Useful results for the determination of excited state geometries from resonance Raman spectra: Application to inorganic complexes

Abstract

The time-dependent formulation of Raman scattering is used to derive simple expressions for fundamental and overtone intensities that depend on potential energy features in the Franck–Condon region and the homogeneous damping constant due to the bath modes. From the Raman excitation profiles, the dependence of the full width at half-maximum on the damping constant is calculated. The results are applied to the rich resonance Raman spectra and Raman excitation profiles of transition metal complexes, in particular, Cs3[Re2OCl10] and Cs4[W2OCl10], to determine the magnitude of the geometric changes occurring upon excitation of the molecule from the ground to the excited electronic state. For each compound, the multidimensional harmonic potential surface and damping constant derived for the excited electronic state are then used to simulate the observed Raman excitation profiles and resonance Raman spectrum.