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Inelastic collisions in natural H2 are studied from the experimental and theoretical points of view between 10 and 140 K. Rotational populations and number densities measured by Raman spectroscopy along supersonic expansions of H2 provide the link between experimental and theoretical rotranslational state-to-state rate coefficients of H2 in the vibrational ground state. These rates are calculated in the close- scattering approach with the MOLSCAT code employing a recent ab initio H2–H2 potential. The calculated rates are assessed by means of a master equation describing the time evolution of the experimental rotational populations. The feasibility for obtaining the rates on the sole basis of the experiment is discussed. The dominant processes j1j2→j1′j2′ in the investigated thermal range are found to be 21→01>30→12>31→11, proving the importance of double processes such as 30→12. Good agreement is found between theory and experiment, as well as with earlier ultrasonic measurements of relaxation times. A spectral representation is proposed in order to visualize quantitatively the collisional contributions in any nonequilibrium time evolving process. [ABSTRACT FROM AUTHOR]

Here we present the first line-by-line measurements of interference parameters Y0k describing line-mixing effects in the weak overlapping regime for He-broadened CO lines in the 0–1 and 0–2 bands at 296 K. A detailed analysis of the line shape at intermediate perturber pressures (up to about 10 atm) has been performed, starting from previous theoretical calculations, which has demonstrated the possibility of an individual measurement of Yk parameters. The method is based on the existence of a component of the line shift, quadratic with the perturber pressure (density) and proportional to Y0k. Comparison of our measurements with results predicted from coupled-states calculations shows good overall agreement. Linear pressure shifts have also been simultaneously measured. The uncertainty on the data is important since linear shifts are very small; however, some features can be considered as significant although we have no clear understanding of them. Possible explanations are discussed. [ABSTRACT FROM AUTHOR]