Collisional effects on spectral line shape from the Doppler to the collisional regime: A rigorous test of a unified model

International audience; The paper presents high resolution Raman investigations of the Q(1) line of H-2 in Ar mixture from low density (Doppler regime) to high density (collisional regime) analyzed with a unique line shape profile. Measurements are performed by stimulated Raman gain spectroscopy between 300 and 1000 K in a wide density range (from 0.2 to 11 amagat). All the observed spectral features are accurately described by a unified model recently proposed by two of the authors. This model accounts for a velocity-memory process, not restricted to the usual hard and soft limits. It also includes correlation between velocity- and phase-changing collisions. An exhaustive analysis of vario…

H-2 vibrational spectral signatures in binary and ternary mixtures: theoretical model, simulation and application to CARS thermometry in high pressure flames

International audience; A summary of the main results obtained by the two groups in the field of H-2 vibrational spectral line signatures for various mixtures. in connection with CARS diagnostics of H-2-O-2 combustion systems, is presented. H-2-X Systems may have specific large inhomogeneous spectral features, due to the dependence of the line broadening and line shifting on the (H-2) radiator speed, particularly at high temperature. Thus, careful attention has to be paid to rigorously analyze such features, both from the experimental point of view (Dijon) and from the theoretical one (Besancon). Applications of the present results to high-pressure H-2/air flame thermometry are also briefly…

Collisional line broadening and line shifting in N2-CO2 mixture studied by inverse Raman spectroscopy

Abstract Collisional effects in the Raman Q-branch of N 2 perturbed by CO 2 have been studied by high-resolution stimulated Raman spectroscopy. The Raman spectra recorded in the 0.3–1.0 atm and 295–1000 K pressure and temperature ranges are fitted with a theoretical profile taking into account line broadening, frequency shift and line mixing due to rotational energy transfers. The data at low density are used as basic data for the modeling of rotationally inelastic rates through sets of adjustable parameters. We have used in this study the two main models developed in the last decade and known as modified exponential gap (MEG) and energy corrected sudden (ECS) laws. Experimental spectra rec…

Study of collisional effects on band shapes of the ν1/2ν2 Fermi dyad in CO2 gas with stimulated Raman spectroscopy. III. Modeling of collisional narrowing and study of vibrational shifting and broadening at high temperature

High resolution stimulated Raman spectra (SRS) of the ν1/2ν2 Fermi dyad of CO2 have been recorded in the 0.4–22. amagat density range at 700 K and in the 0.6–16 amagat density range at 900 K. The data have been successfully analyzed with a theoretical model taking into account both rotational line mixing through the energy corrected sudden‐polynomial (ECS‐P) law for the relaxation matrix and vibrational line broadening γv and line shifting δv. The two vibrational parameters have been accurately determined from fit to the experimental spectra. These new high temperature data together with previous data obtained at 295 and 500 K [B. Lavorel et al., J. Chem. Phys. 93, 2176 (1990); B. Lavorel e…

The methane Raman spectrum up to 5500 cm-1. Application to the diagnostic of temperature in combustion media

High-resolution stimulated Raman spectroscopy of O2

Abstract The S S and O O branches of the fundamental vibrational band of molecular oxygen in its electronic ground state have been resolved for the first time in Raman spectroscopy. The spectra have been observed, at room temperature and low pressure, with a stimulated Raman scattering (S.R.S.) spectrometer including a multipass cell. From these accurate Raman data combined with microwave data, we have improved the values of the vibrational, rotational, spin-spin, and spin-rotation interactions constants in the v = 1 vibrational state. Moreover, Raman Q branches of the first and second hot-bands have been recorded, allowing us to determine a set of molecular parameters for the v = 2 and v =…

The methane Raman spectrum from 1200 to 5500 cm(-1): A first step toward temperature diagnostic using methane as a probe molecule in combustion systems

