Continuous‐wave optical parametric oscillator based infrared spectroscopy for sensitive molecular gas sensing

Over the past 10 years, with the advent of new crystals designs and a new generation of pump lasers, continuous‐wave (cw) optical parametric oscillators (OPOs) have developed into mature monochromatic light sources. Nowadays, cw OPOs can fulfill a wide variety of criteria for sensitive molecular gas sensing. It can access the mid‐infrared wavelength region, where many molecules have their fundamental rotational‐vibrational transitions, with high power. This high power combined with wide wavelength tuning and narrow linewidth creates excellent conditions for sensitive, high‐resolution spectroscopy. OPOs combined with robust methods, such as photoacoustic spectroscopy and cavity‐enhanced spectroscopy, are well suited for field measurements and remote‐sensing applications. The wide tunability of cw OPOs allows detection of larger molecules with broad absorption band structures, and its fast scanning capabilities allow rapid detection of trace gases, the latter is a demand for life‐science applications. After a short introduction about the physical principle of cw OPOs, with its most recent physical developments, this review focuses on sensitive molecular gas sensing with a variety of spectroscopic applications in atmospheric and life sciences.     

Spectroscopic diagnostics of barrier discharge plasmas in mixtures of zinc diiodide with inert gases

The spectral characteristics of the emission of gas discharge atmospheric pressure plasmas in mixtures of zinc diiodide vapor with inert gases (He, Ne, Ar, Kr, and Xe) are investigated. The formation of a gas discharge plasma and the excitation of the components of a working mixture were performed in a high-frequency (with a repetition frequency of sinusoidal voltage pulses of 100 kHz) barrier discharge. The gas discharge emission was analyzed in the spectral range 200–900 nm with a resolution of 0.05 nm. Emission bands of ZnI(B-X) exciplex molecules and I₂* excimer molecules, lines of inert gases, and emission bands of XeI* exciplex molecules (in Xe-containing mixtures) were revealed. It is ascertained that the strongest emission of ZnI* molecules is observed in ZnI₂/He(Ne) mixtures. The regularities in the spectral characteristics of the gas discharge plasma emission are considered.     

Broadly tunable mid-infrared VECSEL for multiple components hydrocarbon gas sensing

A new sensing platform to simultaneously identify and quantify volatile C1 to C4 alkanes in multi-component gas mixtures is presented. This setup is based on an optically pumped, broadly tunable mid-infrared vertical-external-cavity surface-emitting laser (VECSEL) developed for gas detection. The lead-chalcogenide VECSEL is the key component of the presented optical sensor. The potential of the proposed sensing setup is illustrated by experimental absorption spectra obtained from various mixtures of volatile hydrocarbons and water vapor. The sensor has a sub-ppm limit of detection for each targeted alkane in a hydrocarbon gas mixture even in the presence of a high water vapor content.     

Electron swarm parameters in SiH4-rare gas mixtures andcollision cross sections for monosilane molecules

Previously measured drift velocities and longitudinal diffusion coefficients in SiH₄-Ar mixtures were reanalyzed, and the new vibrational excitation cross sections for monosilane molecules were obtained. Not only were the new cross sections consistent with swarm parameters, but also the ratio of their magnitudes at the resonance peak agreed with earlier measurements of the electron beam experiment. Having known the vibrational excitation cross sections, the analysis of the primary ionization coefficient measured in SiH₄-Kr mixtures led to a consistent inelastic cross section, which possibly corresponds to the total section for neutral dissociations for the molecule. It was confirmed that the derived set of the cross sections also gave good agreement with the electron swarm parameters measured in pure monosilane gas     

Free‐Electron Gas Spectrum Uniqueness in the Mixture of Noble Gases

Gas mixtures can reach the Maxwell's specter shape in case of low‐ionized mono‐atomic mixtures in the weak electric field. The parameters pertaining to the Maxwell spectrum of free electrons' gas straightforwardly settle on the insulating characteristics of the examined gas mixture at the fundamental level. In this paper, a condition for breakdown has been accomplished taking as a starting point the ionization coefficients derived accordingly, as well as the conditions for breakdown in keeping with the Townsend mechanism. The dc breakdown voltage value of noble gases mixture has been measured in the experimental part of the paper. The hypothesis that the free‐electron gas spectrum is unique in the noble gas mixture and is of Maxwell's type has been verified. (© 2016 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Application of Mn nano-flower sculptured thin films produced on interdigitated pattern as cathode and anode electrodes in field ionization gas sensor

