Argon broadening of the CO R(0) and R(7) transitions in the fundamental band at temperatures between 80 and 297 K: comparison between experiment and theory

We present measurements of Ar-broadening parameters for the R(0) and R(7) lines in the fundamental band of ¹³CO at eight temperatures from 80 to 297 K. The broadening parameters are determined by simultaneous least-squares fitting of spectra recorded using a frequency stabilized diode laser spectrometer. The comparison of the broadening parameter values for R(7) derived at room temperature and different pressures from different line profiles shows that an empirical line profile, which takes into account narrowing effects (Dicke narrowing and absorber speed dependence) but neglects any correlation between collisions, is able to describe the observed lines with constant values of the narrowing and broadening parameters over a 10-500 Torr pressure range. Starting from a recent ab initio potential energy surface, theoretical thermally averaged close coupling values of the Ar broadening parameter are calculated for the same temperatures. The comparison between experimental and calculated values shows an overall agreement of 1.5%.     

基于TDLAS平衡差分技术的CO气体检测

利用可调谐半导体激光吸收光谱(TDLAS)结合平衡差分探测技术测量了1.578 μm附近的CO气体3-0带P(4)跃迁在不同压强和不同浓度下的吸收光谱信号。由于平衡差分探测方法可以有效地抑制激光光强波动、温度漂移和机械振动等共模噪声,从而提高了光谱探测灵敏度。通过与直接吸收信号相比,平衡差分的信噪比提高了3.4倍,探测极限为87 ppmv。测量了浓度为1%压强为40,55,70和85 Torr时的CO气体,结果显示在70 Torr时其光谱信号最强。并且,利用直接吸收和平衡差分技术测量了不同浓度的CO气体在总压强在70 Torr时的光谱信号,发现平衡差分技术光谱强度与浓度的关系线性度符合较好,其测量误差小于5%。为了进一步验证系统的稳定性,连续采集了324 s的光谱信号,最后通过Allan方差分析,发现本实验系统的最佳探测时间为38 s,探测极限为47.8 ppmv。     

The high-resolution, jet-cooled infrared spectrum of pentafluoroethane

The jet-cooled spectrum of pentafluoroethane (C₂HF₅) has been recorded between 1100 and 1325 cm⁻¹ at a resolution of 0.0022 cm⁻¹. A rotational temperature of approximately 10 K was achieved by expanding 50 Torr of C₂HF₅ in 500 Torr of helium. Transitions belonging to five different fundamental vibrations have been assigned and fit to a Watson Hamiltonian: the ν₃ band at 1309.880494(189) cm⁻¹, ν₄ at 1200.734645(67) cm⁻¹, ν₅ at 1142.78147(33) cm⁻¹, ν₁₃ at 1223.334098(115) cm⁻¹, and ν₁₄ at 1147.394185(163) cm⁻¹. The fit of the ν₄ band has an rms deviation of 0.000436 cm⁻¹ compared to the uncertainty in the experimental line position of 0.0002 cm⁻¹. Satisfactory fits were achieved for the other four bands (ν₃, ν₅, ν₁₃, ν₁₄) at this cold temperature, with most of the centrifugal distortion constants fixed at the ground state values. Joint fits with previous work were attempted for the ν₄ and ν₁₃, successfully in the former case and unsuccessfully in the latter.     

Resonance absorption of coherent infrared radiation by thin polypropylene films and its technological applications

Tunable CO₂ and non-tunable CO₂ lasers were used for the irradiation of thin polypropylene films. The wavelength of the IR radiation was adjusted in such a way that it coincided exactly with the absorbance peak in the spectrum of the polypropylene pattern. In this way, conditions of resonance absorption of IR radiation by polymer films were produced. Strong thermal effects in PP were observed under irradiation at the resonance wavelength. The threshold value of IR power, which causes thermal phenomena in irradiated films was established. We pulled films exposed to established threshold values with a constant speed in the plane normal to the laser beam. Highly developed relief and thin traces were formed depending on the pulling speed. Traces with a width smaller than the wavelength of the incident laser beam were obtained. The IR spectra of irradiated PP films were studied with a FTIR spectrometer. Changes in the spectra of PP films were established using correlation analysis of spectral data. The phenomenon could be applied for obtaining highly developed surface relief, storage of information in polymer films and welding of polymer materials.     