International audience; We present a study of the spontaneous Raman spectra of (CH4)-C-12 from 1200 to 5500 cm(-1) at various temperatures. This study is of interest from a fundamental as well as from a practical point of view with regards to the temperature diagnostic in hydrocarbon combustion. The present investigation shows that the spontaneous (CH4)-C-12 Raman spectra are very sensitive to temperature and that the complexity of methane spectra is not an obstacle to use methane as a probe molecule in laser-diagnostic techniques. Our study consists in determining the polarisability parameters of methane (CH4)-C-12, unknown at the present time, from spontaneous Raman spectra recorded at pr…

Inhomogeneous speed effects on H-2 vibrational line profiles in ternary mixtures

International audience; A study of speed inhomogeneous broadening of the hydrogen vibrational line profiles in the collisional regime for ternary mixtures is reported. The Q(1) line of H-2 in H-2-Ar-N-2, H-2-He-Ar, and H-2-He-N-2 mixtures is investigated by high resolution stimulated Raman spectroscopy for various concentrations and temperatures. A model, successfully used for binary mixtures, is extended to ternary mixtures. An excellent agreement is obtained between theory and experiment for H-2-Ar-N-2, by using the collisional parameters previously obtained from binary mixtures study. For H-2-He-Ar and H-2-He-N-2, H-2-He collisions play a "hardening" effect in the H-2 soft speed memory m…

Stimulated Raman and Cars Spectroscopy of ν1 and 2ν2 (A1) Bands of 12CF4

Two experimental coherent Raman techniques, stimulated Raman and coherent anti-Stokes Raman spectroscopy (CARS), were employed to study the Raman spectrum of CF 4 in the 900 cm −1 region. The stimulated Raman and CARS spectra of the ν 1 band of CF 4 were recorded at high resolution. The analysis of these spectra enabled some spectroscopic constants of this band to be refined and higher order constants to be determined for the first time. The first high-resolution CARS spectrum of the 2ν 2 (A 1 ) harmonic band is also presented. The rotational transitions of this band up to J = 40 were assigned and the first set of spectroscopic constants for this sub-level were determined. These results imp…

HIGH RESOLUTION STIMULATED RAMAN SPECTROSCOPY WITH A 3 MHz ACCURACY WAVEMETER

Optical rotary power at the resonance of the terbium F-7(6)-> D-5(4) line in terbium gallium garnet

0038-1101; The Tb3+ absorption line F-7(6)-->D-5(4) Of the Terbium Gallium Garnet crystal is excited with an Argon ion laser. The Verdet's constant has been determined and reported against 1/lambda(2), showing no significant resonant behaviour at absorption resonance. The utility and the constraints of the crystal at this particular resonant wavelength are pointed out. (C) 1998 Elsevier Science Ltd. All rights reserved.

Accurate spectroscopic constants of nitrogen determined from stimulated Raman spectra of the fundamental and first hot bands

Nitrogen spectra of the Q-branch of the fundamental and the first hot bands were recorde with a high-resolution stimulated Raman spectrometer at atmospheric pressure and ca. 1300 K. The absolute frequencies of the Raman lines were measured with high accuracy, leading to a refinement of spectroscopic constants. A temperature estimation was also performed from the Raman intensities.

Temperature measurement in gas mixtures by femtosecond Raman-induced polarization spectroscopy

The potential of femtosecond Raman-induced polarization spectroscopy (RIPS) for the simultaneous determination of temperature and concentrations was investigated. These measurements were related to the rotational time response of the molecular gas mixture, which was measured as a function of the pump-probe time delay. The change of the polarizability anisotropy with respect to the vibrational levels was taken into account. The results of temperature measurements in pure CO2 showed good agreement with the values obtained by a thermocouple. The RIPS technique was also applied to a CO2-N2 gas mixture to determine simultaneously temperatures and concentrations at temperatures up to 600 K. The a…

Rotational collisional line broadening at high temperatures in the N2 fundamental Q-branch studied with stimulated Raman spectroscopy

