0000000000005509
AUTHOR
Jeanine Bonamy
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…
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…
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.
Dual-broadband rotational CARS modelling of nitrogen at pressures up to 9 MPa. II. Rotational Raman line widths
International audience; Rotational coherent anti-Stokes Raman spectroscopy (CARS) is a well-established spectroscopic technique for thermometry at pre-combustion temperatures an atmospheric pressure. However, at pressures of several MPa, a previous investigation revealed large discrepancies between experimental data and the theoretical model. A re-evaluation has been made of these data (at room temperature and in the range 1.5-9 MPa) with two improvements to the spectral code. The first is the inclusion of an inter-branch interference effect, which is described in detail in Paper I. The second is the use of experimental S-1-branch Raman line widths measured at 295 K, with a temperature depe…
Line coupling in Anisotropic Raman Branches
Direct connection between collisional Raman cross sections and state‐to‐state rotational ones permits, within the sudden approximation, to evidence drastic decouplings from isotropic to anisotropic lines. These decouplings are consistent with the results obtained by using the strong collision model. Convenient energy corrections to the sudden approximation are used for N2 to calculate the resulting effects on the isotropic and anisotropic Q‐branch profiles in a large density range (several hundred bars). The comparison of the calculations with experimental coherent anti‐Stokes Raman scattering (CARS) and stimulated Raman (SRS) spectra of nitrogen exhibits a good agreement. Such effects coul…
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…
A Rotational Thermalization Model for the Calculation of Collisionally Narrowed Isotropic Raman-Scattering Spectra - Application to the Srs-N2 Q-Branch
Abstract A model for the calculation of collisionally narrowed isotropic. Raman scattering spectra is proposed. In this model, the rotational transition probabilities are calculated within the strong collision approximation, allowing the rotational energy transfer rates to be expressed in terms of the sole individual Q( J ) line broadening coefficients. These transfer rates satisfy both detailed balance principle and unitarity of the scattering matrix in contrast with most of the previous approaches. Under further approximation concerning the rotational distribution of the collisional frequency, simpler expressions for transfer rates are deduced, which do not satisfy necessarily both unitar…
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…
Hydrogen CARS thermometry in H2-N2 mixtures at high pressure and medium temperatures: influence of linewidths models
International audience; In order to improve the accuracy of H2 CARS thermometry, H2 Q-branch CARS spectra have been recorded for various H2-N2 mixtures in a high-pressure cell at different pressures and temperatures (up to 40 bar and 875 K). Due to the low spectral resolution of broadband CARS experiments, the relevant spectral lineshape factor is the linewidth ratio G(Q(3))/G(Q(1)), since Q(1) and Q(3) are the most intense lines of the Q-branch spectrum in this temperature range. For the first time, the speed-inhomogeneous effects are accounted for in the simulation of the CARS profiles. The evaluated temperatures are in good agreement with reference values obtained by thermocouples. The s…
A direct study of the vibrational bending effect in line mixing: The hot degenerate 1110 ← 0110 transition of CO2
Abstract The study of the isotropiv Raman Q -branch of a hot band Π ← Π allows one to establish a direct connection between the vibration-rotation angular momentum coupling and the resulting spectra. Due to the l -doubling, the Q -branch is split into two subbranches characterized by either even or odd rotational quantum number j . The vibrational bending reduces the rotational transfer rates inside each of these subbranches by a factor of about two and induces an inter-subbranch coupling. The expected propensity rule towards conservation of the parity index for high rotational levels is well observed. Calculated spectra are in excellent agreement with CARS experiments for the v 1 + v 2 ← v…
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…