The ACE-FTS atlas of the infrared solar spectrum

The ACE-FTS is a space-borne Fourier transform spectrometer onboard SCISAT-1. The satellite was launched in August 2003 and since February 2004 the ACE-FTS has been performing solar occultation measurements in order to infer the chemical composition of the terrestrial atmosphere. The individual spectra recorded at the highest limb tangent altitudes (above 160 km) are by definition “high sun” spectra and contain no atmospheric contribution. In this work, an empirical solar spectrum covering the 700 to 4430 cm⁻¹ spectral range has been constructed from an average of 224,782 individual ACE-FTS solar spectra. Line assignments have been made for about 12,000 lines. The spectrum and two line lists are provided in the supplemental material attached to this work. Due to the excellent noise level achieved in the ACE-FTS solar atlas presented here, numerous weak absorption features are assigned which were not detectable in the ATMOS solar observations.     

Millimeter-wave spectrum of Ne–CO: new measurements

The b-type rotational transitions of the van der Waals complex, Ne–CO have been measured using the intracavity OROTRON jet spectrometer in the frequency range of 80–115 GHz. The high sensitivity of this technique enabled us to detect all three Ne isotopic modifications of the complex, ²⁰Ne–CO, ²²Ne–CO, and ²¹Ne–CO in natural abundance. The observed and assigned transitions belong to the Q-branch of the K = 1–0 subband and include also R (0) and P (2) lines. The newly obtained data were analysed together with previously observed millimeter-wave b-type and microwave a-type rotational transitions.     

The molecular symmetry group of the CO dimer and the assignments of the intermolecular vibrations

Vibrational assignments for some of the lowest energy levels of the CO dimer have been derived purely spectroscopically on the basis of the molecular symmetry, nuclear spin statistics, observed selection rules, and sequence of the transition doublets. Most of the previous assignments of Surin et al. [L.A. Surin, D.N. Fourzikov, T.F. Giesen, S. Schlemmer, G. Winnewisser, V.A. Panfilov, B.S. Dumesh, G.W.M. Vissers, A. van der Avoird, J. Phys. Chem. A 111 (2007) 12238-12247] are confirmed in the present work, and are supported by much clear evidences. One significant revision of that analysis in the present work is identification of the torsional (out-of-plane) excited state, which had been assigned previously to an excited state of the geared (in plane) internal rotation.     

1．3μm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.     

N2-broadening coefficients in the ν4 band of CH4 at room temperature

Using a diode laser spectrometer, we have studied with a great accuracy the N₂-broadening coefficients in the ν₄ band of methane. The experiments were performed at room temperature for lines in the P- and R-branches. We have measured 39 lines in the spectral range 1237–1373 cm⁻¹ with J values between 1 and 12. Each line under study was recorded at four different nitrogen pressures, ranging from 20 to 91 mbar. The collisional half-widths were obtained by fitting individually a theoretical profile on the experimental profile of each line at each N₂-pressure. We fitted the usual Voigt profile, but also the Rautian and Galatry lineshape models which take into account the collisional narrowing due to the molecular confinement (Dicke effect). The Rautian and Galatry fits are always better adjusted on the experimental profiles. For some lines, when the overlapping could not be disregarded, a fit of the blended profiles was performed using the same lineshape models. The collisional broadening coefficients obtained with Galatry and Rautian models are nearly equal and always higher than those derived from Voigt profile. Finally, we compare our results with previous determinations realized for several absorption bands.     

基于可调谐激光二极管吸收光谱的乙炔在线检测系统

基于可调谐半导体激光吸收光谱技术,研制了一种近红外乙炔气体检测系统。通过分析近红外波段乙炔分子的吸收谱线特性,选择了1.534 μm附近乙炔分子的吸收峰作为吸收谱线。该系统主要由分布反馈激光器、激光器驱动器、单光程对射式气室、光电探测模块及数字式锁相放大器构成。为了测试该检测系统的性能,配备了乙炔气体样品并开展了气体检测实验。实验结果显示,该系统的最小检测下限为0.02%;在体积分数为0.02%～1%范围内,二次谐波幅值与乙炔气体浓度呈现出良好的线性关系。通过长达20 h的稳定性实验测试了检测系统稳定性。鉴于近红外波段石英光纤传输损耗很小,可以将气室及光路部分与电路部分分离,从而可以进行远程气体检测,这是基于量子级联激光器、热光源的乙炔检测系统难以实现的。该系统采用了自主研制的分布反馈激光器驱动器和锁相放大器,结构简单,性价比高,便与集成,在工业现场乙炔浓度检测方面有着良好的应用前景。     

