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.     

The ground state of molecular hydrogen

The v = 0?0 quadrupole spectrum of H₂ has been recorded using a 0.005-cm^?1 resolution Fourier transform spectrometer. The rotational lines S(1) through S(5) are observable in the spectra, in the region 587 to 1447 cm^?1. The spectral position for S(0) was also obtained from its v = 1-0 ground-state combination difference. The high accuracy of the H₂ measurements has permitted a determination of four rotational constants. These are (in cm^?1) B₀ = 59.33455(6); D₀ = 0.045682(4); H₀ = 4.854(12) × 10^?5; L₀ = ?5.41(12) × 10^?8. The hydrogen line positions will facilitate studies of structure and dynamics in astrophysical objects exhibiting infrared H₂ spectra. The absolute accuracy of frequency calibration over wide spectral ranges was verified using 10-μm CO₂ and 3.39-μm CH₄ laser frequencies. Standard frequencies for 5-μm CO were found to be high by 12 MHz (3.9 × 10^?4 cm^?1).     

Die zeitliche Entwicklung einer Townsend-Entladung

Oscillographic studies of the current of a Townsend-discharge—started by 10³ to 10⁵ electrons within some mμsec—demonstrate the temporal development of the discharge in separated generations of electrons. Experiments were made in N₂, CH₄, CO₂ and mixtures of N₂/CH₄, and A/Air (gap-length 1·8 to 3 cm, pressure 50 to 400 mm Hg). A careful curve-fitting with calculated currents proves the agreement between measured and calculated curves. This correspondence shows that the discharge is governed by a) ionisation by collisions and b) secondary-photoeffect at the cathode.     

Absolute, spatially resolved, in situ CO profiles in atmospheric laminar counter-flow diffusion flames using 2.3?μm TDLAS

We developed a new, spatially traversing, direct tunable diode laser absorption spectrometer (TDLAS) for quantitative, calibration-free, and spatially resolved in situ measurements of CO profiles in atmospheric, laminar, non-premixed CH₄/air model flames stabilized at a Tsuji counter-flow burner. The spectrometer employed a carefully characterized, room temperature distributed feedback diode laser to detect the R20 line of CO near 2,313?nm (4,324.4?cm^?1), which allows to minimize spectral CH₄ interference and detect CO even in very fuel-rich zones of the flame. The burner head was traversed through the 0.5?mm diameter laser beam in order to derive spatially resolved CO profiles in the only 60-mm wide CH₄/air flame. Our multiple Voigt line Levenberg?CMarquardt fitting algorithm and the use of highly efficient optical disturbance correction algorithms for treating transmission and background emission fluctuations as well as careful fringe interference suppression permitted to achieve a fractional optical resolution of up to 2.4?×?10^?4 OD (1??) in the flame (T up to 1,965?K). Highly accurate, spatially resolved, absolute gas temperature profiles, needed to compute mole fraction and correct for spectroscopic temperature dependencies, were determined with a spatial resolution of 65???m using ro-vibrational N₂-CARS (Coherent anti-Stokes Raman spectroscopy). With this setup we achieved temperature-dependent CO detection limits at the R20 line of 250?C2,000?ppmv at peak CO concentrations of up to 4?vol.%. This permitted local CO detection with signal to noise ratios of more than 77. The CO TDLAS spectrometer was then used to determine absolute, spatially resolved in situ CO concentrations in the Tsuji flame, investigate the strain dependence of the CO Profiles and favorably compare the results to a new flame-chemistry model.     

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3.2~3.7 μm中红外相干光源输出,最大差频输出功率约为1 μW.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3 028.751 cm^-1 v₃基频吸收线作为分析谱线,10 cm光程的检测限为0.8 ppm.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.     

Thermal and optical properties of femtosecond-laser-structured PMMA

Thermal diffusivity of laser micro- and nano-structured regions in polymethylmethacrylate (PMMA) was measured by the temperature wave method with a lateral resolution reduced to ～10 μm using an array of micro-sensors. The volume fraction of laser modified phase was maximized by implementing tightly focused femtosecond laser pulses inside PMMA and maintaining distance of few micrometers between the irradiation spots. The absolute value of thermal diffusivity of PMMA 1.066±0.08×10^?7 m²/s was reliably determined with the miniaturized sensors. Regions laser structured by single pulses had no trace of carbonization, almost the same thermal diffusivity as the host PMMA, and a stress-induced birefringence Δn～10^?4 modulated with period ～2 μm.     

