A rapid,spatially dispersive frequency comb spectrograph aimed at gas phase chemical reaction kinetics

This New Views article will highlight some recent advances in high sensitivity gas detection using direct infrared absorption frequency comb laser spectroscopy, with a focus on frequency comb use in chemical reaction kinetics and our own contribution to this field. Our recently implemented detection technique uses a combination of a 12.9?GHz free spectral range virtually imaged phased array and diffraction grating to spatially disperse the mid-infrared frequency comb onto a camera. Individual frequencies or ‘comb teeth’ of a 250?MHz repetition-rate frequency comb are able to be resolved. High molecular sensitivity is achieved by increasing the interaction path length using a Herriott multipass cell. High spectral resolution, broadband spectral coverage, and high molecular sensitivity are all achieved on an adjustable 1–50 µs timescale, making this frequency comb apparatus ideal for measuring chemical reaction kinetics where multiple absorbing species can be monitored simultaneously. This New Views article will also discuss some of the challenges and decisions that chemists might face in implementing this advanced physics technology in their own laboratory.

Spatially dispersed 250 MHz mid-infrared frequency comb laser, with absorption of some frequencies by a dilute sample of methane.     

红外扫描和频振动光谱系统的激光线宽与光谱分辨率

本文报道了一个简化的利用可见光和红外光带宽来计算和频光谱分辨率的公式. 公式显示和频振动光谱的Voigt线宽可以通过振动模式的均匀线宽(洛伦兹线宽)、非均匀线宽(高斯线宽)、红外光与可见光的高斯线宽计算获得. 利用本实验室新搭建的频率分辨及偏振分辨的皮秒和频光谱系统验证了该公式的准确性. 实验结果显示,本激光系统获取的红外光的高斯线宽为1.5 cm^-1. 本激光系统的光谱分辨率约为4.6 cm^-1,结果与胆固醇单层膜光谱获取的光谱分辨率(3.5~5 cm^-1)基本一致.     

差频可调谐太赫兹技术的新进展

太赫兹技术在最近30年来得到快速发展, 并在医学、生物、农业、材料、安检、通信、天文等领域得到广泛应用. 从太赫兹源的频谱特性可以分为窄带(单频)太赫兹源和宽带太赫兹源. 从频谱技术方面来说, 相干的宽带和窄带太赫兹谱是一种互补性关系, 具有各自的技术特点和应用范围. 宽带太赫兹谱可以用于快速获取较宽频谱范围的分子振转谱, 实现混合特征谱的快速检测或成像. 窄带太赫兹源具有很好的光谱灵敏度和分辨率, 适用于太赫兹抽运-探测、分子振转能级谱精细结构分辨 以及太赫兹远程探测和成像. 因此研制具有可调谐的高峰值功率的窄带太赫兹源是适用于探测和识别分子振转能级指纹谱的应用需求, 而差频技术是获得高功率和宽调谐窄带太赫兹源最重要的技术之一. 为了突出该技术的最新进展, 本综述引证论文仅仅限于近5 年来基于差频技术产生太赫兹波的研究进展, 分为光学激光差频源和量子级联激光器差频源两大部分. 对于光学激光差频源, 分别对目前文献报道的各种双波长差频源和太赫兹产生用的非线性晶体进行分类介绍, 并给出所采用的技术和实验结果; 对于量子级联激光器差频源, 分别介绍了量子级联激光器中的差频产生技术和波长调谐技术的最新进展. 量子级联激光器差频太赫兹源是目前实现量子级联激光器在太赫兹波段室温运转的惟一技术, 是实现小型化、窄带宽调谐和室温运转太赫兹源的新发展领域, 值得关注.     

Laser systems specialized for laser spectroscopy at storage rings

Laser spectroscopy at storage rings often suffers from a limited resolution due to Doppler-broadened resonances. Broadening is caused by the velocity spread of the ions stored in the beam. In the following, the present status of our work on laser systems specialized on the specific needs of laser spectroscopy at storage rings is reported. Two pulsed laser systems were developed. One is a dye laser whose spectral bandwidth can be switched by inserting different Littrow-prisms into the resonator. An increase in bandwidth up to a factor of 45 was achieved. This laser was used for fast qualitative scans and high resolution measurements. The other laser system is a Nd : YAG laser pumped optical parametric oscillator. It is a tunable laser system covering the spectral range from 410 to 4000 nm. Furthermore, a continuous wave laser with a frequency shifted feedback cavity is described. It shows broadband emission with an adjustable bandwidth of up to 4.5 GHz. This laser can be advantageous for laser cooling of ion beams. This revised version was published online in August 2006 with corrections to the Cover Date.     

