Calculation of absorption and resonance Raman cross sections of ClO2 in the gas‐phase and in solution: including Duschinsky effects

Abstract

AbstractThe time‐correlation function formalism has been used to calculate resonance Raman cross sections, excitation profiles, and electronic absorption spectra of the OClO molecule in the gas‐phase and in different solvents like cyclohexane, chloroform, and water. The multidimensional time domain integrals that arise in these calculations have been evaluated for the case in which an X2B1Ã2A1 electronic transition takes place between displaced‐distorted‐rotated harmonic potential energy surfaces. Ab initio calculations have been performed to provide the spectroscopic constants required for the evaluation of these integrals. The calculated absorption spectra and resonance Raman cross sections have been compared with the experimental results. Copyright © 2009 John Wiley & Sons, Ltd.