Self broadened N 2 Q-branch spectra are measured by high resolution stimulated Raman spectroscopy in the pressure region 0.25-1.9 atm. and in the temperature range 295-1310 K. Non additivity of the Q(J) components due to line overlap arising in the highest pressure range explored is carefully taken into account. Excellent fit of the whole spectra is thus obtained for each pressure with linearly density-dependent line widths. Semi-classical calculations of the line-broadening coefficients lead to consistent values with all the measured ones. These calculations are extended to higher J values and to higher temperatures (up to 2500 K). At last, a simple phenomenological model based on a polyno…

Measurement of vibrational line profiles inH2–rare-gas mixtures: Determination of the speed dependence of the line shift

High-resolution inverse Raman experiments for ${\mathrm{H}}_{2}$ diluted in Ar have revealed unusual Q-line profile features at various concentrations which have been interpreted in terms of speed-changing collisions. A more general approach including both speed- and phase-changing collisions has led to an alternative interpretation of these features. In order to further analyze the role of these various collisional mechanisms, new experiments have been performed. Pure ${\mathrm{H}}_{2}$ and ${\mathrm{H}}_{2}$ perturbed by Ne, Ar, and Xe have been investigated at various temperatures between 295 and 800 K.

Determination of concentrations in ternary and quaternary molecular gas mixtures using femtosecond Raman spectroscopy

European Conference on Nonlinear Optical Spectroscopy MAR 18-19, 2002 VILLIGEN, SWITZERLAND; Measurements of concentrations in gas mixtures of three and four molecular components are presented. They rely on a femtosecond time-resolved pump-probe technique based on Raman-induced polarization spectroscopy. The rotational time response of the molecular gas mixture is measured as a function of the pump-probe time delay. No selective frequency tunability is needed as the molecular rotational spectra are excited within the laser bandwidth. The results obtained from experiments performed at room temperature in N2O-CO2-N2 and N2O-CO2-O2-N2 mixtures are presented and the accuracy of the method is di…

Optical rotary power at the resonance of the Terbium 7F6→5D4 line in Terbium Gallium Garnet

Abstract The Tb 3+ absorption line 7 F 6 → 5 D 4 of the Terbium Gallium Garnet crystal is excited with an Argon ion laser. The Verdet's constant has been determined and reported against 1/ λ 2 , showing no significant resonant behaviour at absorption resonance. The utility and the constraints of the crystal at this particular resonant wavelength are pointed out.

Experimental and theoretical study of line mixing in methane spectra. III. The Q branch of the Raman nu(1) band

International audience; The shape of the nu(1) Raman Q branch of CH4 perturbed by Ar and He at room temperature has been studied. Stimulated Raman spectroscopy (SRS) experiments have been made in the 2915-2918 cm(-1) spectral region for total pressures from 0.4 to 70 atm and mixtures of approximate to 5% CH4 with He and Ar. Analysis of the spectra demonstrates that the shape of the Q branch is significantly influenced by line mixing and much narrower than what is predicted by the addition of individual line profiles. For the first time, a model is proposed for the calculation and analysis of the effects of collisions on the considered spectra. In this approach, the rotational part of the re…

Enhancement of sensitivity in high-resolution stimulated Raman spectroscopy of gases: Applicaion to the 2ν2 (1285 cm−1) band of CO2

The application of a multiple-pass gas cell to quasi-cw stimulated Raman scattering is demonstrated to be a powerful method for significantly increasing the sensitivity. As a consequence, such a device offers the possibility of working in the 0.1–1 Torr pressure range for weak bands. As a striking example, experimental results are given for the 2ν2 band of CO2 at 1285 cm−1. The band is almost completely resolved with a very good signal-to-noise ratio. The Raman frequencies and the collisional broadening coefficients are determined as a function of quantum number J. Moreover, the possibility of auto-stimulated Raman effect on CO2 at moderate pressure via the sharp ν1 band (1388 cm−1) is demo…