Ultra-high-precision mid-IR spectrometer II: system description and spectroscopic performance

The development and spectroscopic performance evaluation of an ultra-sensitive, mid-IR spectrometer is reported. The laser system is based upon difference-frequency generation (DFG) at ～3.5 μm by mixing a DFB diode laser at 1562 nm and a DFB fiber laser at 1083 nm using a periodically poled LiNbO₃ crystal. DFG radiation was coupled to a 100?m optical path length astigmatic Herriott cell. Sensitive and selective spectroscopic detection of formaldehyde was performed with second-harmonic detection using Peltier-cooled HgCdTe detectors. By applying computer lock-ins, dual-beam optical noise subtraction, focus matching, thermal stabilization, active wavelength control, and advanced signal processing a sensitivity corresponding to an absorbance ～1.6×10^-7 is achieved for 260 s of averaging.     

A widely tunable (5-12.5 μm) continuous-wave mid-infrared laser spectrometer based on difference frequency generation in AgGaS2

A widely tunable (5-12.5 μm) continuous-wave (cw) mid-infrared (mid-IR) laser spectrometer based on difference frequency generation (DFG) by mixing an external-cavity diode laser (ECDL) with a Ti:Sapphire laser in an AgGaS₂ crystal is described. The wide tunability was achieved by tuning laser wavelength associated with crystal angle tuning under type II phase matching condition. A maximum output power of about 66 nW was obtained at 8.06 μm. High resolution spectrum of methane (CH₄) over more than 10 cm⁻¹ near 7.7 μm has been recorded to evaluate the performance of the developed DFG-based mid-IR laser spectrometer.     

Automatically tunable continuous-wave optical parametric oscillator for high-resolution spectroscopy and sensitive trace-gas detection

We present a high-power (2.75 W), broadly tunable (2.75–3.83 μm) continuous-wave optical parametric oscillator based on MgO-doped periodically poled lithium niobate. Automated tuning of the pump laser, etalon and crystal temperature results in a continuous wavelength coverage up to 450 cm^-1 per poling period at <5×10^-4 cm^-1 resolution. The versatility of the optical parametric oscillator as a coherent light source in trace-gas detection is demonstrated with photoacoustic and cavity ring-down spectroscopy. A 17-cm^-1-wide CO₂ spectrum at 2.8 μm and multi-component gas mixtures of methane, ethane and water in human breath were measured using photoacoustics. Methane (at 3.2 μm) and ethane (at 3.3 μm) were detected using cavity ring-down spectroscopy with detection limits of 0.16 and 0.07 parts per billion by volume, respectively. A recording of ¹²CH₄ and ¹³CH₄ isotopes of methane shows the ability to detect both species simultaneously at similar sensitivities. PACS 42.65.Yj; 42.72.Ai; 42.62.Fi     

Detection of trace nitric oxide concentrations using 1-D laser-induced fluorescence imaging

Spectrally resolved laser-induced fluorescence (LIF) with one-dimensional spatial imaging was investigated as a technique for detection of trace concentrations of nitric oxide (NO) in high-pressure flames. Experiments were performed in the burnt gases of premixed methane/argon/oxygen flames with seeded NO (15 to 50 ppm), pressures of 10 to 60 bar, and an equivalence ratio of 0.9. LIF signals were dispersed with a spectrometer and recorded on a 2-D intensified CCD array yielding both spectral resolution and 1-D spatial resolution. This method allows isolation of NO-LIF from interference signals due to alternative species (mainly hot O₂ and CO₂) while providing spatial resolution along the line of the excitation laser. A fast data analysis strategy was developed to enable pulse-by-pulse NO concentration measurements from these images. Statistical analyses as a function of laser energy of these single-shot data were used to determine the detection limits for NO concentration as well as the measurement precision. Extrapolating these results to pulse energies of ～?16 mJ/pulse yielded a predicted detection limit of ～?10 ppm for pressures up to 60 bar. Quantitative 1-D LIF measurements were performed in CH₄/air flames to validate capability for detection of nascent NO in flames at 10–60 bar.     

