IMPACT THEORY OF RAMAN LINE BROADENING

Abstract

The impact theory of Anderson for the pressure broadening of absorption and emission spectra is extended to the Raman spectra. Expressions are derived for the line shape and the optical cross sections in the classical path approximation. The central problem is the calculation of the average value of the evolution operator of the molecular system. It is shown that a simple derivation of the usual impact formula for this average value is obtained by averaging over all collisions as well as over all collision times. The perturbations of the intermediate states of the radiation processes are of importance only for resonant Raman scattering and may be neglected for non-resonant scattering. For freely rotating molecules the Raman scattering arising from electric dipole interaction can be decomposed into "isotropic", "magnetic dipole", and "electric quadrupole" scattering, corresponding to the j = 0, 1, and 2 irreducible parts of the Raman tensor. The optical cross sections for these three types of Raman scattering are different and are given by the reduced matrix elements, corresponding to j = 0, 1, and 2, of the optical cross-section operator, where j is the sum of the angular momenta in the initial and the complex conjugate of the final state of the radiation process.