光频链接的双光梳气体吸收光谱测量

双光梳光谱技术以其无运动部件快速采样、高分辨率探测等优势成为宽带激光光谱测量中的热点技术.但受限于常用微波锁定双光梳光源间的噪声特性,双光梳光谱技术仍难以发挥其探测潜能.本文报道一种光频域互相链接的双光梳光谱探测方案.通过将两台激光器的偏置频率同时锁定到一个窄线宽激光器上,既免去了结构复杂且成本高昂的非线性自参考系统,又将双光梳间的共同参考点设置到了光频范围,抑制了双光梳光谱采样抖动,实现光谱探测性能的提升.~(13)C_2H_2的ν_1+ν_3 P支光谱数据测量数据分析结果表明:谱线位置与文献结果符合良好,光谱分辨率为0.086 cm~(-1),信噪比200:1(62.5 ms,100幅平均),相应的秒均噪声等效吸收系数达6.0×10~(-6)cm~(-1)·Hz~(-1/2).该工作为双光梳光谱测量的实际应用提供了一种高精度、低成本、易于实现的解决方案.     

Laser intracavity absorption spectroscopy

Emission spectra of multimode lasers are very sensitive to spectrally selective extinction in their cavity. This phenomenon allows the quantitative measurement of absorption. The sensitivity of measurements of intracavity absorption grows with the laser pulse duration. The ultimate sensitivity obtained with a cw laser is set by various perturbations of the light coherence, such as quantum noise, Rayleigh scattering, four-wave mixing by population pulsations, and stimulated Brillouin scattering. It depends on the particular laser type used, and on its operative parameters, for example pump power, cavity loss, cavity length, and length of the gain medium. Nonlinear mode-coupling dominates the dynamics of lasers that feature a thin gain medium, such as dye lasers, whereas Rayleigh scattering is more important in lasers with a long gain medium, such as doped fibre lasers, or the Ti:sapphire laser. The highest sensitivity so far has been obtained with a cw dye laser. It corresponds to 70000 km effective length of the absorption path. The ultimate spectral resolution is determined by the spectral width of mode emission, which is 0.7 Hz in this dye laser. High sensitivity and high temporal and spectral resolution allow various practical applications of laser intracavity spectroscopy, such as measurements and simulations of atmospheric absorption, molecular and atomic spectroscopy, process control, isotope separation, study of free radicals and chemical reactions, combustion diagnostics, spectroscopy of excited states and nonlinear processes, measurements of gain and of spectrally narrow light emission. Intracavity absorption in single-mode lasers shows enhanced sensitivity as well, although not as high as in multimode lasers. Received: 10 May 1999 / Published online: 29 July 1999     

The effect of spectral resolution on the Raman spectra of polyaromatic hydrocarbons and beta‐carotene mixtures

The spectroscopic basis for extraterrestrial life‐detection through the molecular signatures of relevant biomaterials is dependent upon several instrumental facilities which could effect the diagnostic interpretation of key Raman bands from relevant substances occurring together in the geological record. To this effect, the Raman spectra of several polyaromatic hydrocarbons have been investigated under different conditions of spectral resolution using FT‐Raman‐spectroscopy operating at 1064 nm laser excitation wavelength. The observed Raman spectra are considerably altered under different conditions of spectral resolution; in particular, the discrimination between several polyaromatic hydrocarbons and beta‐carotene no longer becomes possible as the spectral resolution decreases. These results are relevant for the evaluation of miniaturised Raman spectrometers for space flight missions and incorporation into instrumentation for landers and rovers being proposed for future missions to Mars. Copyright © 2010 John Wiley & Sons, Ltd.     

Identification of overlapping optical lines in molecular spectra by means of the coherent population trapping of quantum levels

A new method of molecular beam spectroscopy with the ultrahigh resolution is theoretically suggested. This method is based on the phenomenon of the coherent population trapping of molecular levels and allows the identification of the overlapping optical lines in complex spectra (typical for polyatomic molecules), even when frequency intervals between the centers of given lines are less than their natural line widths. The theoretical analysis is carried out on the basis of the Schrödinger equation for the three-level molecular A-system interacting with the two-frequency laser radiation. The conditions of the practical realization and possible applications of the suggested spectroscopy method are discussed.     

基于高精细度光腔锁频激光的分子吸收光谱测量

利用高精细度光腔锁定激光频率,实现了对分子吸收光谱的高精度测量.光腔采用低热膨胀系数的殷钢结构设计和温度控制,实现了腔长度的稳定;通过将激光频率锁定在光腔纵模上,实现了高频率精度和高灵敏度的光腔衰荡光谱测量.利用该装置示范性地测量了二氧化碳分子在6470.42 cm~(-1)附近的光腔衰荡光谱和色散光谱,得到了高精度的谱线参数,并和数据库谱线参数进行了对比.     