Preliminary analysis of CH3D from 3250 to 3700 cm

The infrared spectrum of CH₃D from 3250 to 3700 cm⁻¹ was studied for the first time to assign transitions involving the ν₂ + ν₃, ν₂ + ν₅, ν₂ + ν₆, ν₃ + 2ν₆ and 3ν₆ vibrational states. Line positions and intensities were measured at 0.011 cm⁻¹ resolution using Fourier transform spectra recorded at Kitt Peak with isotopically enriched samples. Some 2852 line positions (involving over 900 upper state levels) and 874 line intensities were reproduced with RMS values of 0.0009 cm⁻¹ and 4.6%, respectively. The strongest bands were found to be ν₂ + ν₃ at 3499.7 cm⁻¹ and ν₂ + ν₆ at 3342.5 cm⁻¹ with integrated strengths, respectively, of 8.17 × 10⁻²⁰ and 2.44 × 10⁻²⁰ (cm⁻¹/molecule · cm⁻²) at 296 K (for 100% CH₃D). The effective Hamiltonian was expressed in terms of irreducible tensor operators and adapted to symmetric top molecules. Its present configuration in the MIRS package permitted simultaneous consideration of the four lowest polyads of CH₃D: the Ground State (G.S.), the Triad from 6.3 to 9.5 μm, the Nonad from 3.1 to 4.8 μm and now the Enneadecad (19 bands) from 2.2 to 3.1 μm. The CH₃D line parameters for this interval were calculated to create a new database for the 3 μm region.     

Preparation and comparative structural properties of porous SnO2 microrods and submicrorods

A facile two-step approach has been used for the synthesis of porous SnO₂ rods: the initial room-temperature precipitation of precursor SnC₂O₄ and its subsequent thermal decomposition at 550 °C. Both the as-obtained porous SnO₂ microrods (length ～10.0?±?3.5 μm, diameter ～1.1?±?0.4 μm) and submicrorods (length ～5.8?±?1.9 μm, diameter ～0.4?±?0.1 μm) are the crystalline mixtures of major tetragonal and minor orthorhombic crystal phases, showing a tetragonal fraction of 84.7 and 87.0 %, respectively. When applied as a lithium-ion battery anode, the porous submicrorods (specific surface area ～13.6 m² g^?1) can deliver an initial discharge capacity of 1,730.7 mAh g^?1 with a high coulombic efficiency of 61.6 % and show the 50th discharge capacity of 662.8 mAh g^?1 at 160 mA g^?1 within a narrow potential range of 10.0 mV to 2.0 V. Similarly, even the anode of porous microrods (specific surface area ～11.8 m² g^?1) can still exhibit an initial discharge capacity of 1,661.1 mAh g^?1 at 160 mA g^?1 with a coulombic efficiency of 60.9 %. Regardless of the polymorphic nature, the acquired porosity may only alleviate the huge volume change of anodes for the first cycle; thus, the structural parameters of average size and specific surface area can be feasibly associated with the enhanced lithium storage capability. Anyway, these indicate a facile oxalate precursor method for the controlling synthesis and high performance of rodlike SnO₂ for lithium-ion batteries.     

Simultaneous detection of trace gases using multiplexed tunable diode lasers and a photoacoustic cell containing a cantilever microphone

We report what we believe to be a novel demonstration of simultaneous detection of multiple trace gases by near-IR tunable diode laser photoacoustic spectroscopy using a cell containing a cantilever microphone. Simultaneous detection of carbon monoxide (CO), ethyne (C₂H₂), methane (CH₄) and combined carbon monoxide/carbon dioxide (CO+CO₂) in nitrogen-based gas mixtures was achieved by modulation frequency division multiplexing the outputs of four near-IR tunable diode lasers. Normalized noise-equivalent absorption coefficients of 3.4×10^?9, 3.6×10^?9 and 1.4×10^?9 cm^?1?W?Hz^?1/2 were obtained for the simultaneous detection of CO, C₂H₂ and CH₄ at atmospheric pressure. These corresponded to noise-equivalent detection limits of 249.6 ppmv (CO), 1.5 ppmv (C₂H₂) and 293.7 ppmv (CH₄) respectively over a measurement period of 2.6 s at the relevant laser power. The performance of the system was not influenced by the number of lasers deployed, the main source of noise arising from ambient acoustic effects. The results confirm that small-volume photoacoustic cells can be used with low optical power tunable diode lasers for rapid simultaneous detection of trace gases with high sensitivity and specificity.     

