A quasiharmonic model calculation for non-markovian far-infrared spectra of HCl in Kr and Xe liquids

Abstract

The far-infrared spectra (0–200 cm⁻¹) of dilute solutions of HCl in liquid Kr and Xe have been calculated by applying of a non-markovian spectral theory called PTOC (partial time ordering cumulants) and by using a quasiharmonic model for the liquid structure recently reported by us (A. Calvo Hernández et al., 1987, J. chem. Phys., 86, 4597) and successfully applied to HCl−Ar solution (Ibid., 86, 4607). The bath correlation functions which appear in the spectral theory involve a reduced set of parameters regarding both the HCl−Kr and HCl−Xe interactions and the liquid structure. From comparison between theoretical and experimental spectra it is possible to deduce quantitative values for the above parameters. The pronounced rotational fine structure of the experimental spectra for HCl in Kr and Xe liquids is quite well explained by the actual model.