基于差频中红外激光的痕量气体高分辨光谱检测研究

研究了基于差频光源的高分辨中红外激光光谱检测系统,差频中红外光源使用两台近红外半导体激光器作为种子光源,采用PPLN晶体作为非线性混频器件,结合准相位匹配技术实现了3.2～3.7μm中红外相干光源输出,最大差频输出功率约为1μW.以CH4为例检验了系统的高分辨红外光谱检测特性,选择CH4分子3028.751cm-1 v3基频吸收线作为分析谱线,10cm光程的检测限为0.8ppm.光谱数据分析表明,系统检测限主要受到标准具光学噪音的限制.     

甲胺水合离子团簇的结构模型及红外光谱研究

本文利用量子化学计算方法，研究了甲胺和水复合离子团簇[(CH₃NH₂)(H₂O)_n]⁺的几何结构、能量和红外光谱，揭示了结构生长模型、氢键作用机制和质子转移机理. 研究结果表明，在[(CH₃NH₂)(H₂O)_n]⁺团簇中，甲胺甲基上的一个氢原子转移到氨基上，形成分子内质子转移的CH₂NH₃⁺离子核心结构模型，水分子作为氢键受体，与质子化氨基NH₃⁺形成氢键. CH₃NH₂⁺离子核心结构模型没有CH₂NH₃⁺离子核心结构模型稳定. 在团簇的红外光谱中，CH振动、自由NH振动、氢键结合的NH振动和OH振动模式在CH₃NH₂⁺和CH₂NH₃⁺两种离子核心结构模型的理论计算红外光谱中明显不同，因此可用于鉴别甲胺水合离子团簇的结构模型，有助于理解甲胺和水复合团簇的氢键网络结构.     

聚酰胺6的红外光谱

根据对聚酰胺类高聚物红外光谱的类比和对聚酰胺6试样进行氘化和碘处理后红外光谱的改变,以及根据对拉伸过的聚酰胺6薄膜试样的偏振红外光谱的观察,我们对聚酰胺6红外光谱中400cm^-1—1400cm^-1之间的主要吸收带,作了如下解释:1370cm^-1吸收带为ν_(cщN);1265cm^-1和1205cm^-1吸收带为δ_N-H+ν_(cщN)(酰胺Ⅲ);1170cm^-1吸收带为ν_(cN);730cm^-1吸收带为γ_(CH2)[当(CH₂)_n的n≥4时];690cm^-1吸收带为δ_N-H(面外);580cm^-1吸收带亦为δ_N-H(面外)。     

Pd修饰Cu电极的电化学CO2还原

利用微分电化学质谱和电化学原位衰减全反射红外光谱技术探究了Cu和CuPd催化剂上CO₂和CO的电化学还原行为. 红外光谱观察到了生成甲醇、甲烷与乙烯的CH_x中间物种. 在CuPd电极CO₂还原过程中，红外光谱的CO吸附峰起始电位比Cu正移大约300 mV，说明CuPd能够有效促进CO₂还原；CO饱和溶液中，Cu和CuPd电极CO起始吸附电位基本相同；两电极上CO谱带出现的电位与CO₃^2-的谱带降低的电位基本相同，说明CO的吸附需要CO₃^2-的脱附. 利用电化学在线质谱发现在CuPd电极上CO还原产生CH₄和CH₃OH的起始电位比Cu电极正移约200 mV. 推测催化活性的提升可能是由于Pd的引入改变了Cu的d能带，且Pd吸附更多的H，从而促进CO₂还原，使CO能够与H结合并被深度还原.     

中心波长2.33 μm附近CO和CH4分子的同时探测

 采用分布反馈式半导体激光器作为探测光源,结合程长为100 m的离散型多通吸收池,采用直接吸收光谱技术,对室温下中心波长2.33 μm附近各种低体积分数的CO及混合气体（CO,CHCH₄和N₂）的直接吸收光谱进行了测量。选择CO在4 288.289 8 cm^-1位置的吸收谱线和CH₄在4 287.650 15 cm^-1处的吸收谱线进行痕量探测,在40 698 Pa的总压力下,实验测得CO的探测极限为8.15×10^-6(信噪比约为216）,CH4的探测极限为18.48×10^-6(信噪比约为147）。     

CH4-Ne体系的三维从头算势能面与光谱的模拟

本文在从头算CCSD(T)/AVXZ(X=T,Q)水平上计算了CH₄-Ne体系的三维势能面,同时在基组中加入了键函数,并且将基组外推到完全基组极限水平. 通过最小二乘法拟合摩斯长程势能函数形式,获得了三维分析势能面,其中对664个从头算格点的拟合的标准偏差仅为0.042 cm^-1. 随后,采用径向离散变量表象和角度有限基组表象相结合的杂化基函数方法,并基于Lanzcos迭代的方法获得了CH₄-Ne体系的振转能级,所预测的红外光谱与实验值非常吻合. 本文首次给出了CH₄-Ne体系的微波光谱数据. CH₄-Ne体系三维摩斯长程势能面分析的表达式为今后CH₄在Ne团簇动力学性质以及其碰撞诱导吸收光谱的研究中奠定了基础.     

