THEORETICAL LINE-SHAPES FOR ROTATIONAL SPECTRA OF HCL IN AR

An interaction potential for HCl-Ar recently derived from spectra of van der Waals complexes [J. M. Hutson, J. Chem. Phys. 89, 4550 (1988)] has been used to obtain converged close-coupling scattering S matrices from which pressure broadening (linewidth, line shift, and line coupling) cross sections have been computed within the Fano-Ben-Reuven formalism. Linewidths agree well with experimental data with the exception of the 0-1 line at low temperatures (an error of about 15% at 125 K). Line shifts, especially the largest, for the 0-1 line, are also in reasonable accord with experimental data. Line coupling is predicted to be quite small. The coupled-states molecular scattering approximation is found to be accurate except at very low collision energies. The infinite-order sudden approximations, on the other hand, is not reliable for this system. Inelastic scattering out of the spectroscopic levels accounts for only a fraction of the linewidth at thermal energies, especially in the lower rotational levels. © 1990 American Institute of Physics.