Rotational CARS for simultaneous measurements of temperature and concentrations of N2, O2, CO, and CO2 demonstrated in a CO/air diffusion flame

Rotational coherent anti-Stokes Raman spectroscopy (CARS) has over the years demonstrated its strong potential to measure temperature and relative concentrations of major species in combustion. A recent work is the development and experimental validation of a CO₂ model for thermometry, in addition to our previous rotational CARS models for other molecules. In the present work, additional calibration measurements for relative CO₂/N₂ concentrations have been made in the temperature range 294-1246 K in standardized CO₂/N₂ mixtures. Following these calibration measurements, rotational CARS measurements were performed in a laminar CO/air diffusion flame stabilized on a Wolfhard-Parker burner. High-quality spectra were recorded from the fuel-rich region to the surrounding hot air in a lateral cross section of the flame. The spectra were evaluated to obtain simultaneous profiles of temperature and concentrations of all major species; N₂, O₂, CO, and CO₂. The potential for rotational CARS as a multi-species detection technique is discussed in relation to corresponding strategies for vibrational CARS.     

Temperatures in a hollow-catmode discharge

Rotational and vibrational temperatures of He, O₂. and CO₂have been examined in carbon and molybdenum cathodes as functions of pressure and discharge current. The rotational temperature is strongly dependent on the conditions. The rotational temperatures of CO⁺, N ₂ ⁺ , C₂, CN, and OH are identical in simultaneous measurements.     

Study of a non-equilibrium pulsed nanosecond discharge at atmospheric pressure using coherent anti-Stokes Raman scattering

Time-resolved CARS measurements of rotational and vibrational temperatures of nitrogen in nanosecond pulsed discharge at atmospheric pressure are reported. Experiment is first performed with a discharge in pure air where spatial and temporal evolution of temperature distribution is recorded by delaying the probe lasers relative to the discharge pulse in the range 10 ns to 1 ms. The experiments demonstrate that a strong vibrational non-equilibrium can be sustained in N₂ at 1 bar. The effect of different colliding partners on the vibrational relaxation of N₂ is studied for discharges in CH₄/air mixtures with different equivalence ratio. The observed temperature distributions suggest that thermal equilibrium is not fully achieved in this mixture. Effect of the discharge on the ignition of a premixed CH₄/air flame is also investigated for various equivalence ratio.     

Cars measurement of vibrational temperatures in electric discharges

The measurement of vibrational and rotational temperatures of D₂ at the center of an electrical discharge has been demonstrated by a new diagnostic technique: Coherent Anti-Stokes Raman Spectroscopy (CARS). On the assumption of equilibration among vibrational levels, T_v was estimated to be approximately 1050 K, whereas T_r was determined to be near ambient (?400 K).     

CARS diagnostics of a CO2-laser pyrolytic experiment for the production of nanosized ceramic powders

Spatial distributions of rotational temperatures and molecular number densities of C₂H₂ and H₂ were measured with CARS during the production of ultrafine SiC powders in a laser pyrolytic process flame. By means of a CO₂ laser, the reaction gases SiH₄ and C₂H₂ (or alternatively C₂H₄) are converted into SiC and H₂. From the CARS measurements temperature gradients are determined between 8.8 × 10⁵ K/m and 1.6 × 10⁶ K/m with corresponding heating rates of 1.8 × 106 K/s and 1.3 × 10⁶ K/s. The CARS data also allow an estimation of the gas expansion behaviour in the reaction zone. Moreover, they show that diffusive velocity components of the hydrogen in the hot reaction zone do not exceed 0.4 m/s.     

Vibrational kinetics of the active media of CW CO<Subscript>2</Subscript> lasers

The vibrational kinetics of CW CO₂ lasers has been analyzed within the framework of a temperature model. The necessity of taking into account the coupling of the vibrational modes of the CO₂ molecule in determining the occupation numbers and the store of vibrational energy in individual modes is shown. Expressions that connect vibrational temperatures with the rates of excitation and relaxation of the lower vibrational levels of modes have been obtained. The ratios between the vibrational temperatures on selective excitation of the 00° 1 level and on excitation of CO₂ molecules in an electric discharge as well as the character of the dependences of vibrational temperatures on the pumping-energy value are discussed.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 72–79, January–February, 2005.     