二氧化钛薄膜表面甲醇吸附的和频振动光谱

自行搭建了用于研究表面光催化的宽带红外和频振动光谱并可以原位紫外光激发的装置. 利用自制的结构紧凑小巧的高真空样品池,可以在10 kPa氧气氛围下经原位紫外光照除掉 射频磁控溅射制备的二氧化钛薄膜表面的有机污染物. 通过在室温下改变甲醇气压和指认吸附在薄膜表面的甲醇的和频振动光谱,发现薄膜表面有两种吸附的甲醇,分子形式吸附的甲醇(CH₃OH)和解离吸附的甲醇(CH₃O). 当甲醇的覆盖度由低变高时,分子形式吸附的甲醇的CH₃的对称伸缩振动和费米共振峰红移了6～8 cm^-1. 真空下,薄膜表面的甲氧基和表面的氢原子可以重新结合并以甲醇分子的形式脱附. 研究表明二氧化钛薄膜体系存在两个平衡：气相甲醇和表面吸附的甲醇分子之间,以及表面吸附的甲醇分子和甲氧基之间.     

CH3OH在ZnO(0001)表面的光催化解离

本文利用266 nm波长的激光及程序升温脱附的方法研究了甲醇在ZnO(0001)表面的光催化反应. TPD结果显示部分的CH₃OH以分子的形式吸附在ZnO(0001)表面,而另外一部分在表面发生了解离. 实验过程中探测到H₂,CH₃^·,H₂O,CO,CH₂O,CO₂和CH₃OH这些热反应产物. 紫外激光照射实验结果表明光照可以促进CH₃OH/CH₃O^·解离形成CH₂O,在程序升温或光照的过程中它又可以转变为HCOO^-. CH₂OH_Zn与OH_ad反应在Zn位点上形成H₂O分子. 升温或光照都能促进CH₃O^·转变为CH₃^·. 该研究对CH₃OH在ZnO(0001)表面的光催化反应机理提供了一个新的见解.     

光纤浓度传感器的实验研究

本文报道了采用光谱吸收法测量气体吸度的光纤传感器系统。在该系统中,可调谐的激光二极管作光源,几何长度0.8832m的怀特池作为吸收池。对CH₄气体的测量灵敏度达3.7×10^-9,还介绍了达到这一探测灵敏度的信号调制与探测技术,理论上对该系统的最小可探测压强作了估算。     

掺铒硫系玻璃的制备及其微结构光纤的中红外信号放大特性研究

为进一步揭示硫系玻璃基掺Er³⁺微结构光纤对于中红外波段信号的放大特性, 采用熔融淬火法研制了Er³⁺离子掺杂的Ga₅Ge₂₀Sb₁₀S₆₅硫系玻璃, 测试了玻璃样品的吸收光谱和2.7 μm波段荧光光谱, 利用Judd-Ofelt和Futchbauer-Ladenburg理论分别计算得到了Er³⁺离子的辐射跃迁概率、辐射寿命以及2.7 μm波段受激发射截面. 在此基础上, 建立了一个980 nm抽运下该玻璃基掺Er³⁺微结构光纤2.7 μm波段中红外信号的放大模型, 理论上研究了其作为2.7 μm波段中红外信号增益介质时的光放大特性. 结果显示, 硫系玻璃基掺Er³⁺微结构光纤具有优异的高增益和宽带放大品性. 在200 mW抽运功率激励下的100 cm光纤长度上, 最大小信号增益超过了40 dB, 高于30 dB信号增益的放大带宽达到了120 nm (2696—2816 nm). 研究表明, Ga₅Ge₂₀Sb₁₀S₆₅硫系玻璃基掺Er³⁺微结构光纤是一种理想的可应用于2.7 μm波段中红外宽带放大器的增益介质.     