Combining a DS-DBR laser with QPM-DFG for mid-infrared spectroscopy

Studies into the suitability of a novel, widely tunable telecom L-band (1563?C1613?nm) digital supermode distributed Bragg reflector (DS-DBR) laser for spectroscopy in the mid-IR are presented. Light from the DS-DBR laser was mixed with 1064?nm radiation in a periodically poled lithium niobate (PPLN) crystal to generate mid-IR light by quasi phase matching difference frequency generation (QPM-DFG). The resultant continuous wave radiation covered the range 3000?C3200?cm^?1 with powers of up to 2.6???W. The use of such laser light for spectroscopic applications was illustrated by performing absorption experiments on both narrow-band and broad-band absorbers, namely methane (CH₄) and methanethiol (CH₃SH). Wavelength modulation spectroscopy (WMS) on CH₄ demonstrated that the modulation characteristics of the DS-DBR laser observed in the near-IR were transposed to the mid-IR and yielded a sensitivity of 3.1×10^?6?cm^?1?Hz^?1/2 over a 47?cm path length. In the CH₃SH spectrum, the absorption feature at 3040?cm^?1 was identified as a potential useful region for monitoring this biomarker in exhaled breath at reduced pressures.     

Time-resolved photography of X-ray emission from CO2 laser generated plasma

The construction and use of an X-ray pinhole camera with a nanosecond shutter is described. Photographs of X-ray emission from plasma generated by a CO₂ laser (at incident intensities of ? 10¹³ W cm^?2) were recorded with time and space resolution of 6 ns and ～ 20 μm respectively, and the structure of localised X-ray emission regions was measured. These observations are related to contemporary theories of non-linear laser-plasma interactions.     

Optimization of optical characteristics of In0.29Ga0.71As0.99N0.01/GaAs straddled nano-heterostructure

Designing of a nanoscale Quantum Well (QW) heterostructure with a well thickness of ～60?Å is critical for many applications and remains a challenge. This paper has a detailed study directed towards designing of In_0.29Ga_0.71As_0.99N_0.01/GaAs straddled nanoscale-heterostructure having a single QW of thickness ～60?Å and optimization of optical and lasing characteristics such as optical and mode gain, differential gain, gain compression, anti-guiding factor, transparency wavelength, relaxation oscillation frequency (ROF), optical power and their mutual variation behavior. The outcomes of the simulation study imply that for the carrier concentration of ～2?×?10¹⁸cm^?3 the optical gain of the nano-heterostructure is of 2100?cm^?1 at the wavelength is of 1.30?μm. Though the obtained gain is almost half of the gain of InGaAlAs/InP heterostructure, but from the wavelength point of view the InGaAsN/GaAs nano-heterostructure is also more desirable because the 1.30?μm wavelength is attractive due to negligible dispersion in the silica based optical fiber. Hence, the InGaAsN/GaAs nano-heterostructure can be very valuable in optical fiber based communication systems.     

T-shape microresonator-based quartz-enhanced photoacoustic spectroscopy for ambient methane monitoring using 3.38-μm antimonide-distributed feedback laser diode

This paper reports on the development of a gas sensor involving a newly available 3.38-μm distributed feedback laser in combination with a novel T-shape microresonator-based quartz-enhanced photoacoustic spectroscopy (T-mR QEPAS), capable of simultaneous monitoring of multi-species (such as CH₄, H₂CO, HCl, C₂H₄) using the same QEPAS spectrophone. As a first demonstration, monitoring of ambient methane (CH₄) was achieved at atmospheric pressure with a 1σ detection limit of 400 ppbv (parts per billion by volume) in an integration time of 10 s and a water vapor concentration of 1.15 vol% (11,500 ppm) in the atmosphere, which is very suitable for field measurement of CH₄ emission.     