The photolitography method was used for producing interdigitated configurations for cathode and anode electrodes of a field ionization gas sensor in which Mn helical nano-flowers with 3-fold symmetry were deposited using oblique angle deposition together with rotation of the substrate about its surface normal, with each rotation divided into six sections. These sections were alternately rotated at high and low speeds. Three different distances were chosen in the design between anode and cathode electrodes, namely 40, 100 and 200 μm. Physical structure and morphology of electrodes were studied by field emission scanning electron microscope and atomic force microscope analyses.The breakdown voltage of the system was studied for nitrogen, oxygen, argon, air and carbon mono-oxide gases. Investigations with these gases at different distances between anode and cathode and different gas pressures confirmed Paschen's Law. Results showed that at low pressures, decreasing the gap between electrodes increases the breakdown voltage. With fewer gas molecules between the electrodes the number of interactions between particles is reduced and higher energies are required for ionization of gas molecules. At high pressures, the breakdown voltage is decreased because of an increased number of molecular interactions. The sensor demonstrated good selectivity between the different gases and selectivity was enhanced with increasing gas pressure. A direct relationship was found at low pressures (e.g., 0.1 mbar) between the breakdown voltage and the gas ionization energy while at high pressures (e.g., 1000 mbar) this relationship was reversed.     

Molecular transport in pulsed optical lattices

This paper presents an overview of our recent theoretical and experimental work investigating the application of deep, periodic optical dipole potentials (optical lattices) produced by intense pulsed optical fields for the transport of neutral molecular gases. Our review outlines the deceleration of molecules in a molecular beam to create slow cold molecules and also acceleration for production of hyperthermal molecular beams with velocities in excess of 10 km/s for material processing. We describe how bulk motion can be induced in a gas by a traveling optical lattice, even when the gas is not fully trapped by the lattice. In all these cases energy and momentum can be deposited from laser radiation that is not resonant with any internal states. When significant numbers of gas collisions occur during the lattice/laser pulse, gas heating accompanied by the formation of gas jets in free space and bulk drift in a capillary can be induced. Finally, we describe a new nonintrusive laser diagnostic method for measurement of gas properties based on analysis of light scattered from density perturbations induced by lattices. PACS 32.80.Lg; 42.50.Vk; 51.10.+y; 42.65.Es; 33.20.Fb     

Use of traps to study positron annihilation in astrophysically relevant media

We discuss possible experiments which can exploit recently-developed techniques to accumulate, store, and manipulate low-energy positrons to measure the parameters associated with positron annihilation radiation from media of astrophysical interest. Media discussed include collections of dust grains, partially ionized gases, He, H₂, and other molecular gases and gas mixtures, including polycyclic aromatic hydrocarbon (PAH) molecules relevant to the interstellar medium.     

Gas counter for low temperature Conversion Electron M?ssbauer Spectroscopy experiments

The operation of a gas counter, designed for Conversion Electron M?ssbauer Spectroscopy measurement at low temperature, has been investigated. The experimental setup is described and tested with two pure gases, He and Ne, and two mixtures, He-5%CH₄ and He-5%N₂. The impacts on the counter performances of the applied voltage, the gas composition and pressure as well as the gas renewing are investigated between 41?K and 300?K. This investigation is made using ¹¹⁹Sn M?ssbauer source and metallic tin absorber. The appropriate operating conditions of the present counter have been established for temperatures down to 41?K for both pure gases, and 61 and 85?K for He-5%N₂ and He-5%CH₄ respectively.     

确定SF6-CO2预放电参数的激光脉冲方法

在均匀电场中,用高能激光脉冲释放初始电子以研究负电性气体的电子崩的发展,决定预放电过程的基本参数(游离系数α,吸附系数η和漂移速度v等)是一个有用的方法,本文对此方法做了详细的分析。采用这种方法对SF₆-CO₂混合气体做了研究,获得了10⁸个以上的初始电子及其分布,并给出了α/P,η/P和ν与E/P(E=电场强度,P=气体压力)的关系。本文还对所用的测量系统做了讨论,提出了改进办法。 关键词：     

Measuring polarization in the x‐ray range: simulation for the impact gas mixture and pressure in gaseous detectors

The development of new technology in micropattern gaseous detectors makes it possible to measure x‐ray polarization for energies where the photoelectric effect is the main mechanism of interaction with matter. In a previous work, we showed that a modification of the Geant4 simulation code is a useful toolkit to simulate the photoelectric interaction of linearly polarized x‐rays with micropattern gas detectors. In particular, by properly taking into account the direction of the photoelectron, we developed a new calculation of the final state. We simulated one experimental setup found in the literature and showed that the simulation results obtained are in agreement with the experimental data. In this work, we present new results on simulation of a mixture of two gases with different pressures and study the impact in the modulation factor. The simulations were done for both low and high Z mean mixture. With these gas mixtures, we observed that the modulation factor was greater for a low Z mixture than that with a high Z, but the efficiency was opposite. We also observed that the modulation factor for high Z was influenced by the absorption edge of the photoelectric cross section. Copyright © 2009 John Wiley & Sons, Ltd.     