Mid-infrared virtually imaged phased array spectrometer for rapid and broadband trace gas detection

We present and characterize a two-dimensional (2D) imaging spectrometer based on a virtually imaged phased array (VIPA) disperser for rapid, high-resolution molecular detection using mid-infrared (MIR) frequency combs at 3.1 and 3.8?μm. We demonstrate detection of CH₄ at 3.1?μm with >3750 resolution elements spanning >80 nm with ～600 MHz resolution in a <10 μs acquisition time. In addition to broadband detection, we also demonstrate rapid, time-resolved single-image detection by capturing dynamic concentration changes of CH₄ at a rate of ～375 frames per second. Changes in absorption above the noise floor of 5×10^-4 are readily detected on the millisecond time scale, leading to important future applications such as real-time monitoring of trace gas concentrations and detection of reactive intermediates.     

Doppler-limited spectra of the ν3 vibration of 12CH4 and 13CH4

The tetrahedral splittings in the P and R branches of the ν₃ band of natural methane have been examined with Doppler-limited resolution using a difference-frequency spectrometer. The spectra obtained by this difference-frequency mixer are compared to recent high-resolution grating spectrometer studies of ¹²CH₄ and enriched ¹³CH₄. The resolution, selectivity and precision are improved over the conventional methods. The mixing spectrometer utilizes tunable, narrow linewidth infrared radiation generated in the nonlinear optical crystal, LiNbO₃ as the beat frequency between a CW argon ion and a tunable dye laser. This spectrometer covers the 2.2 to 4.2 μm infrared spectrum with an instrumental resolution of 5 × 10^?4 cm^?1 and continuous scans up to ～1 cm^?1 and with ir power ～1 μW.     

A trace methane gas sensor using mid-infrared quantum cascaded laser at 7.5 μm

Presented is a compact instrument developed for in situ high-stable and sensitive continuous measurement of trace gases in air, with results shown for ambient methane (CH₄) concentration. This instrument takes advantage of recent technology in thermoelectrically cooled pulsed Fabry–Perot (FP) quantum cascaded (QC) laser driving in a pulse mode operating at 7.5 μm to monitor a well-isolated spectral line near the ν4 fundamental band of CH₄. A high-quality liquid nitrogen cooled mercury cadmium telluride mid-infrared detector with time discriminating electronics is used along with a total reflection coated gold ellipsoid mirror offering 20 cm single pass optical absorption in an open-path cell to achieve stability of 5.2 × 10^?3 under experimental condition of 200 ppm measured ambient CH₄. The instrument operates continuously, and integrated software for laser control using direct absorption provides quantitative trace gas measurements without calibration. One may substitute a QC laser operating at a different wavelength to measure other gases. The instrument can be applied to field measurements of gases of environmental concern.     

Application of a characterized difference-frequency laser source to carbon monoxide trace detection

A tunable continuous wave(cw) mid-infrared(MIR) laser based on difference-frequency generation(DFG) in a 1.5-cm long AgGaS2 nonlinear crystal for trace gas detection is reported.Two visible and near-infrared diode lasers were used as pump and signal sources.The MIR-DFG laser was tunable in a wavelength range of 4.75 μm-4.88 μm.The phase-matching(PM) condition was non-critically achieved by adjusting the temperature of the crystal for fixed pairs of input pump and signal wavelengths.The required PM temperatures of the generated MIR-DFG wavelengths have been calculated by using three sets of recent Sellmeier equations and the temperature-dispersion equations of AgGaS2 given by Willer U,et al.(Willer U,Blanke T and Schade W 2001 Appl.Opt.40 5439).Then the calculated PM temperatures are compared with the experimental values.The performance of the MIR-DFG laser is shown by the trace detection of the P(16) carbon monoxide(12C16O) absorption line in a laboratory-fabricated absorption cell.The enhanced sensitivity of about 0.6×10 4 was obtained through the long path absorption provided by consecutive reflections between coated cylindrical mirrors of a constructed cell.     

Generation of broadly tunable picosecond mid-infrared laser and sensitive detection of a mid-infrared signal by parametric frequency up-conversion in MgO:LiNbO3 optical parametric amplifiers

Picosecond optical parametric generation and amplification in the near-infrared region within 1.361-1.656 μm and the mid-infrared region within 2.976-4.875 μm is constructed on the basis of bulk MgO：LiNbO 3 crystals pumped at 1.064 μm.The maximum pulse energy reaches 1.3 mJ at 1.464 μm and 0.47 mJ at 3.894 μm,corresponding to a pumpto-idler photon conversion efficiency of 25%.By seeding the hard-to-measure mid-infrared radiation as the idler in the optical parametric amplification and measuring the amplified and frequency up-converted signal in the near-infrared or even visible region,one can measure very week mid-infrared radiation with ordinary detectors,which are insensitive to mid-infrared radiation,with a very high gain.A maximum gain factor of about 7 脳 10 7 is achieved at the mid-infrared wavelength of 3.374 μm and the corresponding energy detection limit is as low as about 390 aJ per pulse.     