High-resolution solid-state 13C14N and 13C15N heteronuclear correlation spectroscopy

Two-dimensional heteronuclear correlation spectroscopy is applied to coupled carbon and nitrogen nuclei in single crystals of amino acids and peptides. High resolution is available because the spectra have the carbon chemical shift along one frequency axis and the nitrogen chemical shift (and the second-order quadrupole shift in the case of ¹⁴N) along the second frequency axis. These two-dimensional spectra enable direct measurements of resonance frequencies and dipole-dipole couplings that are useful in providing information about the structure, dynamics, and spectral characteristics of molecules.     

Far infrared laser lines and assignments of CH3OH: a review

Methyl alcohol is the most important lasing molecule in the Far-Infrared (FIR) spectral region, and the most widely used for investigation and for applications. Since the last critical review of 1984, over seventy papers have been published dealing with the FIR laser lines and the infrared spectroscopy of CH₃OH. In 1984 we could list about 330 FIR laser lines, 98 of which were measured in frequency and 105 assigned. Since then more than 70 papers were published increasing the number of the known laser lines to 575 (103 measured in frequency). Also the FIR and IR spectroscopy was largely improved thanks to the analysis of high resolution FT spectra, and the number of the correctly assigned laser lines has been increased to 224. The wavenumbers of the assigned lines can now be predicted with an accuracy of about 0.001 cm^–1 or better, thus approaching the accuracy of the experimental frequency measurements.     

Image-guided optical spectroscopy provides molecular-specific information in vivo: MRI-guided spectroscopy of breast cancer hemoglobin, water, and scatterer size

A multimodality instrument that integrated optical or near-infrared spectroscopy into a magnetic resonance imaging (MRI) breast coil was used to perform a pilot study of image-guided spectroscopy on cancerous breast tissue. These results are believed to be the first multiwavelength spectroscopic images of breast cancer using MRI-guided constraints, and they show the cancer tumor to have high hemoglobin and water values, decreased oxygen saturation, and increased subcellular granularity. The use of frequency-domain diffuse tomography methods at many wavelengths provides the spectroscopy required for recovering maps of absorbers and scattering spectra, but the integration with MRI allows these data to be recovered on an image field that preserves high resolution and fuses the two data sets together. Integration of molecular spectroscopy into standard clinical MRI can be achieved with this approach to spectral tomography.     

Tunable carbon monoxide overtone laser sideband system for precision spectroscopy from 2.6 to 4.1 microm

We report a source of tunable laser radiation for high-precision molecular spectroscopy in the 2.6- 4.1-microm spectral region. Laser light from a CO overtone laser is mixed with microwaves, generating tunable sidebands of ~1 mW of power. We achieve very high absolute frequency accuracy by frequency-offset locking the CO laser to a CO(2) laser secondary frequency standard. The uncertainty of the laser frequency is less than 30 kHz (Dnu/nu=3x10(-10)) , and the laser linewidth is of the order of 100 kHz. This tunable and ultrastable laser system is suitable for very accurate molecular spectroscopy and metrology in a most interesting wavelength region. We demonstrate an application of the system to saturated-absorption spectroscopy of a rovibrational transition of carbonyl sulfide.     

A practical guide to robust detection of GABA in human brain by J-difference spectroscopy at 3 T using a standard volume coil

gamma-Aminobutyric acid (GABA) is the major inhibitory neurotransmitter in human brain and has been implicated in several neuropsychiatric disorders. In vivo human brain GABA concentrations are near the detection limit for magnetic resonance spectroscopy ( approximately 1 mM), and because of overlap with more abundant compounds, spectral editing is generally necessary to detect GABA. In previous reports, GABA spectra edited by J-difference spectroscopy vary considerably in appearance. We have evaluated the factors that affect GABA spectra and the conditions necessary for robust acquisition of J-difference spectra from arbitrary brain regions. In particular, we demonstrate that variations in spectral quality can be explained in part by the incoherent addition of transients that results from shot to shot frequency and phase variations. An automated time-domain spectral alignment strategy that enables reproducible acquisition of high-quality GABA spectra at 3 T with a standard 30-cm T/R volume coil is presented. Representative GABA spectra from human frontal lobe, an area where susceptibility-induced frequency and phase variations are especially troublesome, that demonstrate the robustness of the acquisition and data handling strategy used in this study are presented.     

