On far‐wing Raman profiles by CO2

The anisotropic scattering spectrum of the symmetric stretching ν1 band by CO2 was recorded up to the far Stokes wing, and its theoretical analysis was attempted through the non-Markovian energy-corrected sudden approximation—a useful approach which has thus far been successfully applied to the anisotropic scattering spectrum by N2, up to the far wing. Despite the excellent agreement observed in N2 here, a substantial inconsistency between theory and experiment was found in the wing of the spectrum. Although the influence of other missing processes or neighboring bands cannot be totally excluded, our findings rather suggest that highly anisotropic perturbers, such as CO2, are improperly described when they are handled as point-like molecules, a cornerstone hypothesis in the approach employed. Copyright © 2002 John Wiley & Sons, Ltd.