On-line monitoring of cyclotron target-gas output by means of tunable lead salt diode laser absorption spectroscopy

We demonstrate what is, to our knowledge, the first use of mid-infrared laser absorption spectroscopy for trace-gas measurements of cyclotron target outputs used for the generation of radioactive carbon-11 in positron emission tomography (PET). The spectrometer was based upon a liquid-nitrogen-cooled lead salt diode laser generating single-mode radiation in the wavenumber range of 2230–2240 cm^?1. The sample flowed to a multiple-pass optical cell with a total path length of 15.23 m and the laser radiation was detected by two liquid-nitrogen-cooled InSb photodetectors. We present the results of CO, N₂O and CO₂ measurements on PET trace cyclotron output and discuss future work on ¹¹CO and ¹¹CO₂ detection.     

Mid-infrared trace gas detection using continuous-wave difference frequency generation in periodically poled RbTiOAsO4

A tunable mid-infrared continuous-wave (cw) spectroscopic source in the 3.4–4.5 μm region is reported, based on difference frequency generation (DFG) in a quasi-phase-matched periodically poled RbTiOAsO₄ (PPRTA) crystal, DFG power levels of 10 μW were generated at approximately 4 μm in a 20-mm long PPRTA crystal by mixing two cw single-frequency Ti:Al₂O₃ lasers operating near 713 nm and 871 nm, respectively, using a laser pump power of 300 mW. A quasi-phase-matched infrared wavelength-tuning bandwidth (FWHM) of ∼12 cm^-1 and a temperature tuning rate of 1.02 cm^-1/°C were achieved. Experimental details regarding the feasibility of trace gas detection based on absorption spectroscopy of CO₂ in ambient air using this DFG radiation source are also described. Received: 23 October 2000 / Revised version: 22 January 2001 / Published online: 27 April 2001     

Cavity-enhanced optical frequency comb spectroscopy in the mid-infrared application to trace detection of hydrogen peroxide

We demonstrate the first cavity-enhanced optical frequency comb spectroscopy in the mid-infrared wavelength region and report the sensitive real-time trace detection of hydrogen peroxide in the presence of a large amount of water. The experimental apparatus is based on a mid-infrared optical parametric oscillator synchronously pumped by a high-power Yb:fiber laser, a high-finesse broadband cavity, and a fast-scanning Fourier transform spectrometer with autobalancing detection. The comb spectrum with a bandwidth of 200 nm centered around 3.76 μm is simultaneously coupled to the cavity and both degrees of freedom of the comb, i.e. the repetition rate and carrier envelope offset frequency, are locked to the cavity to ensure stable transmission. The autobalancing detection scheme reduces the intensity noise by a factor of 300, and a sensitivity of 5.4×10^?9 cm^?1?Hz^?1/2 with a resolution of 800 MHz is achieved (corresponding to 6.9×10^?11 cm^?1?Hz^?1/2 per spectral element for 6000 resolved elements). This yields a noise equivalent detection limit for hydrogen peroxide of 8 parts-per-billion (ppb); in the presence of 2.8 % of water the detection limit is 130 ppb. Spectra of acetylene, methane, and nitrous oxide at atmospheric pressure are also presented, and a line-shape model is developed to simulate the experimental data.     

Apodized 2f/1f wavelength modulation spectroscopy method for calibration-free trace detection of carbon monoxide in the near-infrared region: theory and experiment

We introduce the basics of an apodized 2f/1f wavelength modulation method for the spectroscopy of the R(9) transition line in the first overtone band of carbon monoxide (¹²C¹⁶O) in near-infrared (NIR) region around 2.33 μm. Performance of the method is investigated for high gas concentrations beyond the optically thin limit to generalize common 2f/1f wavelength modulation spectroscopy (WMS) reported by Rieker et al. (Appl Opt 48:5546, [28]). Numerical simulations are performed based on real experimental parameters associated with a NIR spectrometer designed in our laboratory. The results primarily show a more linear response and less error than occurred in the common WMS-2f/1f method for an optically thick sample. It is also theoretically shown that the apodized method enables sharpening the spectrum without peak displacement compared to the common WMS-2f/1f method. The validity of the method is verified experimentally by the trace detection of an air-broadened R(9) CO absorption line centered at 4,294.637 cm^?1 at atmospheric pressure and room temperature. The effect of a so-called scaling k-factor on the sharpening of WMS-2f/1f signal is investigated through trace simulation and detection of CO and methane (CH₄) lines in the scanning range of a distributed feedback laser. The obtained results show very good agreement between simulation and experiment.