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

摘要

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 H_2.We demonstrate that the billiard-ball (BB) approximation of the H_2-H_2 and H_2-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 H_2-H_2 and H_2-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 H_2. 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.