Vibrational Relaxation Times of Deuterium and Hydrogen. A Comparison of Theory and Experiment

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Abstract
A comparison of experimental and theoretical vibrational collision numbers has been carried out for deuterium and hydrogen and also for interactions of those gases with argon and krypton. Agreement is obtained for the latter while definite discrepancies appear for the D2—D2 and H2–H2 interactions. This discrepancy is rather large at the lowest temperatures; however, extrapolation of the experimental data indicates that at temperatures of the order of 10 000°K agreement is attained. The intermolecular interaction constants used in comparing theory and experiment are shown to be consistent with those derived from measurements on rotational relaxation times for hydrogen and hydrogen—rare-gas mixtures. Using these interaction constants a value of 67 collisions is obtained for the rotational collision number of hydrogen in the limit of very high temperature.