Collisional narrowing and spectral shift in coherent anti-stokes Raman spectra of molecular nitrogen up to 2500 bar and 700 K

CARS spectra of the N₂ Q-branch up to 2500 bar and 700 K have been measured. Calculated spectra based on theoretical models show significant disagreement with measured spectra above 300 bar so that CARS temperature measurements are in error by 130 K at 700 K and –150 K at 295 K. The spectral shift of the Q-branch reaches an asymptotic value corresponding to that measured in liquid nitrogen.     

Hydrogen CARS thermometry in a high-pressure H2–air flame. Test of H2 temperature accuracy and influence of line width by comparison with N2 CARS as reference

This work describes a further step towards the determination of the temperature accuracy of H₂ Q-branch CARS (Coherent Anti-Stokes Raman Scattering) at high pressure with regard to the influence of the H₂ line widths. In laminar steady H₂/air flames in the pressure range 1–15 bar and at fuel-rich conditions with stoichiometries between two and four, quasi-simultaneous temperature measurements were performed with H₂ and N₂ CARS. The temperature values deduced from H₂ CARS are in good agreement with the reference temperature from N₂ CARS. The influence of different line-width contributions on the accuracy of H₂ Q-branch thermometry was investigated in detail. Received: 10 April 2001 / Revised version: 22 May 2001 / Published online: 18 July 2001     

Determination of temperature and concentration of molecular nitrogen,oxygen and methane with coherent anti-stokes raman scattering

Temperature and concentration measurements by Coherent Anti-Stokes Raman Scattering (CARS) of molecular nitrogen, oxygen and methane were carried out. A comparison of corrected thermocouple and CARS temperature measurements in a high-temperature furnace up to 2000 K is presented. The temperature dependent CARS spectra of N₂ and O₂ are evaluated by a simulation program. Agreement between CARS and thermocouple temperatures is obtained within 40 K for N₂ and 80 K for O₂. Good agreement is found between measurements and calculations of the decrease of CARS intensity with temperature. Various quick-fit methods for N₂-and O₂-temperature measurements from temperature sensitive spectral parameters were tested. Temperature dependent CARS spectra of thev ₁-fundamental of methane are recorded and the methane CARS intensity as function of temperature is measured.     

Parameter studies in practical nitrogen CARS thermometry using standard and advanced fitting codes

A systematic study of the influence of the collisional narrowing and the cross coherence effect on the temperature analysis of N₂-Q branch-CARS spectra at atmospheric pressure is presented. A comparison of calculated spectra over a temperature range 300–2000 K reveals that the standard theory neglecting these effects leads to temperature errors of +1.7% under flame conditions, when the nonresonant background is suppressed. This result is supported by the analysis of experimental CARS temperature measurements on a standard laminar diffusion flame. Furthermore, the temperature misreadings originating from erroneous slit function parameters and laser linewidth were investigated.     

Laser-induced fluorescence determination of flame temperatures in comparison with CARS measurements

Temperature profiles in several premixed low pressure H₂/O₂/N₂ flames and in an atmospheric pressure CH₄/air flame were determined by laser-induced fluorescence (LIF) and by CARS experiments. In the LIF study, temperatures were derived from OH excitation spectra, CARS temperatures were deduced from N₂ Q-branch spectra. The present study is the first quantitative comparison of these two methods for temperature determination in flames burning at pressures up to 1 bar. The resulting temperatures showed good agreement.     

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.     

CARS spectral fitting with multiple resonant species using sparse libraries

The coherent anti‐Stokes Raman spectroscopy (CARS) technique is often used in the study of turbulent flames. Fast and accurate algorithms are needed for fitting CARS spectra for temperature and multiple chemical species. This paper describes the development of such an algorithm. The algorithm employs sparse libraries whose size grows more slowly with number of species than a regular library. It was demonstrated by fitting synthetic ‘experimental’ dual‐pump CARS spectra containing four resonant species (N₂, O₂, H₂ and CO₂), both with added noise and without it, and by fitting experimental spectra from a H₂ air flat flame produced by a Hencken burner. In the four‐species example, the library was nearly an order of magnitude smaller than the equivalent regular library (fitting times are correspondingly faster), and the fitting errors in the absence of added noise were negligible compared to the random errors associated with fitting noisy spectra. When fitting noisy spectra, weighted least squares fitting to signal intensity, as opposed to least squares fitting or least squares fitting to square root of intensity, minimized random and bias errors in fit parameters. Copyright © 2011 John Wiley & Sons, Ltd.     

