利用石英增强光声光谱技术在2.0μm处实现高灵敏CO_2检测的实验研究

基于石英增强光声光谱技术,以中心波长为2.0μm的窄线宽分布反馈式半导体激光器(DFB)为激励光源,采用波长调制及二次谐波解调技术通过改变激光器工作电流实现波长扫描完成了痕量CO2气体检测系统,并通过优化实验参数确定了常压下激光最佳调制深度,实现了高灵敏CO2浓度的检测。通过改变待测气体中的水汽浓度,研究了水汽对CO2气体探测结果的影响,结果显示在水汽浓度低于0.2%范围内,CO2气体光声信号随H2O浓度的上升而明显增强,当浓度高于此值后,H2O浓度的增加对CO2光声信号的增强作用几乎维持不变。数据显示,常温常压下H2O分子通过提高分子弛豫率最多可将二氧化碳R16吸收线的光声信号幅值提高约2.1倍。优化后的装置可以很好的实现大气中CO2浓度的检测。该装置获得的最小探测灵敏度为19ppm(1σ,300ms积分时间),相应的归一化噪声等效吸收系数为4.71×10-9 cm-1·W·Hz-1/2。     

基于中红外QCL激光和新型多通池高灵敏度测量CO和N_2O的研究

利用量子级联激光器(QCL)结合新型小型化光学多通吸收池高灵敏度同时测量CO和N2O痕量气体。所用激光为工作在4.3 mm附近的宽调谐、无跳模外腔量子级联激光器,激光在较短的时间内(1 s)连续波长扫描,并覆盖N2O(2203.73333 cm-1)和CO(2203.161 cm-1)两种分子的吸收谱线,从而实现对N2O和CO的同时测量。利用物理基长为12 cm的新型小型化光学多通吸收池,探测光在吸收池内来回反射243次,有效光程达到29 m。利用波长调制吸收光谱和二次谐波探测技术实现了对N2O和CO的高灵敏度探测,测量系统的最低可探测浓度极限约为2.0×10-9(N2O)和1.7×10-9(CO)。     

高灵敏度快速扫描光腔衰荡光谱方法探测大气CH_4含量

搭建了基于近红外连续激光器的高灵敏度快速扫描光腔衰荡光谱仪(SC-CRDS)。通过压电陶瓷(PZT)快速扫描腔长,并用跟踪电路使腔长自动跟踪激光波长变化,实现衰荡光谱的快速测量。利用CH4在1653.73 nm(6046.95 cm-1)附近的光谱吸收峰,用该装置对CH4气体含量进行测量。通过测量多个光谱点确定吸收线中心吸收峰值和激光波长,并反馈补偿激光中心波长使其稳定在吸收线,成功解决了由于激光器波长/频率严重漂移导致的不能持续准确测量问题。利用标准浓度的CH4样品校准其1653.73 nm吸收峰谱线强度。该光腔衰荡光谱仪装置结构简单,性能稳定,CH4浓度检测限达到1.0×10-9,可用于长时间监测室外空气中的CH4浓度。     

基于量子级联激光器的温室气体测量方法研究

中红外为分子的基频吸收波段,可被用于痕量气体的高灵敏度检测。介绍了基于中红外室温连续量子级联激光器(CW-QCL)结合波长调制技术(WMS)的光谱检测方法,研究了消除气体间交叉干扰的方法,并进行了相关的验证实验。利用中心波长在1274cm-1波段附近的量子级联激光器搭建了一套开放光路温室气体探测实验系统,进行101m开放式测量实验,实现了对大气中CH4、N2O的同步在线测量,检测限分别为3.87×10-9和1.28×10-9,验证了实验系统和实验方法的可行性,为实现区域高灵敏温室气体监测奠定了基础。     

1.31μm附近CO2的高灵敏度吸收光谱

采用可连续调谐半导体二极管激光器作为探测光源,将长程多通池吸收光谱、波长调制和谐波探测技术相结合,建立了一套具有高检测灵敏度和高分辨率的测量气态分子光谱及进行微量分析的研究装置.可以测量6.67×102Pa下～10-27 cm-1·(molecule·cm-2)-1的强度,最小可探测吸收达到～10-8.并利用该装置测量了CO2气体在1.31 μm附近的近红外吸收光谱,并用最小二乘法拟合实验数据获得了这一波段谱线的参数.同时测量的谱线参数与HITRAN数据库相比,发现15条数据库上没有报道的弱谱线.     