Optical diagnostic of temperature in rocket engines by coherent Raman techniques

Abstract This article reviews the study of Raman line shapes of molecular species involved in reactive media, such flames or engines, at high temperature and high pressure. This study is of interest from a fundamental as well as from a practical point of view with regards to the CARS temperature diagnostic of GH2–LOX combustion systems. We will particularly draw attention to recent investigations by means of Stimulated Raman Spectroscopy (SRS) in H2–H2O mixtures at temperature up to 1800 K. Whereas H2–X systems usually exhibit large inhomogeneous effects, due to the speed dependence of the collisional parameters, the absence of such apparent inhomogeneous signatures in the H2–H2O system all…

H2-He vibrational line-shape parameters: Measurement and semiclassical calculation

High-resolution inverse Raman spectroscopy has been used to obtain the line shifting and line broadening coefficients of H{sub 2} perturbed by He. Measurements have been made for the {ital Q}-branch transitions ({ital J}=0{r_arrow}5) in a density range of 10 to 20 amagat and from 296 to 995 K. Up to 795 K we have directly deduced from the experimental broadening coefficients the inelastic rotational state-to-state and vibrational dephasing rates. At higher temperatures, owing to the larger number of channels of relaxation which occur, the results have been analyzed using a scaling law. The line shift and broadening coefficients exhibit a square root and a linear dependence on temperature, r…

Determination of concentrations in ternary and quaternary molecular gas mixtures using femtosecond Raman spectroscopy

Measurements of concentrations in gas mixtures of three and four molecular components are presented. They rely on a femtosecond time-resolved pump–probe technique based on Raman-induced polarization spectroscopy. The rotational time response of the molecular gas mixture is measured as a function of the pump–probe time delay. No selective frequency tunability is needed as the molecular rotational spectra are excited within the laser bandwidth. The results obtained from experiments performed at room temperature in N2O–CO2–N2 and N2O–CO2–O2–N2 mixtures are presented and the accuracy of the method is discussed. Copyright © 2002 John Wiley & Sons, Ltd.

Collisional broadening and shifting parameters of the RamanQbranch ofH2perturbed byN2determined from speed-dependent line profiles at high temperatures

The broadening and shifting of the {ital Q} branch of H{sub 2} diluted in N{sub 2} are studied at temperatures between 300 and 1200 K. (i) In order to account for the observed anomalies (asymmetric profiles and nonlinearity of the linewidth versus perturber concentration), the results are interpreted using a speed-dependent model in its general form. This model introduces the speed dependence of the shift and the broadening. In contrast with the previous H{sub 2}{endash}rare-gas studies, the high-temperature measurements prove the necessity to include speed-dependent broadening that was ignored in the previous studies. (ii) Concomitantly, we report as well pure H{sub 2} results including Ra…

High-Resolution Stimulated Raman Spectroscopy of Methane 13CD4 in the Pentad Region

Abstract We present the first Raman spectrum of 13CD4 recorded at room temperature in the pentad region by inverse Raman spectroscopy, thus including the ν1 (A1), 2ν2 (A1), 2ν4 (A1), and ν2 + ν4(F1 + F2) Q branches. It is noteworthy that the overtone bands 2ν2 and 2ν4 are observed for the first time in a methane-like molecule by a coherent Raman process. The wide frequency range investigated, covering 45 cm−1 in three parts, contains more than 300 lines with uncertainty less than 10−3 cm−1 in most cases. These Raman data are combined with high-resolution infrared data in a weighted least-squares fit of the vibration-rotation constants of the pentad, thanks to a relevant partially reduced ef…

CARS spectroscopy of CH4 for implication of temperature measurements in supercritical LOX/CH4 combustion

International audience; Experimental and theoretical investigations of coherent anti-Stokes Raman spectroscopy of CH4 have been carried out. Experimental spectra were measured in a heated high-pressure test cell and compared with numerical simulations. Good agreement was obtained for the temperature and the pressure dependence of CARS spectra in the ranges 300-1100 K and 0.1-5.0 MPa. The observed dependencies provide useful guidance for CARS thermometry, allowing quantitative measurements of temperature in high-pressure combustors. Application of multiplex CH4 CARS thermometry for single-shot measurements in a LOX/CH4 combustion at high pressure was demonstrated at supercritical conditions …