CARS studies of vibrationally excited nitrogen at low pressures

Coherent anti-Stokes Raman spectroscopy (CARS) was used to measure the vibrational temperature of microwave-excited nitrogen in a N₂–CO–He mixture. CARS spectra, originating from the N₂-vibrational levelsv=0 up tov=3, have been recorded by both narrowband scanning of the resonance region as well as by broadband OSA detection. For the microwave-excited N₂ molecules a vibrational temperatureT _v (N ₂ = (2130±110K) and a lower limit of detection forN ₂(v = 3) = 1.2 x 10¹⁵ cm^–3 was established. The CARS results were independently confirmed by simultaneously recorded and spectrally resolved CO infrared fluorescence studies.     

H2 CARS thermometry in a fuel-rich,premixed, laminar CH4/air flame in the pressure range between 5 and 40 bar

To establish H₂ CARS thermometry at high pressure, accumulated H₂ Q-branch CARS spectra were recorded in the exhaust of a fuel-rich CH₄/air flame at pressures between 5 and 40 bar. Temperatures were deduced by fitting theoretical spectra to experimental data points. The Energy-Corrected Sudden (ECS) scaling law was employed to set up an empirical model for the calculation of H₂ linewidths in high-pressure hydrocarbon flames with H₂ as a minority species. Experimental H₂ CARS spectra could be simulated very accurately with this model. The evaluated temperatures agreed well with reference temperatures obtained by spontaneous rotational Raman scattering of N₂.     

CARS investigation of collisional shift of the hydrogen Q‐branch transitions by water at high temperatures

A high‐resolution (∼0.1 cm⁻¹) spectroscopic method based on the application of a Fabry–Pérot interferometer to the spectral analysis of the coherent anti‐Stokes Raman scattering (CARS) signal from an individual Raman transition was used to obtain single‐shot spectra of hydrogen Q‐branch transitions directly in the flame of a pulsed, high‐pressure H₂/O₂ combustion chamber. Simultaneously with the Fabry–Pérot pattern, a broadband CARS spectrum of the complete H₂Q ‐branch structure was recorded in order to measure the temperature of the probe volume. During every cycle of the combustion chamber, a pressure pulse together with single‐shot CARS spectra, providing information on individual line shapes and medium temperature, was recorded. On the basis of the experimental data, the temperature dependences of lineshift coefficients for several Q‐branch lines of hydrogen molecules under collisions with water molecules were determined in the temperature range 2100 < T < 3500 K, and an empirical ‘fitting law’ for H₂ H₂O lineshift coefficients is proposed. Copyright © 2010 John Wiley & Sons, Ltd.     

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.     

Rotational CARS N2 thermometry: validation experiments for the influence of nitrogen spectral line broadening by hydrogen

Rotational coherent anti‐Stokes Raman spectroscopy (CARS) in fuel‐rich hydrocarbon flames, with a large content of hydrogen in the product gases (∼20%), has in previous work shown that evaluated temperatures are raised several tens of Kelvin by taking newly derived N₂ H₂ Raman line widths into account. To validate these results, in this work calibrated temperature measurements at around 300, 500 and 700 K were performed in a cell with binary gas mixtures of nitrogen and hydrogen. The temperature evaluation was made with respect to Raman line widths either from self‐broadened nitrogen only, N₂ N₂ [energy‐corrected‐sudden (ECS)], or by also taking nitrogen broadened by hydrogen, N₂ H₂ [Robert–Bonamy (RB)], Raman line widths into account. With increased amount of hydrogen in the cell at constant temperature, the evaluated CARS temperatures were clearly lowered with the use of Raman line widths from self‐broadened nitrogen only, and the case with inclusion of N₂ H₂ Raman line widths was more successful. The difference in evaluated temperatures between the two different sets increases approximately linearly, reaching 20 K (at T ∼ 300 K), 43 K (at T = 500 K) and 61 K (at T = 700 K) at the highest hydrogen concentration (90%). The results from this work further emphasize the importance of using adequate Raman line widths for accurate rotational CARS thermometry. Copyright © 2010 John Wiley & Sons, Ltd.     

The application of single-pulse CARS for temperature measurements in a turbulent stagnation flame

N₂ Q-branch CARS spectra have been recorded and evaluated for temperature determination in a turbulent, premixed CH₄/air stagnation flame with a burner of 40 mm diameter and 22 kW thermal load. Temperature histograms on the flame axis at different distances from the stagnation plate have been measured. Problems of practical applicability are addressed, including those arising from the limited spatial resolution of the BOXCARS geometry, from an insufficient dynamic range of the diode array detector, and from a memory effect of the detector in the case of measurements in highly turbulent flame areas with strong intermittency. Some information is given on the computerized acquisition and on the evaluation of the large amounts of data that are necessary for extensive investigations in large combustion systems.     