基于单一量子级联激光器的大气多组分气体（CO、N2O、H2O）同时测量方法

近红外波段的气体吸收强度低,不利于痕量气体的测量。利用分子在中红外波段的基频吸收特性,使用单个新型室温连续输出量子级联激光器（CW-QCL）结合波长调制光谱技术（WMS）和长程光学吸收池,建立了一套高灵敏度和高精度的大气多组分温室气体同时检测的激光光谱系统。该系统的输出波数范围为2202.8～2205.6 cm^-1,覆盖了CO、N₂O和H₂O的中心吸收谱线。实验测试结果表明：在1 s的时间分辨率下,CO、N₂O和H₂O的测量精度分别为1.83×10^-8,1.86×10^-9,1.19×10^-4;当满足最佳积分时间（100 s）时,系统的最低检测限可以达到1.8×10^-9（CO）,0.16×10^-9（N₂O）,1.5×10^-5（H₂O）。通过长时间测量和分析可知,所提系统部件简单,使用方便,满足大气多组分气体...     

基于TDLAS-WMS的中红外痕量CH_4检测仪

为了对痕量甲烷(CH4)进行非接触式检测,采用可调谐二极管激光吸收光谱(TDLAS)与波长调制光谱(WMS)的检测技术,利用CH4位于中红外波段1 332.8cm-1吸收谱线,设计并研制出痕量CH4检测仪。该仪器使用中心波长为7.5μm的中红外量子级联激光器(QCL),通过调谐系数-0.2cm-1·A-1,采用固定工作温度调节其注入电流(0.6~1.6 A)的方式使其发光光谱扫描CH4气体吸收谱线(1 332.8cm-1)。在光学结构方面,该仪器采用光程为76m的herriott长光程密闭气体吸收气室,配合差分检测光路,降低了由激光光源波动引起的噪声,确保对痕量CH4进行检测。实验中,实现了40×10-9最低检测下限,检测结果的相对误差为0.09%,稳定度优于2.8%,验证了该仪器的可行性。     

高灵敏度离轴积分腔输出光谱技术

利用离轴积分腔输出光谱技术,采用同时扫描激光和谐振腔腔长的方法,使用分布反馈布拉格二极管激光器探测了1.573μm附近CO2的吸收光谱,得到很好的信噪比和灵敏度,探测灵敏度达到4×10-8cm-1(信噪比为2,1 s积分时间)。用非线性最小二乘拟合吸收谱线方法对积分腔输出光谱已经不再适用,会造成自加宽系数变宽为实际自加宽系数的2.39倍左右,对空气加宽系数测量影响较小。为了得到正确的谱线线宽参量,应该对吸收系数进行拟合,该结论从理论和实验上得到了证明。     

基于半导体激光的腔增强吸收光谱技术研究

用近红外可调谐分布反馈(DFB)半导体激光器作光源,用反射率为99.7%左右的平凹镜组成的稳定光学谐振腔作吸收池,建立了一套腔增强吸收光谱(CEAS)系统.根据系统工作时激光器与谐振腔的工作状态,将CEAS技术分为三类:控制波长法,控制腔长法及同时扫描波长和腔长法.以二氧化碳(CO2)和甲烷(CH4)为主要样品气体,用控制腔长法和控制波长法CEAS技术对CO2分子在1.573μm附近的吸收光谱做了测量;用扫描腔长和波长法CEAS技术对CH4气体在1.316μm附近的吸收光谱做了测量;考察了三种方法的探测灵敏度和在定量分析方面的能力.实验结果表明,CEAS技术是一种装置简单,操作方便,灵敏度高,稳定性好的定量吸收光谱技术,探测灵敏度达1.15×10-7cm-1.     

高灵敏度调谐式连续波腔衰荡光谱技术

建立了一套以分布反馈式(DFB)激光器为光源的高灵敏度连续波腔衰荡光谱测量系统,该系统利用DFB激光器的电流调谐特点使激光在衰荡腔内谐振,利用其电流调制的特点实现入射光的关断,进行衰荡测量.对标准具效应消除前后的系统进行了测试,结果表明,前后系统等噪声探测灵敏度分别为2.56×10-7cm"和1.27×10-8 cm-1.以衰荡腔的纵模间隔为扫描步长对6591.43 cm-1处N2O的氮气加宽线宽系数进行了测量,测量结果分别为0.0819 cm-1和0.0808 cm-1,对测量结果与HITRAN2004数据库中参数间的差别进行了讨论.     