Resonance enhanced coherent anti-stokes raman scattering and laser induced fluorescence applied to CH radicals: a comparative study

Resonance enhanced CARS and LIF have been applied to the CH radicals in a microwave excited Ar/H/CH plasma ( Pa, kW). Both techniques yield similar nonthermal rotational population distributions of CH(X) in its vibrational ground state (), which can be described by two rotational temperatures, K being in the order of the gas temperature for rotational states with , and a considerably higher for the higher rotational states. This result is in good agreement with previous resonance CARS and LIF measurements in similar plasmas. With resonance CARS additional measurements on CH in the state could be performed yielding a vibrational temperature of 2440 K, the total CH density was about m. The detection limits of both techniques are determined, in our case about CH radicals per quantum state in the detection volume, and their advantages and disadvantages are discussed. Received: 29 April 1996 / Accepted: 19 June 1996     

High temperature O2-CARS thermometry

O₂ temperature measurements at T=1910K have been performed by coherent anti-Stokes Raman scattering (CARS) inside a homogeneously heated gas volume of a tube furnace. The oxygen CARS spectrum can now be modeled accurately within the higher vibrational levels of the Q-branch manifold populated at flame temperatures using recently available spectroscopic data and collisional broadening coefficients.     

Study of processes of translational,rotational, and vibrational relaxation based on CARS spectra line shapes

This paper reviews the various physico-chemical processes responsible for actual linewidths encountered in high-resolution coherent anti-Stokes Raman spectroscopy (CARS). Most of the experimental data are based on linewidth measurements using a pulseamplified CARS spectrometer with an emission bandwidth (FWHM) of 2×10^–3 cm^–1. Detailed rotational and vibrational relaxation constants have been obtained from the analysis of theQ-branch profiles of C₂H₂, N₂, CH₄, and SiH₄.     

Dual-pump coherent anti-Stokes Raman scattering thermometry in a sooting turbulent pool fire

We present a dual-pump coherent anti-Stokes Raman scattering (CARS) instrument, which has been constructed for the probing of temperature fluctuations in turbulent pool fires of meter-scale. The measurements were performed at the Fire Laboratory for Accreditation of Models and Experiments (FLAME) facility at Sandia National Laboratories, which provides a canonical fire plume in quiescent wind conditions, with well-characterized boundary conditions and access for modern laser-diagnostic probes. The details of the dual-pump CARS experimental facility for the fire-science application are presented, and single-laser-shot CARS spectra containing information from in-fire N₂, O₂, H₂, and CO₂ are provided. Single-shot temperatures are obtained from spectral fitting of the Raman Q-branch signature of N₂, from which histograms that estimate the pdf of the enthalpy-averaged temperature fluctuations at the center of the fire plume are presented. Results from two different sooting fire experiments reveal excellent test-to-test repeatability of the fire plume provided by FLAME, as well as the CARS-measured temperatures. The accuracy and precision of the CARS temperatures is assessed from measurements in furnace-heated air, where the temperature can be accurately determined by a thermocouple. At temperatures in excess of 500 K, the furnace results show that the CARS measurements are accurate to within 2-3% and precise to within ±3-5% of the measured absolute temperature.     

Measurement of rotational temperature in CO2 waveguide laser medium

A small-signal gain in CO₂ waveguide laser medium has been measured on rotational-vibrational transitions in the P-branch of the (0, 0, 1)-(0, 2⁰, 0) band. It has been found that the rotational temperature is well defined in the waveguide laser system where high excitation power is injected and a large amount of energy is flowing through vibrational, rotational, and translational degrees of freedom. The rotational temperature is slightly higher than the translational temperature.     

Investigation of radial profiles of vibrational and rotational temperatures in nitrogen DC glow discharge

Spatially resolved measurements of vibrational and rotational temperature determined from the N₂(C) nitrogen bands intensities have been performed by means of optical scanner of original construction. It has been found that radial variations of studied bands are independent of pressure and discharge current under our experimental conditions, i.e. in the pressure range (100–300) Pa and for discharge current up to 40 mA. Moreover, it has been found that vibrational as well as rotational temperatures stay almost constant in the radial direction. No radial changes of both temperatures can be explained by good thermal conductivity of the positive column of DC glow discharge. This research was supported by grants: Charles University No. GAUK 194/01, Ministry of Education of Czech Republic MSM 11320002, and Grant Agency of Czech Republic GAČR 202/03/0827. The theme of presented article was included in the EU project No. G1RT-CT-2002-05083 “Plasmatech”.     

Multiplex rotational CARS of N2, O2, and CO with excimer pumped dye lasers: Species identification and thermometry in the intermediate temperature range with high temporal and spatial resolution

Pure rotational CARS spectra of N₂, O₂, air, and CO have been obtained using excimer laser pumped dye-lasers. The combination of the folded BOXCARS phase matching geometry with the broad-band laser multiplex method allowed high spatial and temporal resolution. Species and concentration analysis as well as thermometry up to 700 K is demonstrated, and possible applications are discussed.     

