A pure H2O isolated line-shape model based on classical molecular dynamics simulations of velocity changes and semi-classical calculations of speed-dependent collisional parameters.
It is well known that the Voigt profile does not well describe the (measured) shapes of isolated lines. This is due to the neglect of the intermolecular collision-induced velocity changes and of the speed dependence of the collisional parameters. In this paper, we present a new line profile model for pure H(2)O which takes both of these effects into account. The speed dependence of the collisional parameters has been calculated by a semi-classical method. The velocity changes have been modeled by using the Keilson-Storer collision kernel with two characteristic parameters. The latter have been deduced from classical molecular dynamics simulations which also indicate that, for pure H(2)O, the correlation between velocity-changing and state-changing collisions is not negligible, a result confirmed by the analysis of measured spectra. A partially correlated speed-dependent Keilson-Storer model has thus been adopted to describe the line-shape. Comparisons between simulated spectra and measurements for four self-broadened lines in the near-infrared at various pressures show excellent agreements.
Femtosecond time resolved coherent anti-Stokes Raman spectroscopy of H(2)-N(2) 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.
Modeling the spectral line shapes with speed-dependent broadening and Dicke narrowing
Shapes of pressure- and Doppler-broadened spectral lines are obtained by solving exactly a three-dimension transport and (or) relaxation equation. The speed dependence of collisional broadening and shifting caused by dephasing collisions and Dicke narrowing caused by velocity-changing collisions are taken into account within the impact approximation. The RautianSobelman and KeilsonStorer models are used to describe velocity-changing collisions. We show in the high density or hydrodynamic limit that both models lead to a profile that is the weighted sum of Lorentz profiles if the collisional broadening is much greater than the frequency of velocity-changing collisions and to the ordinary Lorentz profile in the opposite case. This shows that the relative size of the optical and kinetic cross section is important in determining the shape of absorption curves. The analytical solutions may be useful in modeling absorption profiles for remote sensing of the atmosphere. PACS No.: 32.70Jz