6533b852fe1ef96bd12aab58

RESEARCH PRODUCT

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

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description

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, respectively, and a significant {ital J} dependence. Semiclassical calculations based on an accurate {ital ab} {ital initio} potential lead to line-shape parameters consistent with experiment. They allow a clear understanding of their observed temperature dependence.