声弛豫过程影响下的气体平衡态热容合成方法及其在气体检测中的应用

声扰动形成的分子振动弛豫过程使得气体热容成为依赖于声频率的有效热容,导致随频率变化的声速频散和声弛豫吸收。本文基于单弛豫过程合成算法,提出一种基于两频点声速和声吸收测量值的气体平衡态热容合成方法。该方法两个测量声频点只需在声弛豫吸收显著的频率范围即可分别合成可激发气体分子内外自由度热容,并有效消除声弛豫过程对气体平衡态热容测量结果的影响。对于室温下由CO₂、CH₄、Cl₂、N₂和O₂组成的多种气体,合成的气体热容值与基于Planck-Einstein公式的热力学理论计算结果相符,相比实验数据最大相对误差为3.51%。合成的转动和振动热容还可应用于气体分子几何结构、振动频率大小和混合气体摩尔分数的检测。      

第一性原理研究气体小分子吸附的石墨烯负载金属原子体系

石墨烯负载的单个金属原子体系(M-gra)具有高的结构稳定性,显正电性的金属原子可作为活性位用在气敏器件和催化材料.本文采用基于密度泛函理论的第一性原理方法研究单个有毒气体小分子(NO和CO)在M-gra表面的吸附特性.研究结果表明:单个NO分子吸附的稳定性高于CO分子,由于其能够从反应衬底获得更多的转移电荷,因此,M-gra衬底对NO分子表现出高的灵敏度.此外,不同小分子吸附能够改变M-gra体系的电荷密度和自旋电荷分布,进而使得气体分子吸附体系表现出不同大小的磁矩.通过对比气体分子吸附前后M-gra体系的磁矩变化,能够有效判断吸附分子和反应衬底的类型.     

Coherent transients in gases

A great variety of coherent transient processes in atomic and molecular gases is investigated. The degeneracy with respect to magnetic sublevels, which is typical of working levels of atomic and molecular transitions in gases, leads to new phenomena. In particular, the non-Faraday rotation of the coherent-response polarization vector at the 0 ↔ 1 transition is investigated in the presence of the longitudinal magnetic field in the ¹⁷⁴Yb vapor for both photon echo and stimulated photon echo. A specific relaxation channel that involves the depolarizing collisions emerges in a gas due to the degeneracy of working levels. Such collisions are especially important for atoms and are also observed in molecules. The anisotropy of the depolarizing collisions leads to a new phenomenon of the collision photon echo, which is experimentally demonstrated for the 0 ↔ 1 transition in the ¹⁷⁴Yb mixtures with atomic buffers. The velocity-dependent relaxation rates are observed for various coherent phenomena in molecular gases. The coherent control of a few coherent transient processes is implemented.     

Molecular gas sensing below parts per trillion: radiocarbon-dioxide optical detection

Radiocarbon ((14)C) concentrations at a 43 parts-per-quadrillion level are measured by using saturated-absorption cavity ringdown spectroscopy by exciting radiocarbon-dioxide ((14)C(16)O(2)) molecules at the 4.5 μm wavelength. The ultimate sensitivity limits of molecular trace gas sensing are pushed down to attobar pressures using a comb-assisted absorption spectroscopy setup. Such a result represents the lowest pressure ever detected for a gas of simple molecules. The unique sensitivity, the wide dynamic range, the compactness, and the relatively low cost of this table-top setup open new perspectives for ^{14}C-tracing applications, such as radiocarbon dating, biomedicine, or environmental and earth sciences. The detection of other very rare molecules can be pursued as well thanks to the wide and continuous mid-IR spectral coverage of the described setup.     

