F. Chaussard

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

The paper presents high resolution Raman investigations of the Q(1) line of H2 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 various possible mechanisms on the line shape is achieved. These mechanisms are the Dicke narrowing, the radiator speed dependence of the collisional broadening and shifting parameters, the collisionally induced speed-class exchange and the nonimpact effect. The present test shows the high consistency of the unified model, since it allows one to get...

An isolated line-shape model based on the Keilson–Storer function for velocity changes. II. Molecular dynamics simulations and the Q(1) lines for pure H2

This paper presents comparisons between molecular dynamics simulations (MDSs) and the Keilson and Storer (KS) model for collision-induced translational velocity changes in pure H(2) at room temperature from four different points of view. The first considers various autocorrelation functions associated with the velocity. The second and third comparisons are made for the collision kernels and for the time evolutions of some conditional probabilities for changes in the velocity modulus and orientation. Finally, the evolutions, with density, of the half widths of the Q(1) lines of the isotropic Raman (1-0) fundamental band and of the (2-0) overtone quadrupole band are investigated. The results demonstrate that, while the KS approach gives a poor description of detailed velocity-to-velocity changes, it leads to accurate results for the correlation functions and spectral shapes, quantities resulting from large averages over the velocity. On the opposite, collision kernels derived from MDS lead to accurate predictions of all considered quantities. The results open promising perspectives for modeling of the spectral shapes of other systems. They also stress the value of direct calculations of speed-dependent broadening and shifting parameters from the intermolecular potential to avoid their determination from measured spectra and permit fully meaningful tests of the models.

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

A speed-dependent line profile combining soft and hard fully correlated Dicke-narrowing collisions was recently successfully tested on Ar-broadened H2 spectra in a wide density and temperature range. A further test for mixtures of H2 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 H2 from low to high density at various temperatures. The same consistency of the speed-dependent line profile as for H2–Ar is obtained for H2–N2 through a remarkable agreement with all the data by using a unique set of four parameters (the collisional width and shift, the kinetic frequency, and a characteristic velocity memory parameter). The present study is a preliminary step for the hydrogen CARS thermometry in H2–air flames at high pressure.

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 adjustable parameter, starting from semiclassical state-to-state rates. Two empirical constants which account for the shift and broadening of the branch due to vibrational effects are introduced and their values are determined from fits of measured spectra. Comparisons between measurements and results computed with and wit...

Femtosecond time resolved coherent anti-Stokes Raman spectroscopy: Experiment and modelization of speed memory effects on H2–N2 mixtures in the collision regime

With the aim of temperature diagnostic, femtosecond time-resolved CARS (coherent anti-Stokes Raman spectroscopy) is applied to probe H2 in H2-N2 mixtures. In a first part, a Lorentzian profile is used to model the femtosecond CARS response. A difference between the experimental broadening and the expected one is observed in the collision regime. The observed broadening increases strongly in an inhomogeneous way with respect to the perturber concentration. This is of considerable importance for temperature measurements. In a second part, we show that in the collision regime, this inhomogeneous broadening is due to the speed dependence of the collisional parameters and the memory effects of the radiator speed. A new modelization of the time-resolved CARS response taking into account the speed memory effects is presented and applied to the temperature diagnostic in H2-N2 mixtures. The numerical results are in good agreement with experiments.

Femtosecond time resolved coherent anti-Stokes Raman spectroscopy of H2–N2 mixtures in the Dicke regime: Experiments and modeling of velocity effects

In this paper, we present measurements and modeling of femtosecond time resolved coherent anti-Stokes Raman spectroscopy (CARS) signal in H(2)-N(2) mixtures at low densities. Three approaches have been used to model the CARS response. The first is the usual sum of Voigt profiles. In the second approach, the speed dependent Voigt profile is used. In the last approach, a model of the temporal CARS signal is developed, which takes into account the velocity changes induced by collisions and the speed dependence of the collisional parameters. The velocity changes are modeled using the Keilson and Storer memory function; the radiator speed dependences of the collisional parameters are determined from their temperature dependences. The results obtained are consistent with previous studies in the frequency domain, showing that the changes of the velocity have important effects for the H(2)/N(2) system in the Dicke narrowing density regime.

H2 vibrational spectral signatures in binary and ternary mixtures: theoretical model, simulation and application to CARS thermometry in high pressure flames

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 described. They present an approach aiming to include the more recent basic results on coherent Raman line shape in CARS diagnostics. in order to improve the accuracy of temperature measurements.

Inhomogeneous speed effects on H2 vibrational line profiles in ternary mixtures

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 H2 in H2–Ar–N2, H2–He–Ar, and H2–He–N2 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 H2–Ar–N2, by using the collisional parameters previously obtained from binary mixtures study. For H2–He–Ar and H2–He–N2, H2–He collisions play a “hardening” effect in the H2 soft speed memory mechanism for H2–Ar or H2–N2. The present experimental results allow us, via the frame of our model, to determine the “hardness” parameter values for H2–He (inaccessible from binary mixtures data) and to get an accurate description of the spectral line shape. This study should be useful for hydrogen coherent anti-Stokes Raman spectroscopy thermometry in H2/...

Optically Probed Laser-Induced Field-Free Molecular Alignment

Molecular alignment induced by laser fields has been investigated in research laboratories for over two decades. It led to a better understanding of the fundamental processes at play in the interaction of strong laser fields with molecules, and also provided significant contributions to the fields of high harmonic generation, laser spectroscopy, and laser filamentation. In this chapter, we discuss molecular alignment produced under field-free conditions, as resulting from the interaction of a laser pulse of duration shorter than the rotational period of the molecule. The experimental results presented will be confined to the optically probed alignment of linear as well as asymmetric top molecules. Special care will be taken to describe and compare various optical methods that can be employed to characterize laser-induced molecular alignment. Promising applications of optically probed molecular alignment will be also demonstrated.

Optical Diagnostics with Ultrafast and Strong Field Raman Techniques

In this chapter, we will discuss some coherent techniques, namely Raman Induced Polarization Spectroscopy (RIPS) and femtosecond Coherent Raman Anti-Stokes Spectroscopy (fs-CARS). We will demonstrate their ability to be used as non-invasive optical diagnostic tools for temperature, density, or concentration measurements, as well as a means of testing collision induced energy transfer models (in a low field regime), and studying the so-called inhomogeneous lineshape effects that are particularly enhanced in the case of hydrogen. We will also show how molecular alignment achieved in a strong field regime can provide additional information about collisional relaxation processes. In all cases, a precise knowledge of the collisional effects is required, and so a general modeling of collisional relaxations will be detailed.