Structural and Mössbauer studies of nanocrystalline Mn<Superscript>4+</Superscript>-doped Li<Subscript>0.5</Subscript>Fe<Subscript>2.5</Subscript>O<Subscript>4</Subscript> particles prepared by mechanical milling

The structure and magnetic properties of spinel-related Mn⁴⁺-doped Li_0.5Fe_2.5O₄ nanocrystalline particles of the composition Li_0.5Fe_2.25Mn_0.1875O₄, prepared by milling a pristine sample for different times, were investigated. The average crystallite and particle size, respectively, decreased form ～40 nm to ～10 nm and ～2.5 μm to ～10 nm with increasing milling time from 0 h to 70 h. Rietveld refinement of the XRD data of the non-milled sample show the Mn⁴⁺ dopant ions to substitute for Fe³⁺ at the octahedral B-sites of the spinel-related structure. The Mössbauer spectra of the milled ferrites indicate that more particles turn superparamagnetic with increasing milling time. The Mössbauer data collected at 78 K suggest that while in the non-milled sample the Mn⁴⁺ ions substitute for Fe³⁺ at the octahedral B-sites, this is reversed as milling proceeds with doped Mn⁴⁺ ions, balancing Fe³⁺ vacancies and possibly Li⁺ ions progressively migrate to the tetrahedral A-sites. This is supported by the slight increase observed in the magnetization of the milled samples relative to that of the non-milled one. The magnetic data suggest that in addition to the increasing superparamagentic component of the milled particles, thermal spin reversal and/or spin canting effects are possible at the surface layers of the nanoparticles.     

Single-QCL-based absorption sensor for simultaneous trace-gas detection of CH4 and N2O

A quantum cascade laser (QCL)-based absorption sensor for the simultaneous dual-species monitoring of CH₄ and N₂O was developed using a novel compact multipass gas cell (MGC). This sensor uses a thermoelectrically cooled, continuous wave, distributed feedback QCL operating at ~7.8 µm. The QCL wavelength was scanned over two neighboring CH₄ (1275.04 cm^?1) and N₂O (1274.61 cm^?1) lines at a 1 Hz repetition rate. Wavelength modulation spectroscopy (f = 10 kHz) with second harmonic (2f) detection was performed to enhance the signal-to-noise ratio. An ultra-compact MGC (16.9 cm long and a 225 ml sampling volume) was utilized to achieve an effective optical path length of 57.6 m. With such a sensor configuration, a detection limit of 5.9 ppb for CH₄ and 2.6 ppb for N₂O was achieved, respectively, at 1-s averaging time.     

Measurements of spatially resolved electron number densities and modes temperatures using optical emission spectroscopy of atmospheric pressure microplasma jet

The electrical gas discharge parameters of direct-current non-thermal microplasma jet in Ar-2%H₂ flow at open atmospheric air was investigated by using spatially resolved optical emission spectroscopy (OES). The jet was confined from microhollow of tungsten-carbide (～500 μm inner diameter) to a molybdenum foil. Despite its small volume, the atmospheric pressure microplasma jet provides a range of power densities, from low to ～10¹² W m^?3 generated either in rare gases or in molecular gases. A high resolution spectrometer (Jobin-Yvon, Czerny-Turner model THR1000, resolution of 0.001 nm, with focal length of 1.0 m and numerical aperture of 0.13 ? f/7.5) was used to allow registration of OH (A ²Σ⁺, ν = 0 → X ²Π, ν′ = 0) rotational bands at 306.357 nm, Ar I 603.213 nm line and N₂ (C ³Π _u , ν = 0 → B ³Π _g , ν′ = 0) second positive system with the band head at 337.13 nm in order to estimate the rotational temperature from the cathode sheath of the plasma jet to the anode. For currents ranging from 20 to 100 mA and for a particular excited levels, the excitation temperature was measured in the negative glow region either from a Boltzmann plot of Ar I 4p–4s and 5p–4s transitions of excited argon or using the Mo I (from 440 to 450 nm) two-lines method of excited Mo atoms sputtered from the cathode surface, giving 24 000 K (100 mA at 100 μm) and 7000 K (20 mA at 500 μm from the cathode). From the N₂ (C ³Π _u , ν = 0 → B ³Π _g , ν′ = 0) rotational transition the rotational temperature along the positive column was estimated. The vibrational temperature of the bulk plasma (1400 to 4500 K) was estimated for a current varying from 20 to 120 mA using the N₂ second positive system with Δν = ?2. Using the broadening of H _β Balmer line it was possible to estimate the electron number density of the negative glow (10¹⁴ to 10¹⁵ cm^?3) as a function of the current.