CARS methane spectra: Experiments and simulations for temperature diagnostic purposes

CARS laboratory experiments were done in the 2905–2925 cm⁻¹ range, in the vicinity of the ν₁ band of the methane molecule, for pressures ranging from 1 to 50 bar, and temperatures up to 1100 K. These experiments were carried out in order to retrieve the pressure evolution of the CH₄ spectrum, as well as to confirm its temperature dependance. After a brief recall on the theory used to compute pressure broadening coefficients and relaxation rates, we consider the ν₃ and ν₄ infrared bands of methane for benchmark calculations purposes. Next, we present recent experimental CARS spectra and calculated ones. Lastly, we discuss flame experiments as well as comparisons of temperature retrieval using N₂ and CH₄ as probe molecules.     

Temperature measurement by single-shot dual-line CARS in low-pressure flows

A CARS method, adapted for diagnostics in low-pressure unsteady flows is described. The technique employs two narrow-band dye lasers and a single-frequency pump laser. Single-shot rotational temperature is obtained from the ratio of the intensities of two isolated Q lines. Temperature-measurement accuracy is discussed. The advantage of referencing the CARS signals from the flow in a cell filled with the same gas is shown. Demonstrative experiments are performed using N₂ at pressures of 10²–10³ Pa.     

Determination of temperature by stimulated raman scattering of molecular nitrogen,oxygen, and carbon dioxide

We have determined the temperature from SRS spectra of N₂-N₂, N₂-CO₂, O₂-O₂, and CO₂-CO₂ recorded in wide pressure and temperature ranges. The fitting procedure takes simultaneously into account the Dicke effect and motional narrowing. We have quantified the accuracy of the MEG and ECS-P models for rotational relaxation. The temperature extracted from each model is compared with thermocouple measurements. The influence of vibrational broadening and shifting is discussed in detail.     

CARS temperature measurement in a LOX/CH4 spray flame

Coherent anti‐Stokes Raman scattering (CARS) spectroscopy has been used to investigate cryogenic liquid oxygen/gaseous methane (LOX/CH₄) flames on a medium‐size test facility at a pressure of 0.24 MPa and mass flow of 0.025 kg/s. Single‐shot, broadband CARS spectra with simultaneous detection of the Q‐branches of hydrogen and water molecules were recorded with good signal‐to‐noise ratio. Temperature was deduced from the H₂ and H₂O CARS profiles. The spatial temperature distribution in a comparatively harsh environment has been measured successfully. The measurements took place in the windowed combustion chamber of the DLR M3 test facility, aiming to provide data for validation of rocket combustor modeling. Copyright © 2010 John Wiley & Sons, Ltd.     

Thermal grating and broadband degenerate four-wave mixing spectroscopy of OH in high-pressure flames

2 ∑–X²Π(0,0) band of OH has been studied in premixed methane/air flames using a cw Ar⁺ laser probe. Measurements of flame temperature and pressure were derived from fits of theoretical simulations to the observed time variation of signals over a pressure range of 10 to 40 bar and for different stoichiometry that were in agreement with independent measurements using N₂ CARS and predictions of a one-dimensional flame calculation. Broadband DFWM spectra in the same band of OH were observed up to a pressure of 9 bar, above which signals were obtained only from scattering from thermal gratings. Received: 10 November 1997/Revised version: 28 May 1998     

Coherent anti-Stokes Raman spectroscopy (CARS) of thev 3 band of methane in supersonic molecular beams

Supersonic molecular beams of methane are investigated in the expansion region using coherent anti-Stokes Raman scattering (CARS). Raman spectra of thev ₃ vibration with resolved rotational structure at low temperatures are reported. Comparison with calculated CARS spectra shows that the rotational distribution in the beam may be well described by a Boltzmann distribution. Temperatures are the same for all three nuclear spin modifications within the experimental error.     

Time-domain measurements of S-branch N2–N2 Raman linewidths using picosecond pure rotational coherent anti-Stokes Raman spectroscopy

Time-resolved dual-broadband picosecond pure rotational CARS has been applied to measure self-broadened S-branch N₂–N₂ Raman linewidths in the temperature range 294–1466 K. The coherence decays were detected directly in the time domain by following the J-dependent CARS signal decay as a function of probe delay. The rotational Raman N₂–N₂ linewidths were derived from these time-dependent decays and evaluated for thermometric accuracy. Comparisons were made to the energy-corrected sudden (ECS) and modified exponential gap (MEG) dynamical scaling laws, and the results were used to quantify the sensitivity of nanosecond rotational CARS thermometry to the linewidth model employed. The uncertainty based on the linewidth model used in pure N₂ was found to be 2 %. The merits and limitations of this rapid method for the determination of accurate Raman linewidths are discussed.