Velocity-changing collisions in pure H² and H²-Ar mixture.

We show how to effectively introduce a proper description of the velocity-changing collisions into the model of isolated molecular transition for the case of self- and Ar-perturbed H² .We demonstrate that the billiard-ball (BB) approximation of the H²-H² and H²-Ar potentials gives an accurate description of the velocity-changing collisions. The BB model results are compared with ab initio classical molecular dynamics simulations. It is shown that the BB model correctly reproduces not only the principal properties such as frequencies of velocity-changing collisions or collision kernels, but also other characteristics of H² and H²-Ar gas kinetics like rate of speed-changing collisions. Finally, we present line-shape measurement of the Q(1) line of the first overtone band of self-perturbed H² . We quantify the systematic errors of line-shape analysis caused by the use of oversimplified description of velocity-changing collisions. These conclusions will have significant impact on recent rapidly developing ultra-accurate metrology based on Doppler-limited spectroscopic measurements such as Doppler-width thermometry, atmosphere monitoring, Boltzmann constant determination, or transition position and intensity determination for fundamental studies. [ABSTRACT FROM AUTHOR]