Measurments of collisional line widths in the stimulated Raman Q-branch of the ν1 band of silane

Self-broadened widths of 28SiH4 in the ν1Q-branch have been measured at room temperature (295 K) using high-resolution stimulated Raman Spectroscopy. These collisional widths have been obtained by fitting a super-position of Voigt profiles to the experimental spectra in the pressure range 28–154 Torr. No evidence for line mixing within the tetrahedral components of a Q(J) line has been found. The line broadening coefficients for J up to 13 depend weakly on the rotational quantum number. The mean value is 103.7 × 10−3 cm−1 atm−1.

Inverse Raman-Spectrum of Cyclopropane in the Region 3000-3050 cm-1

International audience

A POWERFUL TOOL TO STUDY COLLISIONAL PHENOMENA AND FOR COMBUSTION APPLICATIONS : THE HIGH RESOLUTION STIMULATED RAMAN SPECTROSCOPY

Electrostrictive limit in the detection of weak stimulated Raman signals in gases

0377-0486; It is shown experimentally that, in stimulated Raman spectroscopy, electrostriction induced by the pump laser gives rise to a non-resonant signal detected on the probe laser. This phenomenon limits the detectivity of the experiment. A qualitative interpretation is given. (C) 1997 by John Wiley & Sons, Ltd.

Experimental and theoretical study of line mixing in methane spectra. III. The Q branch of the Raman ν1 band

The shape of the ν1 Raman Q branch of CH4 perturbed by Ar and He at room temperature has been studied. Stimulated Raman spectroscopy (SRS) experiments have been made in the 2915–2918 cm−1 spectral region for total pressures from 0.4 to 70 atm and mixtures of ≈5% CH4 with He and Ar. Analysis of the spectra demonstrates that the shape of the Q branch is significantly influenced by line mixing and much narrower than what is predicted by the addition of individual line profiles. For the first time, a model is proposed for the calculation and analysis of the effects of collisions on the considered spectra. In this approach, the rotational part of the relaxation matrix is constructed, with no adj…

Rotational CARS thermometry at high temperature (1800 K) and high pressure (0.1-1.55 MPa)

International audience; Dual-broadband rotational CARS (DB-RCARS) thermometry has been investigated at high temperature and high pressure. Single-shot measurements were performed at 1800 K, in air and nitrogen at pressures up to 1.55 MPa and in oxygen at pressures up to 0.5 MPa. For all conditions, the resonant signal contribution to the spectra clearly dominated over the non-resonant one, implying the high potential for DB-RCARS for temperature and concentration measurements also at the high temperatures and pressures used in the present investigation. The relative standard deviation was generally similar to 2% for single-shot data at pressures from 0.5 to 1.55 MPa. At the investigated tem…

Speed-dependent line profile: A test of a unified model from the Doppler to the collisional regime for molecule-molecule collisions

International audience; A speed-dependent line profile combining soft and hard fully correlated Dicke-narrowing collisions was recently successfully tested on Ar-broadened H-2 spectra in a wide density and temperature range. A further test for mixtures of H-2 in nitrogen molecules (instead of Ar atoms) is presented. This test is also based on high resolution Raman investigation of the isotropic Q(1) line of H-2 from low to high density at various temperatures. The same consistency of the speed-dependent line profile as for H-2-Ar is obtained for H-2-N-2 through a remarkable agreement with all the data by using a unique set of four parameters (the collisional width and shift, the kinetic fre…

CARS methane spectra: Experiments and simulations for temperature diagnostic purposes

International audience; CARS laboratory experiments were done in the 2905-2925 cm(-1) range, in the vicinity of the v, band of the methane molecule, for pressures ranging from I 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 v(3) and v(4) 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…