Numerical investigation of a fast-axial-flow CW CO2 laser

This paper presents the results of the calculation of the parameters of the active medium of a fast-axial-flow CO₂ laser using numerical methods in the framework of a one-dimensional approximation of the set of continuity equations, Bernoulli equation, equation of gas state, energy equation and multi-temperature rate equations with regard to diffusion for the gas flow in the cylindrical discharge tube. The spatial distribution of the small-signal gain and gas temperature along the gas flow direction have been calculated for a given set of initial conditions, namely, gas flow velocity, gas pressure and the tube diameter. In addition, the dependence of small-signal gain, the asymmetric stretch vibrational temperature of CO₂ (T₃) and the gas temperature on the discharge current were studied.     

The application of CARS for temperature measurements in high pressure combustion systems

The determination of accurate temperatures from CARS N₂ Q-branch spectra in premixed flames is discussed for pressures up to 40 bar. The influence of collisional line narrowing in the CARS spectra is modelled by a MEG fitting law. It takes into account collisions of N₂ with CO₂ and H₂O. The analysis of the CARS data showed that the non-resonant background has an increasing influence on temperature with increasing pressure. Little influence on the quality of the fit between theory and experiment was found. Since there is a danger of residual systematic temperature deviations, which cannot be identified from the quality of the fit, spontaneous rotational Raman scattering is employed as an independent measuring technique.     

Application of an optical pulse stretcher to coherent anti-Stokes Raman spectroscopy

An external optical cavity pulse stretcher for nanosecond-long laser pulses has been applied to coherent anti-Stokes Raman spectroscopy (CARS). An increased signal-to-noise ratio was achieved for both vibrational and pure rotational CARS, while the power density of the laser beams remained constant. Moreover, it was demonstrated that the use of the pulse stretcher also leads to improved precision of the determined temperatures and concentrations as a result of repeated excitation of the dye laser.     

CARS spectroscopy of radio-frequency discharge plasma in hydrogen

The population of the vibrational and rotational levels of hydrogen is studied by the narrow-and broadband CARS spectroscopy in capacitive and inductive-capacitive radio-frequency discharge plasmas. Computational codes are developed to analyze and process CARS spectra of hydrogen obtained under conditions of disturbance of thermodynamic equilibrium over internal degrees of freedom of molecules. To interpret the measurement results, a model is developed, which makes it possible to calculate the vibrational temperature in radio-frequency discharge plasmas. It is shown that the broadband CARS spectrometer in combination with the software package developed appreciably reduces the time necessary to determine the vibrational and rotational temperatures.     

Spectroscopic Measurements of Plasma Temperatures in a Radio Frequency Discharge

Argon and mixtures of argon with CH₄, C₂H₂ and N₂ have been excited in a 27.2 MHz radio frequency discharge at pressures of 10 and 5 Torr. Plasma spectra have been recorded and analyzed. The excitation temperatures of Ar I and H, the C₂ and CN vibrational temperatures and the N₂ and CN rotational temperatures have been determined and discussed.     

Infrared-microwave double-resonance probing of the population-depopulaton of rotational states in the NO2 molecule

A 10.6-μm CO₂ laser operating over a power range 5 ≤ p ≤ 135 watts was used to pump some select vibrational transitions in the NO₂ molecule while monitoring the rotational transitions (9_1,9 → 10_0,10), (23_2,22 → 24_2,23), and (40_2,38 → 39_3,37) in the (0, 0, 0) vibrational level and the (8_0,8 → 7_1,7) rotational transition in the (0, 1, 0) vibrational level. These rotational transitions were monitored by microwave probing to determine how the population of states in the rotational manifolds was being altered by the laser. Coincidences between some components of the ν₃-ν₂ band of NO₂ and the CO₂ infrared laser lines in the 10-μm region appeared to be responsible for the strong interaction between the continuous laser beams and the molecular states. Characteristic rate curves for population-depopulation changes in the chosen rotational levels listed above were found for various power levels from the laser pump. Rate coefficients for intensity decay for various laser powers were calculated from experimental data and are presented.     

Single‐beam coherent anti‐Stokes Raman scattering (CARS) spectroscopy of gas‐phase CO2 via phase and polarization shaping of a broadband continuum

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy of gas‐phase CO₂ is demonstrated using a single femtosecond (fs) laser beam. A shaped ultrashort laser pulse with a transform‐limited temporal width of ∼7 fs and spectral bandwidth of ∼225 nm (∼3500 cm⁻¹) is employed for simultaneous excitation of the CO₂ Fermi dyads at ∼1285 and ∼1388 cm⁻¹. CARS signal intensities for the two Raman transitions and their ratio as a function of pressure are presented. The signal‐to‐noise ratio of the single beam–generated CO₂ CARS signal is sufficient to perform concentration measurements at a rate of 1 kHz. The implications of these experiments for measuring CO₂ concentrations and rapid pressure fluctuations in hypersonic and detonation‐based chemically reacting flows are also discussed. Copyright © 2010 John Wiley & Sons, Ltd.