半导体激光器发射光谱实验仪

设计了一种半导体激光器发射光谱实验仪 ,可以用来观测LD发射的荧光光谱、激光光谱 ,以及了解光栅外腔选取单纵模、压窄线宽、波长调谐的机理 .该实验仪结构紧凑 ,物理概念清晰 ,适用于大专院校的光学实验教学     

Diode laser spectroscopy of the ν7a band of fluorobenzene

The diode laser absorption infrared spectrum of fluorobenzene has been recorded near 1230 cm⁻¹ after cooling the molecules in a supersonic pulsed jet. Spectral lines have been assigned to the ν_7a fundamental band. Transitions of J between 32 and 49 have been recorded, that show characteristic line groupings in the P branch. Analysis of the spectrum gives the vibrational band origin and rotational and centrifugal distortion constants of the molecule in the ν_7a = 1 state.     

红外成像光谱测量中Dyson光学系统的研究进展

传统的红外成像光谱仪难以同时实现弱遥感信号下的高信噪比和仪器小型化的要求,基于Dyson同心光学结构的新型遥感红外成像光谱仪具有数值孔径大、信噪比高、结构简单、体积小、重量轻的优点,用于强背景信号下的微弱红外成像光谱信号测量时,可实现传统的红外成像光谱仪难以实现的高信噪比测量。本文概述了Dyson同心光学结构的产生、发展及最新研究动态,重点介绍了Dyson同心光谱仪的原理、研制过程中的难点以及在高性能遥感红外成像光谱测量中的应用,为高性能红外成像光谱仪的研究提供了参考。     

Diode laser jet spectra and analysis of the ν14 fundamental of 1,1,1,2-tetrafluoroethane (HFC-134a)

High resolution infrared spectra have been measured for mixtures of 1,1,1,2-tetrafluoroethane in Ne, expanded in a supersonic planar jet. The ν₁₄ fundamental is an essentially unperturbed C-type band, exhibiting many ΔK_c=±2 transitions. Accurate excited state rotational and distortion constants have been determined from an analysis of about 1250 transitions, by using Watson’s Hamiltonian in the S-reduction. A local perturbation has been observed with a crossing at K^′_a=11 for J^′ values between 17 and 18, and could be accounted for by a x-Coriolis interaction with a perturbing vibrational level of A^′ symmetry at about 1205.53(1) cm⁻¹. Due to the very efficient cooling in the jet, the rotational temperature resulted to be about 20 K, and no evidence of hot-band absorption was found.     

Isotope effects in the infrared spectra of the polar and nonpolar isomers of N2O dimer

The rotationally resolved spectra of ¹⁵N¹⁵N¹⁶O dimer for the polar and nonpolar isomers are studied in the region of the N-N stretching fundamental of the monomer (∼2150 cm⁻¹) using a rapid-scan tunable diode laser spectrometer to probe a pulsed supersonic jet expansion. These spectra are very similar to the corresponding spectra of the normal species, (¹⁴N¹⁴N¹⁶O)₂. Structural parameters and vibrational shifts obtained here are compared with those of the normal species and ab initio values. These results confirm that the nonpolar isomer has a centrosymmetric slipped-antiparallel structure while the polar isomer consists of two slipped and (approximately) parallel monomer units.     

