title: Line-mixing in absorption bands of linear molecules diluted in high-density rare gases: measurements and modeling for OCS-He.
abstract: Absorption coefficients in the bending ν2 and stretching 2ν3 bands of OCS perturbed by He at high pressures up to 300 atm have been measured and analyzed in the impact-approximation region by two theoretical models accounting for the line mixing. In the first approach, the frequency-independent relaxation operator is treated semi-classically [N. N. Filippov and M. V. Tonkov, J. Quant. Spectrosc. Radiat. Transf. 50, 111 (1993)] with adiabatic corrections. To characterize the strength of collisions and the line mixing efficiency a single parameter G is used and its value is estimated from the intermolecular interaction potential. The adiabaticity of collisions and the corresponding correction to the collisional cross sections amplitude are taken into account by two other parameters ν(corr) and σ deduced from fitting to experimental line widths. In the second approach, the symmetrized non-Markovian relaxation operator of Energy-Corrected Sudden type developed for rototranslational Raman spectra of linear rotators [J. Buldyreva and L. Bonamy, Phys. Rev. A 60, 370 (1999)] and satisfying all the basic properties (in particular, the detailed balance relation and the double-sided sum rules) is adapted to absorption spectra for the first time. Its off-diagonal elements are determined via the common adiabaticity factor and the basic transition rates whose parameters are adjusted on experimental values of isolated line widths. Both models provide a very consistent description of OCS-He 2ν3 and ν2 band intensities up to the maximal experimentally studied pressure, with a slightly more realistic picturing of the inter-branch exchange by the second approach.
authors: Institut UTINAM UMR CNRS 6213, Université de Franche-Comté, Besançon, France. jeanna.buldyreva@univ-fcomte.fr
authors: Jeanna V
authors: JV
authors: Buldyreva
authors: Nikolai A
authors: NA
authors: Gennadiev
authors: Nikolai N
authors: NN
authors: Filippov
mesh_terms: D005740:Gases / Q000737:chemistry; D006371:Helium / Q000737:chemistry*; D011789:Quantum Theory; D013461:Sulfur Oxides / Q000737:chemistry*; D014732:Vibration
chemical_list: D005740:Gases; D013461:Sulfur Oxides; D006371:Helium; C010063:carbonyl sulfide