RIGOROUS RESONANCE RAMAN INTENSITIES OF IODINE SOLUTION

Author Institution: Department of Macromolecular Science, Case Western Reserve University; Department of Chemistry, University of MarylandResonance Raman spectra are obtained for iodine in chloroform solution employing a number of exciting frequencies within the electronic absorption region. The excitation profiles (experimental intensity against excitation frequencies) of the fundamental band at 211 $cm^{-1}$ as well as of overtone bands at 422 $cm^{-1}$ and 632 $cm^{-1}$ showed that not only is the peak of the excitation profile consistently shifted but also the corresponding damping value of each profile varies. Theoretical expressions for the frequency dependence of the intensities of Raman lines in rigorous resonance Raman scattering are discussed. In this effort the main contribution to the change in polarizability is obtained from the derivatives of the transition moment with respect to the vibrational normal coordinates instead of the derivatives of the electronic frequency. This leads to excellent agreement between the derived theoretical expressions and the experimental results obtained from the iodine solution