History of spectroscopy and modern micromachined disposable Si ATR-IR spectroscopy

In this article, the historical development of spectroscopy is examined and the spectroscopy devices used today are described. Then, we focus on infrared (IR) spectroscopy, which cannot give valuable signal in aqueous solution. Attenuated total reflection (ATR)-IR technique solves the problem. In addition, we specifically mention newly developed disposable ATR-IR crystals and micromachined silicon (Si) ATR-IR. Disposable crystal systems and microfluidics systems can be integrated with existing miniature ATR analyzers. If the integration is successful, the technique might be used in biomedical measuring instruments, reactions' analyses, and ultra-high-pressure analyses.     

Synthesis,Structural and Optical Studies of Barium Strontium Titanate Borosilicate Glasses Doped with Ferric Oxide

Various barium strontium titanate borosilicate glasses were prepared by a rapid melt-quench technique. Spectroscopic studies have been carried out on investigated glasses for their structural information. Infrared and Raman spectroscopic studies showed that these glasses are formed by glass-forming network of borate and silicate as well as network modifiers in the form of cations of alkaline earth atoms. The borate and silicate networks are modified by barium, strontium, titanium, and iron cations in glass matrix. The network of triborate unit is modified in tetraborate unit by adding ferric oxide in a glassy matrix. The optical studies are performed by ultraviolet-visible spectroscopy and it confirms that the band gap decreases with increase in the concentration of ferric oxide.     

一种实现光声光谱的导数光谱的新方法

提出了一种实现光声光谱的导数光谱的新方法,为了获得光声光谱的导数光谱,利用一台单色仪和一个分光棱镜研制成一个波长-光强分束器,并用这个波长-光强分束器同时获得两束光强相等而波长有微小差别的两束光,这两束光经过一个互补调制器调制后在光声探测器内叠加,可以实现光声信号的差分,扫描单色仪的波长,就可以获得光声吸收光谱的导数光谱。实验证明这种方法可以准确实现光声光谱的一阶导数光谱,而且导数光声光谱比光声吸收光谱具有更高的光谱分辨率。     

激光长程吸收光谱法测量高分辨率大气吸收光谱

用脉冲可调谐光参量振荡器作光源 ,使用光程长达 1km的 8m长吸收池 ,采用分时复用的单探测器探测方法 ,组成测量系统 ,测量了一系列高分辨率的模拟和实际大气的吸收光谱。系统的灵敏度为 0 .5× 10 - 6cm- 1 ,分辨率为 0 .0 2cm- 1 。 1.315 μm附近实际大气的吸收光谱与HITRAN96模拟结果比较 ,强线符合得很好。水汽光谱的大多数强线的分子线强度相对误差在 10 %以下。     

Determination of Total Petroleum Hydrocarbon (TPH) and Polycyclic Aromatic Hydrocarbon (PAH) in Soils: A Review of Spectroscopic and Nonspectroscopic Techniques

Abstract: In the analysis of petroleum hydrocarbon–contaminated soils for total petroleum hydrocarbons (TPHs) and polycyclic aromatic hydrocarbons (PAHs), the roles of spectroscopic and nonspectroscopic techniques are inseparable. Therefore, spectroscopic techniques cannot be discussed in isolation. In this report, spectroscopic techniques including Raman, fluorescence, infrared, and visible and near-infrared (Vis-NIR) spectroscopies, as well as mass spectroscopy (coupled to a gas chromatograph) and nonspectroscopic techniques such as gravimetry, immunoassay, and gas chromatography with flame ionization detection are reviewed. To bridge the perceived gap in coverage of the quantitative applications of Vis-NIR spectroscopy in the rapid determination of TPHs and PAHs in soils, a detailed review of studies from the period 1999–2012 are presented. This report also highlights the strengths and limitations of these techniques and evaluates their performance from the perspective of their attributes of general applicability, namely economic portability, operational time, accuracy, and occupational health and safety considerations. Overall, the fluorescence spectroscopic technique had the best performance (85% total score) in comparison to the others, and the gravimetric technique performed the least (60% total score). Method-specific solutions geared toward performance improvement are also suggested.     