The millimeter wave spectrum of the CO dimer

The millimeter wave spectrum of the isotopically substituted CO dimer, (¹³C¹⁶O)₂, has been studied for the first time, confirming and extending a recent infrared study. Eighty-seven transitions in the 77-180 GHz region have been assigned and analyzed in terms of a model-independent term value scheme involving 57 rotational levels with J=0-8. The levels can be classified into 7 “stacks” which have symmetry classifications of either A⁻/B⁺ or A⁺/B⁻ and K-values of either 0 or 1. For the normal isotope, symmetry and nuclear spin statistics cause alternate rotational levels to be missing, but for (¹³C¹⁶O)₂ all levels are present with an intensity alternation of 1:3 between A and B symmetries. The four A⁻/B⁺ stacks have not previously been observed, and the lowest of them establishes the tunneling splitting of (¹³C¹⁶O)₂ to be 3.769 cm⁻¹, slightly larger than the (¹²C¹⁶O)₂ value of 3.731 cm⁻¹. A large amount of precise experimental data is now available for the CO dimer, which should lead to greater theoretical insight into its structure and tunneling dynamics.     

可调谐半导体激光吸收光谱法监测燃烧过程中CO浓度的变化

可调谐半导体激光吸收光谱技术(tunable diode laser absorption spectroscopy, TDLAS)是利用二极管激光器的波长调谐特性,获得被选定的待测气体特征吸收线的吸收光谱,从而对待测气体进行定性或定量分析。它具有高灵敏、高分辨以及快速检测等特点,已经广泛用于大气中多种痕量气体的检测以及泄漏气体的检测,也是在燃烧环境下对气体进行非侵入式实时测量的理想方法。TDLAS技术与开放式的多次反射池相结合,并利用自平衡探测加波长调制的新型检测方法,测量了酒精喷灯燃烧过程中产生的CO浓度,从测量结果中发现酒精喷灯火焰中CO的浓度成一定的周期性,并且得到火焰中CO的平均浓度为49.4(10-6体积比)。实验结果表明利用开放式多次反射池,结合自平衡探测加波长调制探测的新方法,满足了酒精喷灯燃烧过程中CO检测的需要,此系统为发展基于TDLAS的燃烧在线诊断技术奠定了基础。     

One-colour resonant two-photon ionization spectrum of the 1-fluoronaphthalene dimer and ab initio calculation

The one-colour resonant two-photon ionization(R2PI) spectrum of the 1-fluoronaphthalene(1FN) dimer has been studied in the wavelength range of 304 to 322 nm by using a supersonic molecular beam and time-of-flight mass spectrometry.Compared with the original band 00(at 313.8 nm) of the S1 ← S0 transition of the 1FN monomer,a red-shifted band was observed in the 1FN dimer spectrum at about 315 nm with a relatively large linewidth,nearly 2 nm.Based on the consideration of inductive effect and ab initio calculations,this red-shifted band is assigned to the first electronic excited transition of the 1FN dimer.A possible geometric structure of the 1FN dimer is also obtained with calculations that the two 1FN molecules are combined through two hydrogen bonds which are formed between the hydrogen atom of a molecule and the fluorine atom of a neighbouring molecule.A time-dependent calculation was also carried out and the results are consistent with the experimental data.     

CO oxidation on Pd(1 1 1), Pt(1 1 1), and Rh(1 1 1) surfaces studied by infrared chemiluminescence spectroscopy

The infrared (IR) chemiluminescence studies of CO₂ formed during steady-state CO oxidation over Pd(1 1 1), Pt(1 1 1), and Rh(1 1 1) surfaces were carried out. Analysis of their emission spectra indicates that the order of the average vibrational temperature () values of CO₂ formed during CO oxidation was as follows: Pd(1 1 1) > Pt(1 1 1) > Rh(1 1 1), and the order is coincident with the potential energy in the transition state expected by the theoretical calculations. Furthermore, it is suggested that the bending vibrational temperature () can also be influenced by the angle of O-C-O (∠_OCO) of the activated complex in the transition state, which has also been proposed by the theoretical calculations.     

中、远红外双波段激光器发射光谱测量与评估

在分析中远红外双波段(氟化氘与一氧化碳)激光器发射光谱的基本特征和分光型谱仪存在高级次光谱混叠等问题的基础上,选定Tensor37干涉型遥测光谱仪并利用黑体标定出仪器响应函数;对中、远红外双波段激光器光谱进行了模拟测量和实际测量,分析评估了双波段激光器的谱线成分、峰值变化、测量精度和相对强度等,为双波段激光器的介质参数计算、运转参数优化以及红外应用提供有效数据。