Exact treatment of linear non-Condon terms in the theory of T≠0 K multimode resonance Raman scattering and optical absorption

Non-Condon terms derived from expanding the electronic transition dipole matrix elements to terms linear in the normal coordinates are included in the time-correlator theory of resonance Raman scattering. Exact T≠0 K multimode model expressions for the optical absorption and first-order resonance Raman profiles are derived, and Tehver’s approximate absorption→profile transform relation is rederived from these expressions. Numerical calculations show that for realistic model parameters for a wide class of systems, this approximate transform relation yields sufficiently accurate first-order RR profile line shapes. On the other hand, it is shown that the approximations necessary for this transform relation are unnecessary for numerical modeling of the optical absorption and resonance Raman profiles, because the exact model expressions are very convenient for computation.