proved to be useful in correctly identifying the origin of the absorption bands.     

基于可调谐半导体激光吸收光谱技术的逃逸氨在线监测研究

可调谐半导体激光吸收光谱技术(TDLAS)具有高选择性、高准确性的优点,为逃逸氨的在线检测提供了可靠的技术手段。首先研究了温度对NH3浓度检测的影响,表明在25³00℃之间,浓度随温度的升高而降低;然后在室温为25℃时,利用TDLAS系统对浓度为10300℃之间,浓度随温度的升高而降低;然后在室温为25℃时,利用TDLAS系统对浓度为10¹00ppm的NH3进行检测,采集得到其二次谐波光谱。比较了单光程和多光程样品池测量结果,得到单光程样品池最低检出限为22.9ppm,多光程样品池的检测限为1.21ppm,多光程样品池能够明显地提高检测精度。结果表明,该系统能够适应现场测量环境。     

Sub-ppb NO2 detection by optical feedback cavity-enhanced absorption spectroscopy with a blue diode laser

We report preliminary results on the first application of optical feedback cavity-enhanced absorption spectroscopy with a blue (411 nm) extended cavity diode laser (ECDL) for NO₂ detection. While this technique was originally developed to operate with distributed feedback diode lasers in the near infrared, it is here extended to ECDLs and applied to the blue spectral region. With a simple and compact optical setup, we demonstrate from the baseline noise a minimum detectable NO₂ concentration of 6×10⁹ molecules/cm³ for a single laser scan (70 ms), which extrapolated under atmospheric conditions corresponds to 200 pptv. Signal averaging should allow further lowering of this limit. Observed absorption spectra display more structure than previous spectra obtained at lower resolution by Fourier-transform spectroscopy at the same wavelength. PACS 07.88.+y; 42.55.Px; 42.62.Fi     

可调谐激光吸收光谱应用于气体二维浓度分布重建研究

基于可调谐半导体激光吸收光谱技术(TDLAS),设计了气体浓度二维分布重建系统。将单路可调谐激光分为24路,交叉穿过目标区域,得到24组直接吸收信号(DA),并采用代数迭代法(ART)计算得到目标区域气体浓度二维分布。搭建了二维气体浓度分布测量试验台,利用中心波长在1.653μm的DFB激光器作为光源,选取HITRAN数据库CH4的2v3带R(3)线作为计算谱线进行数值模拟和试验验证,并对重建结果进行了误差分析。结果表明重建系统能很好的实现气体二维浓度分布重建测量。     

High-resolution spectroscopy of CF2Cl2 in a molecular jet

Absorption spectra of CF₂Cl₂ were recorded around 923 cm^–1, with a resolution of 50 MHz. The application of the molecular jet technique considerably simplifies the spectra as compared to room-temperature experiments. Rotational and vibrational temperatures were measured for CF₂Cl₂ pure and seeded in Ar or He. Molecular constants were obtained for thev ₆ vibrational band of the two most abundant chlorine isotopic species, as well as vibrational band origines for thev ₆±v ₄ and thev ₆±v ₅ hot-bands of the CF₂ ³⁵Cl₂ isotope.Guest     

Rapid measurement of cavity ringdown absorption spectra with a swept-frequency laser

A novel cavity ringdown spectrometer, incorporating a miniature continuous-wave swept-frequency laser that is widely tunable, requires less than 1 s to record wide-ranging absorption spectra with high sensitivity in a single rapid sweep of the laser frequency. The free spectral range of the ringdown cavity defines a sampling grid to measure absorbance-dependent ringdown times at successive cavity-resonance frequencies. The spectrometer has a single-ended transmitter-receiver configuration based on retro-reflected optical-heterodyne detection and exploiting fibre-optical telecommunications components. This swept-frequency approach to cavity ringdown spectroscopy yields a simple, low-cost, compact, rugged, versatile instrument for efficient sensing of gases. The performance of the spectrometer is demonstrated by measuring weak near-infrared rovibrational spectra of carbon dioxide gas within the 1.5–1.6 m wavelength range. PACS 42.62.Fi; 07.57.Ty; 07.07.Df     

Infrared multiphoton dissociation of13CF3Cl induced by CO2 laser pulses

Selective infrared multiphoton dissociation of¹³CF₃Cl induced by CO₂ laser pulses adjusted on = 1071.9 cm^–1 has been studied in the energy rangeE between 0.5 and 2 J per laser pulse or fluence range between 5 and 25 J per cm², and in the pressure range between 0.10 and 60 Torr. The effect of these parameters on the isotopic selectivity of the dissociation gives information on the rotational relaxation constants. As for the dissociation probabilities, they vary exponentially withE ^–1. The applicability of such an Arrhenius-type relation is discussed and semi-quantitatively justified.     

