Reorientation and Vibrational Relaxation as Line Broadening Factors in Vibrational Spectroscopy

Abstract

The theory of Gordon which relates the shape of the depolarized components of certain Raman bands to a molecular reorientation correlation function is extended to a number of types of molecular vibrations not previously covered. In addition, the contribution to the line shape for vibrational relaxation and reorientation is obtained for the three types of vibrational spectroscopy, infrared, Raman, and hyper‐Raman, and it is shown that the form of the vibrational relaxation contribution is the same for each spectroscopy. Conditions and assumptions are given under which the line broadening contributions of reorientation and vibrational relaxation can be separated and experimentally determined.