Study of the broadening of the rotational Raman lines of CO 2 perturbed by rare gases

Abstract

This paper presents the results of an experimental and theoretical study of the broadening of the rotational Raman lines of the linear molecule CO 2 perturbed by rare gases: helium, neon and argon. In the first part, the experimental set-up and the method to deduce linewidths from the spectra are presented. This method is similar to that used by Welsh et al. although we take into account the contribution of the molecules in the (01 10) vibrational state for which the rotational quantum number J can be odd. The results for the pressure broadening coefficient are then given for several values of J. We then briefly recall how one can derive collision cross sections from the measured linewidths. The second part is devoted to an attempt to interpret the experimental results in terms of the theory of the Raman linewidths developed by Van Kranendonk. After recalling briefly the assumptions used in that theory and discussing the intermolecular potentials that are used, we present the results of numerical calculations performed with several types of anisotropic interaction potentials between CO 2 and the atom of rare gas. We reach the conclusion that the approximate methods used by Van Kranendonk (matrix elements of the evolution operator S computed by second order perturbation theory) are probably inadequate to calculate the effect of elastic collisions that disorient the molecule. It is suggested that it might be advantageous to consider anisotropic forces of shorter range than the anisotropic London dispersion forces derived from an r -6 potential.