高分辨椭圆弯晶谱仪在激光等离子体实验中的应用

 描述了用于激光等离子体X射线光谱研究的椭圆弯曲晶体谱仪系统。在“神光Ⅱ”第九路激光上对该谱仪进行标定实验，利用CCD相机成功地获得了激光等离子体铝和钛离子的K壳层和金离子M壳层谱；通过研究和辨认谱线，得到了X射线光谱，同时还给出了实验测定的谱仪分辨率。椭圆弯曲晶体谱仪除有高的收集光子效率外，还有更好的谱分辨和空间分辨率。分析了椭圆弯曲晶体谱仪在前沿科学技术和高技术实验中的应用。     

Modulation transfer in Doppler broadened Λ system and its application to frequency offset locking

We investigate modulation transfer through pump induced atomic coherence in pump-probe spectroscopy of Doppler broadened medium of cesium atoms. The mechanism of modulation transfer is discussed for a three level Λ configuration under slow frequency modulation. Modulation transfer is demonstrated by performing frequency modulation spectroscopy (FMS) on a sub-natural linewidth (<2 MHz) electromagnetically induced transparency (EIT) signal. Here the pump laser is modulated by acousto-optic frequency modulation and the modulation is transferred to the probe laser through atomic coherence. Finally the probe laser is locked on the first derivative spectrum of EIT signal. Such atomic frequency offset locking system totally removes the necessity of direct modulation of laser frequency, so that the spectral resolution is limited only by the practical linewidth of the laser systems. Moreover it provides a novel way to eliminate the additional frequency and intensity noise associated with direct frequency dithering, which may limit the experimental resolution.     

应用于碳同位素丰度测量的激光频率刻度系统研究

对应用于激光吸收光谱法碳同位素丰度测量中的激光频率实时刻度系统进行研究. 采用不同自由光谱范围的共焦法布里-珀罗干涉仪对测量过程中的激光扫描频率进行实时测量. 分别采用线性内插法和多项式拟合法对激光频率每次扫描过程中的频率非线性进行分析,通过对4976–4980 cm^-1波段CO₂吸收谱的多次测量平均的实验结果与HITRAN-2008数据库相应的吸收峰数据进行比较,得到两种方法的激光频率刻度精度均可达到10^-4 cm^-1,线性内插法的刻度精度要好于多项式拟合法. 验证了激光频率实时刻度系统在碳同位素丰度测量中应用的可行性. 关键词： 激光频率实时刻度 共焦法布里-珀罗干涉仪 同位素丰度测量 激光吸收光谱法     

Effects of laser linewidth on coherent antiStokes Raman spectroscopy

Expressions for the generated antiStokes spectral density in coherent antiStokes Raman spectroscopy (CARS) are obtained, which take into account the finite linewidths of laser sources and which may be used to analyse observed spectra. Lorentzian and gaussian laser lineshapes are taken as special cases, which enable further analytic results for single and multiline CARS spectra to be derived. Emphasis is placed on scanning and broadband (multiplex) CARS techniques, and the choice of laser sources discussed from the spectral point of view. As examples of multiline spectra an analytical account of a periodic spectrum is presented and temperature measurement from Q-branch spectra is treated.     

太赫兹波段豆油光谱的优化测量

太赫兹时域光谱技术是基于飞秒超快激光技术的有效的光谱检测技术,太赫兹波独特的优势使其成为一种有效的无损检测手段,并被广泛地应用到各个领域。然而在样品检测尤其是液体样品检测过程中,由于Fabry-Perot效应的存在,太赫兹波在样品、样品容器、以及光学元件之间的多次反射,使时域信号产生回波,样品的吸收光谱在频域内产生振荡,有可能会隐藏一些重要的吸收特征。为了解决这一问题,对解卷积算法进行改进,在传统计算模型的基础上,考虑系统中液体池窗片和光学元件对太赫兹波的非线性吸收,将包含回波的太赫兹时域信号描述为太赫兹主脉冲与一系列冲击信号和非线性传递函数的卷积。通过分析,有效去除回波引起的频谱振荡,进一步提高太赫兹波段豆油光学参数的测定精度。实验对比了改进前后0.2～2 THz波段豆油的频谱及吸收谱,实验结果证明,与传统的主脉冲截取法相比,本算法不仅能有效去除回波引起的频谱振荡,且在相同检测条件下,可将太赫兹波段豆油样品的频率分辨率由50 GHz有效提高至10 GHz。该算法不受被测对象参数的影响,同样适用于其他液体的太赫兹时域光谱测量。最后对吸收谱中残余的频谱振荡进行了深入分析。