High efficiency second harmonic generation with a low power diode laser

\valunit{8}{mW} ( corrected for the output mirror reflection) of the cw coherent blue light around by frequency doubling of only from a diode laser. With IR power of we reach the doubling efficiency of . The overall conversion efficiency from the electrical power into the blue light is . By the way of careful analysis of the Blue Light Induced IR Absorption (BLIIRA) in the potassium niobate based external doubling cavity we obtain good agreement with the theoretical conversion efficiency. Received: 29 November 1996     

CF3Cl，CF2Cl2 和CFCl3分子外价壳层轨道特性的电子动量谱学研究

通过比较相同电子成分轨道的实验和DFT-B3LYP/6-311+G*理论的电子动量分布,系统研究了CF3Cl,CF2Cl2 和CFCl3分子外价壳层的轨道特性.研究结果表明CF3Cl,CF2Cl2 和CFCl3分子的Cl（3p）孤对电子轨道随着Cl原子个数增多,分子内相互作用逐渐增强,Cl原子3p轨道电子动量分布的特征逐渐淹没;F孤对电子轨道和的电子动量分布在高动量区出现了一个弱结构,且随Cl原子个数增多和F原子个数减少逐渐消失,这可能是由于部分轨道C-Cl 键电子成分的贡献;除3a1轨道外,C-F成键轨道和的理论的电子动量分布均在低动量端低于实验结果,可能是由于“d-like” 轨道低动量端的扭曲波效应;3a1轨道理论的电子动量分布均在 范围内低于实验结果,可能是由于扭曲波效应和电子关联等效应的影响.     

Infrared diode laser absorption features of N2O and CO2 in a laval nozzle

Design and operation of a pulsed Laval nozzle and the characterization of molecular flow through such a nozzle using IR tunable diode laser (TDL) is the central theme of this work. The results here deal with He diluted N₂O and CO₂ gaseous systems. Boltzmann type plots of the spectral intensity data of both N₂O and CO₂ show non-linear behaviour. We have attempted to understand this non-linear behaviour of Boltzmann plots in terms of (1) instability in the jet and (2) a two-temperature model for the flowing gas, a cold central core and a hot boundary layer close to the nozzle walls. The model based on jet instability represents the data somewhat poorer than the two-temperature model. The parameters derived from fitting our experimental data to the former model could be used to calculate the thermodynamic parameters only through further approximations. Measured absorption line profile of the P(15) line of the v ₂ band of N₂O as a function of axial distance from the nozzle exit gradually shifts from a Lorentzian to a Gaussian type. Velocity distribution of N₂O molecules in a Laval nozzle is determined by differentiating the absorption line profile of the P(15) line (v ₀=576.235 cm^–1) of the v ₂ band of N₂O. Translational temperature of N₂O molecules is determined from the observed spectral profiles.     

可调谐半导体激光吸收光谱遥测二氧化碳通量的研究

可调谐半导体激光吸收光谱技术(TDLAS)具有高分辨率、高灵敏度以及响应时间快等优点.以室温下工作的近红外可调谐半导体激光器为光源,通过波长调制方法对1 578 nm附近CO2气体吸收线的二次谐波信号测量,结合双开放光路技术,实现对不同高度层面700多米长光程范围内CO2气体浓度的快速在线检测.结合大口径闪烁仪测量的莫宁-奥布霍犬长度和特征速度,通过经验公式计算得到CO2气体的通量在-60～60 mg·m-2·s-1范围内波动.实验数据与涡动相关比较表明,两者数据整体变化趋势一致,该方法可以获得较理想的结果.突破了目前对近地面痕量气体通量的监测只能提供局地结果的现象,使大面积范围内痕量气体通量的测量成为可能.