磁旋转腔增强光谱技术

为了提高吸收光谱的探测灵敏度,在弱吸收或短光程吸收的情况下实现高灵敏探测,将腔增强光谱技术与磁旋转光谱技术有效地结合起来,发展了高灵敏的磁旋转腔增强吸收光谱技术,并通过测量O2 的三重禁戒跃迁谱线验证了该技术的探测灵敏度。实验采用环型增强腔,以避免光束的返回对激光器的干扰。给出了腔的耦合匹配条件,以及镜面反射率、腔损耗对增强因子的影响;同时也给出了在实验中对光谱信号的处理方法。测量结果表明,在谐振腔精细度为F=48,腔内总损耗为13%,以及腔镜的耦合效率为 95%的情况下,对 O2 分子最小相对吸收度约为4.5×10-8(1 s积分时间)。     

Sub-Doppler and Doppler spectroscopy of DCN isotopomers in the terahertz region: ground and first excited bending states (v1v2v3)=(0 1 0)

The rotational spectra of the deuterium cyanide isotopic species DCN, D¹³CN, DC¹⁵N, and D¹³C¹⁵N were recorded in the vibrational ground and first excited bending state (v₂=1) up to 2 THz. The R-branch transitions from J=3←2 to J=13←12 were measured with sub-Doppler resolution. These very high resolution (∼70 kHz) and precise (±3-10 kHz) saturation dip measurements allowed for resolving the underlying hyperfine structure due to the ¹⁴N nucleus in DCN and D¹³CN for transitions as high as J=10←9. Additional high JR-branch (J=25←24 to J=28←27) transitions around 2 THz and direct l-type (ΔJ=0, J=19 to J=25) transitions from 66 to 118 GHz were recorded in Doppler-limited resolution. For the ground state of D¹³C¹⁵N, the J=1←0 transition was measured for the first time. The transition frequency accuracies for the other deuterated species were significantly improved. These new experimental data, together with the available infrared rovibrational data and previously measured direct l-type transitions, were subjected to a global least squares analysis for each isotopomer. This yielded precise sets of molecular constants for the ground and first excited vibrational states, including the nuclear quadrupole and magnetic spin-rotation coupling constants of the ¹⁴N nucleus for DCN and D¹³CN. The hyperfine structure due to the D, ¹³C, and ¹⁵N nuclei have not been resolved, but led to a broadening of the observed saturation dips.     

Millimeter wave measurement and assignment of the rotational spectrum of aniline

Previous work involving the rotational spectrum of aniline was limited to the lower frequencies of 8-40 GHz with very few lines being assigned. This work extends the earlier studies. Here we present a much more extensive measurement and assignment of the rotational spectrum of aniline in the frequency range of 75-110 GHz. The observed frequencies have been assigned to the ground (0⁺), first (0⁻), and second excited (1⁺) states in the inversion vibration. With the newly assigned lines, significantly improved rotational constants and all five centrifugal distortion constants have been obtained.     

Rotational spectroscopy of the first excited state of the acetylenic C-H stretch of 3-fluoropropyne performed by infrared-Fourier transform microwave-microwave triple-resonance spectroscopy

The rotational spectra of 3-fluoropropyne in the ground and first excited acetylenic C-H stretch vibrational state have been measured. The pure rotational spectrum of the normal species and the ¹³C isotopomers were measured using FTMW-cwMW double-resonance spectroscopy based on the Autler-Townes (AC Stark) effect. The lineshape properties of this measurement make it possible to determine the transition strength, ΔJ-selection rules, and the relative energy ordering of the quantum states. The frequency accuracy of this technique is tested against a previous pure rotational study of 3-fluoropropyne. The rotational spectrum of vibrationally excited state was obtained through IR-FTMW-cwMW methods. In this technique a single-longitudinal-mode pulsed infrared laser source vibrationally excites the acetylenic C-H stretch with J-selectivity. The rotational spectrum of the excited state is then obtained by FTMW and FTMW-cwMW double-resonance methods. The excited-state measurements have a signal-to-noise ratio comparable to the pure rotational spectrum. The residuals in the excited-state fit are larger than those obtained in the ground-state fit. This greater deviation from a standard asymmetric top spectrum is most likely due to weak perturbations to the acetylenic C-H spectrum.     

Millimeter and submillimeter wave rotational spectrum of pyridine in the ground and excited vibrational states

The pure rotational spectra of the ground and five excited vibrational states of pyridine were measured, assigned and fit in the 75-110 and 260-370 GHz frequency bands. An improved set of spectroscopic constants was obtained for the ground state, and all the rotational and quartic centrifugal distortion constants were obtained for the excited vibrational states.