Spectral characteristics of a broadband exciplex spontaneous emission source upon mixtures of the cadmium dibromide vapor with gases

The spectral characteristics of radiation from atmospheric-pressure gas-discharge plasma in mixtures of cadmium dibromide vapor with gases (Ne, Ar, Kr, Xe, and N₂), as well as the temporal characteristics of the voltage and current, have been investigated. A barrier discharge at the repetition frequency of sine voltage pulses up to 140 kHz has been used to create the gas-discharge plasma and excite the components of the working mixture. The discharge radiation has been analyzed in the spectral range 200–900 nm with a high resolution (0.05 nm). In the spectra, we have revealed radiation from exciplex molecules CdBr(B → X) and CdBr(C → X), atomic lines of cadmium and inert gases, and, in mixtures with xenon, radiation of exciplex molecules XeBr(B → X, B → A). The XeBr(B → X) radiation prevailed in the spectra at mixture temperatures up to 200°C. The further increase of the temperature resulted in the prevalence of the CdBr(B → X) radiation. The most intense CdBr(B → X) radiation was observed in mixtures of CdBr₂/Xe. When the temperature of the mixture was higher than 250°C, the discharge radiation had a silvery-white color. Regularities in the spectral characteristics of the radiation from the gas-discharge plasma are discussed. The high-frequency atmospheric-pressure barrier discharge in mixtures of cadmium dibromide with gases, excited by sine voltage pulses, can be used in multiwave and broadband excilamps, operating in the UV and visible regions.     

相关光谱法在光纤气体传感中的应用

本文提出了一种新的基于相关光谱法的光纤气体检测方案，在对传统相关光谱检测理论进行详细分析的基础上，提出了一种新的实现方案。这种方法继承了传统相关光谱法在信号检测的时候所具有的高选择性的优点，在调制方法上有创新，使得利用宽带光源（LED）在检测甲烷和乙炔等在近红外具有梳状吸收峰的气体时变得简单易行。本文对该系统进行了详尽的理论分析，在合理选择器材的基础上实际构建和调试了一个基于光谱检测的光纤甲烷气体检测系统。文中给出了存在干扰气体情况下检测结果。实践中干扰气体引起的信号变化相当于甲烷信号变化的7．4％，已经达到国际上相关光谱检测现有的最佳值。     

Working gases in thermoacoustic engines.

The best working gases for thermoacoustic refrigeration have high ratios of specific heats and low Prandtl numbers. These properties can be optimized by the use of a mixture of light and heavy noble gases. In this paper it is shown that light noble gas-heavy polyatomic gas mixtures can result in useful working gases. In addition, it is demonstrated that the onset temperature of a heat driven prime mover can be minimized with a gas with large Prandtl number and small ratio of specific heats. The gas properties must be optimized for the particular application of thermoacoustics; it cannot be assumed that high specific heat ratio and low Prandtl number are always desirable.     

基于光谱吸收法和荧光法的甲烷和二氧化硫检测系统的研究

根据污染气体的光谱吸收特性与荧光特性,设计了一套时分复用检测系统,既可以使用光谱吸收法检测甲烷和二氧化硫又可以使用荧光法检测二氧化硫。系统采用组合可切换光源、共用光路、气室及信号处理部分,首先进行光谱吸收和荧光的特性测量,然后进行光谱吸收法检测甲烷与二氧化硫浓度实验,以及紫外荧光法检测二氧化硫浓度实验。经过光谱吸收和荧光的特性测量得出吸收法测二氧化硫和甲烷的吸收峰处的激发波长分别为280nm和1.64μm,荧光法测二氧化硫最佳激发波长为220nm。经光谱吸收法实验可得甲烷浓度与相对强度的线性关系和二氧化硫浓度与输出电压的线性关系,线性度分别为98.7%,99.2%;经荧光法实验可得二氧化硫浓度与电压成线性关系,线性度达到了99.5%。研究表明,该系统能使用于污染气体的光谱吸收检测和紫外荧光检测。将两种测量方式组合在一起,降低了成本与体积,同时此系统也可用于其他气体的检测,有一定的应用价值。     

Ionization and Breakdown in SF6-Air and Freon-Nitrogen Mixtures

The sparking potentials and swarm coefficients (ionization and attachment coefficients) have been measured in sulphurhexafluoride- air and freon-nitrogen mixtures over the range of 110 ? E/p ? 240 V cm-1 torr-l and gas pressures varying between 1 and 20 torr, at 20°C. Addition of strongly attaching salphur-hexafluoride and freon gases increased the sparking potentials and the rate of increase of the attachment coefficient with increasing percentage of the strongly attaching gases in the mixtures was much larger than the rate of change of the first ionization coefficient.